UV FILTER CAPSULE

Abstract

The present invention relates to UV filter capsules, to the use thereof for the preparation of cosmetic or dermatological formulations or dispersions, and to cosmetic or dermatological formulations which comprise the capsules, and to a process for the production thereof.

Claims

1. (canceled)

2. (canceled)

3. The process according to claim 19, wherein the at least one low-solubility organic UV filter mentioned under a) is a triazine derivative, diarylbutadiene derivative, hydroxybenzophenone derivative, and/or methylenebisbenzotriazolyltetramethylbutylphenol derivative.

4. The process according claim 19, where the at least one low-solubility organic UV filter mentioned under a) is a triazine derivative selected from the group comprising 2,4,6-trisianilino-(p-carbo-2-ethyl-1-hexyloxy)]-1,3,5-triazine, dioctylbutamidotriazone, bisethylhexyloxyphenolmethoxyphenyltriazine, 2,4,6-tris(diethyl-4-aminobenzal malonate)-s-triazine, 2,4,6-tris(dimethyl-4-aminobenzal malonate)-s-triazine, 2,4,6-tris(diisopropyl-4aminobenzal malonate)-s-triazine, 2,4,6-tris[3-benzotriazol-2-yl)-2-hydroxy-5methyl)phenyl-amino]-s-triazine, and 2,4,6-tris[3-benzotriazol-2-yl)-2-hydroxy-5-tert-octyl)phenylamino]-s-triazine.

5. The process according to claim 19, where the at least one low-solubility organic UV filter mentioned under a) is a triazine derivative selected from 2,4,6-tris[anilino-(p-carbo-2-ethyl-1-hexyloxy)]-1,3,5-triazine, dioctylbutamidotriazone, or bisethylhexyloxyphenolmethoxyphenyltriazine.

6. The process according to claim 19, where the at least one low-solubility organic UV filter mentioned under a) is a diarylbutadiene derivative, and the diarylbutadiene conforms to the formula II ##STR00014## where R.sub.4 and R.sub.5, independently of one another, denote hydrogen, C.sub.1-C.sub.20-alkyl, C.sub.3-C.sub.10-cycloalkyl, or C.sub.3-C.sub.10-cycloalkenyl.

7. The process according to claim 19, where the at least one low-solubility organic UV filter mentioned under a) is 1,1-dicarboxy(2,2-dimethylpropyl)-4,4-diphenylbutadiene.

8. The process according to claim 19, where the at least one low-solubility organic UV filter mentioned under a) corresponds to a hydroxybenzophenone of the formula III ##STR00015## where R.sup.1 and R.sup.2, independently of one another, denote H, C.sub.1-C.sub.20 alkyl, C.sub.3-C.sub.10-cycloalkyl, or C.sub.3-C.sub.10-cycloalkenyl, where the substituents R.sup.1 and R.sup.2, together with the nitrogen atom to which they are bonded, may form a 5- or 6-membered ring, and R.sup.3 denotes C.sub.1-C.sub.20-alkyl.

9. The process according to claim 19, where the at least one low-solubility organic UV filter mentioned under a) is hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate.

10. The process according to claim 19, where the at least one low-solubility organic UV filter mentioned under a) is a methylenebisbenzotriazolyltetramethylbutylphenol derivative.

11. The process according to claim 19, where the at least one low-solubility organic UV filter mentioned under a) is 2,2-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol].

12. The process according to claim 19, wherein the UV filter capsule contains the at least one low-solubility UV filter mentioned under a) and the emollient mentioned under b) in a weight per cent ratio 10:90 to 90:10.

13. A dispersion comprising UV filter capsules wherein the UV filter capsules comprise a polymeric shell encapsulating a core mixture of: a) 1-90% by weight, based on the core mixture, of at least one low-solubility organic UV filter and b) an emollient compound of the formula I ##STR00016## where n corresponds to an integer from 2 to 12, which is capable of dissolving more than 40% by weight of the low-solubility organic UV filter at room temperature.

14. The dispersion according to claim 13, where the dispersion is aqueous.

15. The dispersion according to claim 13, wherein the proportion of UV filter capsules is 5 to 80% by weight, based on a total amount of the dispersion.

16. A composition comprising at least one low-solubility organic UV filter and at least one suitable vehicle, wherein at least some of a low-solubility organic UV filter is encapsulated in the form of UV filter capsules, wherein the UV filter capsules comprise a polymeric shell encapsulating a core mixture of: a) 1-90% by weight, based on the core mixture, of at least one low-solubility organic UV filter and b) an emollient compound of the formula I ##STR00017## where n corresponds to an integer from 2 to 12, which is capable of dissolving more than 40% by weight of the low-solubility organic UV filter at room temperature.

17. (canceled)

18. (canceled)

19. A process for the production of UV filter capsules, wherein in step a), an oil-in-water emulsion is prepared from a mixture comprising a sol-gel precursor for the production of the polymeric shell, at least one low-solubility UV filter and an emollient which is capable of dissolving more than 40% by weight of the low-solubility organic UV filter at room temperature, in an aqueous solution, in step b), the emulsion prepared in step a) is mixed to give an aqueous solution having a pH of 2 to 4, and optionally in step c), reaction products are separated off from the sol-gel precursor, and the UV filter capsules are isolated 1 wherein the UV filter capsules comprise a polymeric shell encapsulating a core mixture of: a) 1-90% by weight, based on the core mixture, of at least one low-solubility organic UV filter and b) an emollient compound of the formula I ##STR00018## where n corresponds to an integer from 2 to 12, which is capable of dissolving more than 40% by weight of the low-solubility organic UV filter at room temperature.

20. The process of claim 19, wherein the core mixture consists of the organic UV filter and the emollient.

Description

EXAMPLES

[0259] In general: determination of the capsule size

[0260] The particle size determination is carried out by means of laser diffraction in accordance with ISO/DIS 13320, under the conditions as follows: Instrument: Malvern Mastersizer 2000 with Hydro 2000G dispersion unit The sample weighing is carried out as direct addition using a disposable pipette.

[0261] Dispersion medium: water

[0262] Sample preparation: none

[0263] Dispersion aid: none

[0264] Stirrer speed: 800 rpm

[0265] Pump speed: 1800 rpm

[0266] Ultrasound: none

[0267] Refractive index of particles: 1.55

[0268] Absorption: 0.001

[0269] Refractive index of dispersion medium: 1.33

[0270] Measurement time [sec/snaps]:5/5000

[0271] Background measurement time [sec/snaps]:8/8000

[0272] Number of measurements: 1

[0273] Obscuration [%]:8-12

[0274] The in vivo SPF (sun protection factor) was measured by the international method as published in COLIPA 001-2003see in detail Example 6. [COLIPA the European cosmetic toiletry and perfumery association]

[0275] The in vitro (UV)APF was determined in accordance with German standard DIN 67502, Characterisation of the UVA protective action of dermal sunscreens by transmission measurements taking into account the light protection factor, 3rd draft standard, March 2003.

Example 1

[0276] A solution of 400 g of Ethylhexyl Triazone, 400 g of Dimethyl Capramide (Spectrasolv DMDA) and 240 g of tetraethyl orthosilicate is emulsified in a surfactant solution [448 g of deionised water and 11 g of cetyltrimethylammonium chloride (CTAC)] with cooling with the aid of an emulsification tool (Ultra Turax). The finished emulsion is added to water containing hydrochloric acid with stirring. The mixture obtained is stirred at room temperature for 48-72 h. The ethanol formed on hydrolysis of the alkylsilane is then reduced in concentration by distillation. After addition of 20 g of PVP in 300 g of deionised water, the pH of the residue is adjusted to 3.4-3.6 using Na citrate solution, and the mixture is made up with deionised water.

[0277] The active-ingredient content of the suspension is 18% by weight.

[0278] Incorporation into the cosmetic composition can take place in this form.

[0279] The silica capsule can be isolated by conventional methods.

[0280] Particle size: d(0.50)=0.53 m, d(0.90)=1.39 m

Example 2

[0281] In comparison to Example 1, UV filter capsules were produced using solvents known on the market.

[0282] The solubility of Ethylhexyl Triazone in the systems indicated can be determined as follows:

[0283] The test substance is initially incorporated into the solvent (for example cosmetic emollient, as indicated in the table) at room temperature (about 20 C.-25 C.) with stirring in small beakers on a heatable magnetic stirrer (the stirring time here should not exceed about 30 min.). The assessment is carried out visually, i.e. it is checked whether a completely clear solution and without evident particles is present. The amounts, conditions and stirring times employed should be noted. If the substance is readily soluble, the concentration is increased by subsequent incorporation of further substance, for example by addition in 0.1 g steps with stirring. The batch size is usually 10 g, i.e. for a solubility of 1% (w/w): 0.1 g of test substance in 9.9 g of solvent. The assessment is carried out visually, if necessary with the aid of a microscope with lambda plate.

[0284] Determination of the content of the UV filters: HPLC, determination using external standard. Chromatographic system: stainless steel cartridge LiChroCART 250 mm 4 mm, Superspher 100 RP-18 end-capped, particle size 4 m. Column temperature: room temperature.

[0285] Mobile phase: methanol/solution A (80:20); flow rate 1.0 ml/min. Detection: UV detector.

[0286] Sample preparation:

[0287] Sample solution: About 30 mg of the product, weighed accurately, are dispersed with 40 ml of methanol in a 100 ml volumetric flask. This mixture is mixed in an ultrasound bath for 5 minutes. After cooling, the mixture is made up to the mark with methanol. The mixture is diluted correspondingly for the measurement. Before injection, the mixture is filtered using an Anotop 25 syringe filter (pore size 0.02 m).

[0288] Comparative solution: About 30 mg of Ethylhexyl Triazone, weighed accurately, are dissolved in methanol in a 100 ml volumetric flask, and the solution is made up to the mark. 1.0 ml of this solution is diluted to 50 ml with methanol in a 50 ml volumetric flask.

[0289] The evaluation is carried out, for example, using Agilent HPLC ChemStation; i.e. the peak areas are evaluated by the method of external standard evaluation.

[0290] Solubilities of Ethylhexyl Triazone at room temperature (20 to 25 C.) in various solvents and content in the aqueous dispersion

TABLE-US-00003 Ethylhexyl Triazone Solvent solubility at 25 C. Content* Dioctyl Malate 13% 4.4% C12-13 Alkyl Lactate 22% 7.5% Di-C12-13 Alkyl Tartrate 35% 11.9% Spectrasolv DMDA about 55% 18.7% *at a capsule content of 34% and 60% of H.sub.2O

[0291] The contents that can be achieved with the emollient according to the invention, of a maximum of 18.7% at a capsule content of 34% and a water content of 60%, are significantly higher, about 57% higher, than in the case of the previous prior art.

Example 3

[0292] A solution of 240 g of Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine, 560 g of Dimethyl Capramide (Spectrasolv DMDA) and 240 g of tetraethyl orthosilicate is emulsified in a surfactant solution [448 g of deionised water and 11 g of cetyltrimethylammonium chloride (CTAC)] with the aid of an emulsification tool (Ultra Turrax) with cooling. The finished emulsion is added to water containing hydrochloric acid with stirring. The mixture obtained is stirred at room temperature for 48-72 h. The ethanol formed on hydrolysis of the alkylsilane is then reduced in concentration by distillation. After addition of 20 g of PVP in 300 g of deionised water, the pH of the residue is adjusted to 3.4-3.6 using Na citrate solution, and the mixture is made up with deionised water.

[0293] The active-ingredient content of the suspension is 10.8% by weight.

[0294] Incorporation into the cosmetic composition can take place in this form.

[0295] The silica capsule can be isolated by conventional methods.

[0296] Particle size: d(0.50)=0.53 m, d(0.90)=1.39 m

Example 4

Formulation Examples

[0297] A) Hydrogel

TABLE-US-00004 43-06-H-2 Raw material INCI [%] [g] UV filter capsule 10.00 20.00 (17.5% of Ethylhexyl Triazone in Spectrasolv DMDA) Lubrajel DV PROPYLENE GLYCOL, 20.00 40.00 POLYGLYCERYL- METHACRYLATE RonaCare ectoin ECTOIN 0.50 1.00 Water, AQUA (WATER) 68.80 137.60 demineralised Germaben II PROPYLENE GLYCOL, 0.70 1.40 DIAZOLIDINYL UREA, METHYLPARABEN, PROPYLPARABEN 100.00 200.00

[0298] Preparation:

[0299] Initially introduce Lubrajel, and add the other constituents with stirring. In vivo SPF: 4.6; UVA-PF: 1

[0300] B) Oil-In-Water

TABLE-US-00005 0.1% of Neolone 950 43-06-OW-2 Raw material INCI [%] [g] A Eusolex 9020 BUTYL, METHOXY- 2.00 5.00 DIBENZOYL- METHANE Paraffin, viscous PARAFFINUM LIQUIDUM 4.50 11.25 (MINERAL OIL) Pelemol BIP ISOPROPYLPHTALIMIDE, 6.00 15.00 BUTYLPHTALIDE Isopropyl palmitate ISOPROPYL PALMITATE 7.50 18.75 Soya oil GLYCINE SOJA 5.00 12.50 (SOYBEAN OIL) RonaCare TOCOPHERYL ACETATE 1.00 2.50 tocopherol acetate Carbopol Ultrez 10 CARBOMER 0.30 0.75 B UV filter capsule 27.00 67.50 (17.5% of Ethylhexyl Triazone in Spectrasolv DMDA) Water, AQUA (WATER) 38.50 96.25 demineralised Sisterna L70-C AQUA (WATER), SUCROSE 6.00 15.00 LAURATE, ALCOHOL Phenonip PHENOXYETHANOL, 1.00 2.50 BUTYLPARABEN, ETHYLPARABEN, PROPYLPARABEN; METHYLPARABEN C Sodium hydroxide SODIUM HYDROXIDE 1.20 3.00 solution, 10% 100.00 250.00

[0301] Preparation

[0302] Combine phase A apart from the Carbopol, and dissolve the Eusolex 9020. If necessary, warm to about 50 C. Incorporate the Carbopol, and emulsify in the predissolved phase B with stirring. Homogenise. After addition of phase C, homogenise briefly again.

[0303] In vivo SPF: 14.3; UVA-PF: 4.5

[0304] C) Water-In-Oil

TABLE-US-00006 43-06-WO-2 Ingredient INCI [%] [g] A Eusolex T-2000 TITANIUM DIOXIDE, 10.00 25.00 ALUMINA, SIMETHICONE Arlacel P135 PEG-30 2.50 6.25 DIPOLYHYDROXY- STEARATE Abil WE 09 POLYGLYCERYL-4 2.50 6.25 ISOSTEARATE, CETYL PEG/PPG- 10/1 DIME Cetiol A HEXYL LAURATE 10.00 25.00 Cetiol 868 ETHYLHEXYL 14.00 35.00 STEARATE Shea butter BUTYROSPERMUM 1.00 2.50 PARKII (SHEA BUTTER) Paracera M MICROWAX 0.50 1.25 Crodafos CES CETEARYL, ALCOHOL, 1.00 2.50 DICETYL PHOSPHATE, CETETH-10-PH Dow Corning 200 DIMETHICONE 1.00 2.50 (100cs) Dow Corning 345 CYCLOMETHICONE 1.00 2.50 B UV filter capsule 18.90 47.25 (17.5% of Ethylhexyl Triazone in Spectrasolv DMDA) RonaCare ectoin ECTOIN 0.30 0.75 Rona Care allantoin ALLANTOIN 0.20 0.50 Propylene glycol, 1,2- SODIUM CHLORIDE 0.40 1.00 Sodium chloride Titriplex III DISODIUM EDTA 0.05 0.13 Water, demineralised AQUA (WATER) 32.95 82.38 C Phenonip PHENOXYETHANOL, 0.70 1.75 BUTYLPARABEN, ETHYLPARABEN, PRO 100.00 250.00

[0305] Preparation

[0306] Phase A is combined, without Eusolex T-2000, and heated to 80 C. Eusolex T-2000 is then slowly added to the hot oil phase with stirring.

[0307] Phase B is prepared and heated to 75 C. Phase B is then slowly added to phase A with stirring. Homogenise and cool. Phase C is added below 35 C.

[0308] In vivo SPF: 35.4; UVA-PF: 4.5

[0309] D-1) Oil-In-Water

TABLE-US-00007 Emulsion 1 Emulsion 2 comprising comprising 2% of 4% of Ethylhexyl Ethylhexyl Triazone Triazone Trade Name INCI [%] [%] A Cetiol B Dibutyl 9.00 8.00 Adipate Tegosoft TN C12-15 Alkyl 9.00 8.00 Benzoate Myritol 331 Coco- 12.00 12.00 glycerides Eumulgin Lauryl 4.00 4.00 VL 75 Glucoside, Polyglyceryl- 2-Dipoly- hydroxy- stearate, Glycerin Lanette O Cetearyl 2.00 2.00 Alcohol Uvinul T 150 Ethylhexyl 2.00 Triazone B Glycerin 87% Glycerin 3.00 3.00 Titriplex III Disodium 0.10 0.10 EDTA Cremophor Ceteareth-25 1.00 1.00 A 25 Keltrol RD Xanthan Gum 0.30 0.30 Veegum Ultra Magnesium 1.50 1.50 Aluminium Silicate Water Aqua (water) to 100.00 to 100.00 C Citric acid Citric Acid 0.50 0.50 UV filter Aqua (water), 12.10 12.10 capsule Ethylhexyl (16.6% of Triazone, Ethylhexyl Dimethyl Triazone in Capramide, Spectrasolv Silica, PVP, DMDA) Chlor- corresponds to phenesin 2% of UvinulT 150 D Phenonip Phenoxy- 1.00 1.00 ethanol, Methyl- paraben, Ethyl- paraben, Butyl- paraben, Propyl- paraben, Isobutyl- paraben

[0310] Preparation:

[0311] Combine phase A and heat to 80 C. Check whether the solid UV filter has dissolved.

[0312] Combine phase B and likewise heat to 80 C. Emulsify phase B into phase A with stirring and homogenise for 3 min. Cool with stirring, adjust the pH using citric acid, and, at about 30 C., incorporate Eusolex UV-Pearls.sup.TM, Uvinul T 150 and preservatives.

[0313] D-2) Oil-In-Water

TABLE-US-00008 Raw material INCI [%] [g] A Tinosorb S BIS-ETHYLHEXYLOXYPHENOL 2.00 5.00 METHOXYPHENYL TRIAZINE Spectrasolv DMDA DIMETHYL CAPRAMIDE 7.00 25.00 Paraffin, viscous PARAFFINUM LIQUIDUM (MINERAL 3.00 5.00 OIL) Pelemol BIP ISOPROPYLPHTALIMIDE, 6.00 15.00 BUTYLPHTALIDE Soya oil GLYCINE SOJA (SOYBEAN OIL) 5.00 12.50 RonaCare TOCOPHERYL ACETATE 1.00 2.50 tocopherol acetate Carbopol Ultrez 10 CARBOMER 0.30 0.75 B UV filter capsule 27.00 67.50 (10.5% of Tinosorb S in Spectrasolv DMDA) Water, AQUA (WATER) to 100 to 250 demineralised Sisterna L70-C AQUA (WATER), SUCROSE 6.00 15.00 LAURATE, ALCOHOL Phenonip PHENOXYETHANOL, 1.00 2.50 BUTYLPARABEN, ETHYLPARABEN, PROPYLPARABEN; METHYLPARABEN C Sodium hydroxide SODIUM HYDROXIDE 1.20 3.00 solution, 10% 100.00 250.00

[0314] Preparation

[0315] Combine phase A apart from the Carbopol and dissolve the Tinosorb S. If necessary, warm to about 60 C. Incorporate the Carbopol and emulsify the predissolved phase B with stirring. Homogenise. After addition of phase C, homogenise briefly again.

[0316] In vivo SPF:10; UVA-PF:7.1

[0317] E) Water-In-Oil

TABLE-US-00009 Ingredient INCI [%] [g] A Tinosorb S BIS-ETHYLHEXYLOXYPHENOL 2.00 5.00 METHOXYPHENYL TRIAZINE Spectrasolv DMDA DIMETHYL CAPRAMIDE 7.00 25.00 Eusolex T-2000 TITANIUM DIOXIDE, ALUMINA, 10.00 25.00 SIMETHICONE Arlacel P135 PEG-30 2.50 6.25 DIPOLYHYDROXYSTEARATE Abil WE 09 POLYGLYCERYL-4 2.50 6.25 ISOSTEARATE, CETYL PEG/PPG- 10/1 DIME Cetiol A HEXYL LAURATE 3.00 7.5 Cetiol 868 ETHYLHEXYL STEARATE 14.00 35.00 Shea butter BUTYROSPERMUM PARKII 1.00 2.50 (SHEA BUTTER) Paracera M MICROWAX 0.50 1.25 Crodafos CES CETEARYL, ALCOHOL, DICETYL 1.00 2.50 PHOSPHATE, CETETH-10-PH Dow Corning 200 DIMETHICONE 1.00 2.50 (100cs) Dow Corning 345 CYCLOMETHICONE 1.00 2.50 B UV filter capsule 18.90 47.25 (10.5% of Tinosorb S in Spectrasolv DMDA) RonaCare ectoin ECTOIN 0.30 0.75 Rona Care allantoin ALLANTOIN 0.20 0.50 Propylene glycol, 1,2- SODIUM CHLORIDE 0.40 1.00 Sodium chloride Titriplex III DISODIUM EDTA 0.05 0.13 Water, demineralised AQUA (WATER) to 100 to 250 C Phenonip PHENOXYETHANOL, 0.70 1.75 BUTYLPARABEN, ETHYLPARABEN, PROPYLPARABEN 100.00 250.00

[0318] Preparation

[0319] Phase A is combined with stirring, without Eusolex T-2000, and heated at 80 C. until the Tinosorb S has dissolved. Eusolex T-2000 is then slowly added to the hot oil phase with stirring. Phase B is prepared and heated to 75 C. Phase B is then slowly added to phase A with stirring. Homogenise and cool. Phase C is added below 35 C.

[0320] In vivo SPF:36.5 ; UVA-PF:12

[0321] F) Water-In-Oil

TABLE-US-00010 Ingredient INCI [%] [g] A Tinosorb S BIS-ETHYLHEXYLOXYPHENOL 2.00 5.00 METHOXYPHENYL TRIAZINE Spectrasolv DMDA DIMETHYL CAPRAMIDE 7.00 25.00 Eusolex T-2000 TITANIUM DIOXIDE, ALUMINA, 4.00 10.00 SIMEETHICONE RonaCare AP BIS-ETHYLHEXYL 2.00 5.00 HYDROXYDIMETHOXY BENZYLMALONATE Imwitor 372 P GLYCERYL STEARATE CITRATE 3.50 8.75 Imwitor 380 GLYCERYL COCOATE CITRATE 2.00 5.00 Wheat germ oil, TRITICUM VULGARE (WHEAT 2.00 5.00 refined GERM OIL) Propyl PROPYLPARABEN 0.05 0.13 4-hydroxybenzoate B UV filter capsule (10.5% of Tinosorb S 20.00 50.00 in Spectrasolv DMDA) Karion F liquid SORBITOL 3.00 7.50 Keltrol SF XANTHAN GUM 0.50 1.25 Methyl METHYLPARABEN 0.15 0.37 4-hydroxybenzoate Titriplex III DISODIUM EDTA 0.05 0.13 Water, demineralised AQUA (WATER) to 100 to 250 C Sodium hydroxide AQUA (WATER), SODIUM 0.20 0.50 solution, 10% HYDROXIDE to 100.00 to 250.00

[0322] Preparation

[0323] Phase B: Disperse the Keltrol in water. Add the remaining constituents and mix.

[0324] Heat phases A and B separately to 80 C.

[0325] Emulsify phase B into phase A. Homogenise.

[0326] Allow to cool with stirring and adjust the pH to about 6.0 using phase C at below 35 C.

[0327] In vivo SPF:21.3; UVA-PF: 9.9

Example 5

[0328] Determination of the in vitro SPF.

[0329] Determination of the in vitro SPF of cosmetic compositions: The basic measurement principle on which the measurement is based is the determination of the UV transmission by a composition which comprises substances for protection against UV light. The composition here is applied to a suitable substrate in a defined layer thickness, and the absorption is measured in nanometre steps in a suitable UV photometer. The in vitro light protection factor is calculated from the following formula:

[00002]$\begin{array}{c}{\mathrm{SPF}}_{\mathrm{vitro}}=.Math.\frac{\underset{290.Math..Math.\mathrm{nm}}{\overset{400.Math..Math.\mathrm{nm}}{}}.Math.E\left(\right)*S\left(\right)*\left(\right)}{\underset{290.Math..Math.\mathrm{nm}}{\overset{400.Math..Math.\mathrm{nm}}{}}.Math.E\left(\right)*S\left(\right)*\left(\right).Math.\text{/}.Math.\mathrm{MPF}\left(\right)}\\ =.Math.\frac{\underset{290.Math..Math.\mathrm{nm}}{\overset{400.Math..Math.\mathrm{nm}}{}}.Math.E\left(\right)*S\left(\right)*\left(\right)}{\underset{290.Math..Math.\mathrm{nm}}{\overset{400.Math..Math.\mathrm{nm}}{}}.Math.E\left(\right)*S\left(\right)*\left(\right).Math.\text{/}.Math.{10}^{A\left(\right)}}\end{array}$$E\left(\right)=\mathrm{irradiation}.Math..Math.\mathrm{strength}.Math..Math.\mathrm{at}.Math..Math.\mathrm{wavelength}.Math..Math..Math..Math.\mathrm{of}.Math..Math.\mathrm{the}.Math..Math.\mathrm{reference}$$\mathrm{sunlight}.Math..Math.\mathrm{spectrum}$$S\left(\right)=\mathrm{erythemal}.Math..Math.\mathrm{effectiveness}.Math..Math.\mathrm{at}.Math..Math.\mathrm{wavelength}.Math..Math.$$\mathrm{MPF}\left(\right)=\mathrm{monochromatic}.Math..Math.\mathrm{protection}.Math..Math.\mathrm{factor}$$A\left(\right)=\mathrm{absorption}$

[0330] Substrate: PMMA Plexiglass plates, type XT220070 with a size of 7.5 cm2.5 cm (Roehm, Darmstadt), roughened on one side by sand blasting (90150 m glass beads, 30 bar, 30 cm separation). Specification: DIN 67502 Application rate: 1.25 mg/cm.sup.25%

[0331] Sample preparation: as many small droplets as possible of the sample to be determined are applied to the substrate using a suitable pipette or a spatula and distributed homogeneously. The tare weight of the substrate, the application rate in the moist state and after equilibration (20 min at room temperature) should be noted here. The equilibration is carried out in the dark. Each sample is measured on at least three substrates.

[0332] The subsequent measurement of the absorption is carried out by UV photometry (for example Cary 300 Bio (Varian Inc., Palo Alto, USA) with an Ulbricht sphere (Labsphere DRA-CA-301, North Suttin, USA)) over a measurement range of 290-400 nm in 1 nm steps. The spectral band width is 2 nm.

[0333] Before measurement of the sample, a base line should be recorded, using a substrate without sample (100% transmission). The subsequent measurement of the transmission (or absorption) of the samples is carried out at four measurement points per plate. The total of 12 measurement points per sample are evaluated by means of suitable software (for example Excel).

[0334] In vitro SPF [PMMA, 0.75 mg/cm.sup.2]

[0335] Example C=23.0

[0336] Example D=4.5.

Example 6

Determination of the SPF Value in Vivo in Accordance with COLIPA (International Sun Protection Factor (SPF) Test Method, COLIPA, May 2006)

[0337] UV source: 300 watt xenon arc lamp solar simulator (model 601-300 Multiport, Solar Light Co. Inc. Philadelphia, Pa., USA)

[0338] Method

[0339] Preliminary test for determination of the MED (minimum erythemal dose)

[0340] 6 different UV irradiation doses (spot 1 cm in diameter) are used on the back area of the test subjects. The MED is in each case determined visually on the unprotected skin of the test subject 16 to 24 hours after irradiation.

[0341] Main Test

[0342] The main test is carried out on in each case a 35 cm.sup.2 area of the back.

[0343] Product application and standard 70 mg of product are applied to each area in order to give a product amount of 2 mg/cm.sup.2 (+/2.5%), with the product being distributed using a glove.

[0344] Waiting Time

[0345] After completion of application of the product, a waiting time of 15 minutes is observed before the irradiation is begun.

[0346] Before the irradiation, each test area is divided into 6 zones. Each zone is exposed to a different irradiation dose. The irradiation times for the individual test subjects are defined on the basis of the individual MED values determined in the preliminary tests. The evaluation is carried out by trained personnel 16-24 hours after irradiation.

[0347] Results For determination of an SPF value, in each case the results determined on 6 test subjects are used. The SPF values are indicated for the following formulations.

[0348] Formulation 1:

TABLE-US-00011 Phase [% by wt.] Raw materials INCI A 10.0 Miglyol 812 Caprylic/Capric Triglycerides 1.5 Abil350 Dimethicone 3.0 Finsolv TN C12-15 Alkyl Benzoate 1.0 Cremophor CO PEG-40 Hydrogenated Castor Oil 40 B 12.05 UV filter capsule Aqua (water), Ethylhexyl Triazone, (16.6% of Dimethyl Capramide, Silica, PVP, Ethylhexyl Chlorphenesin Triazone in Spectrasolv DMDA) C 5.0 Propylene glycol Propylene Glycol 5.0 Ethanol 0.5 Cremophor A 25 Alcohol Ceteareth-25 to 100 Water Water D 2.0 Sepigel 305 Polyacrylamide, C13-14 Isoparaffin, Laureth-7 E 1.0 Euxyl K300 Phenoxyethanol and Methylparaben and Butylparaben and Ethylparaben and Propylparaben and Isobutylparaben

[0349] Preparation:

[0350] The components of phase A are heated to 80 C.

[0351] The components of phase B are dispersed at room temperature with stirring and added to phase A.

[0352] The components of phase C are homogenised and added to the mixture of phases A and B and homogenised again.

[0353] The components of phases D and E are added to the mixture of phases A+B+C, homogenised again and subsequently cooled to room temperature.

[0354] Viscosity: 42600 mPas

[0355] pH: 6.5

[0356] SPF in vivo according to COLIPA 6.0.

[0357] Formulation 2:

TABLE-US-00012 Phase [% by wt.] Raw materials INCI A 10.0 Miglyol 812 Caprylic/Capric Triglycerides 1.5 Abil 350 Dimethicone 3.0 Finsolv TN C12-15 Alkyl Benzoate 1.0 Cremophor CO 40 PEG-40 Hydrogenated Castor Oil 2.0 Uvinul T150 Ethylhexyl Triazone B to 100 Water Water 5.0 Propylene glycol Propylene Glycol C 5.0 Ethanol Alcohol 0.5 Cremophor A 25 Ceteareth-25 D 2.0 Sepigel 305 Polyacrylamide, C13-14 Isoparaffin, Laureth-7 E 1.0 Euxyl K300 Phenoxyethanol and Methylparaben and Butylparaben and Ethylparaben and Propylparaben and Isobutylparaben

[0358] Preparation:

[0359] The components of phase A are heated to 80 C.

[0360] The components of phase B are dispersed at room temperature with stirring and added to phase A.

[0361] The components of phase C are homogenised and added to the mixture of phases A and B and homogenised again.

[0362] The components of phases D and E are added to the mixture of phases A+B+C, homogenised again and subsequently cooled to room temperature.

[0363] Viscosity: 3450 mPas

[0364] pH: 6.5

[0365] SPF in vivo COLIPA 6.7

[0366] Formulation 3:

TABLE-US-00013 % by wt. Raw materials INCI Phase A 1.0 Cremophor A 6 Ceteareth-6, Stearyl Alcohol 1.0 Cremophor A 25 Ceteareth-25 12.0 Tegin G Glycol Stearate SE 10.0 Miglyol 812 Caprylic/Capric Triglyceride 10.0 Witconol APM PPG-3 Myristyl Ether 1.0 Cetiol SB 45 Butyrosperum Parkii (Shea Butter) 2.0 Uvinul T150 Ethylhexyl Triazone Phase B 3.0 Glycerin 87% Glycerin 1.5 Triethanolamine Care Triethanolamine 3.0 Uvinul MS 40 Benzophenone-4 to 100 Water dem. Aqua dem. Phase C 0.5 Euxyl K300 Phenoxyethanol, Methylparaben, Butylparaben, Ethylparaben, Propylparaben, Isobutylparaben

[0367] Preparation:

[0368] The components of phases A and B are each heated to 80 C. separately from one another, subsequently combined and briefly homogenised.

[0369] The mixture is cooled to 40 C. and homogenised again.

[0370] The component of phase C is added to the mixture of phases A and B, and everything is homogenised together.

[0371] Viscosity (Brookfield SP6): 3350 mPas

[0372] pH: 7.0

[0373] SPF in vivo COLIPA 6.6

[0374] Formulation 4:

TABLE-US-00014 % by wt. Raw materials INCI Phase A 1.0 Cremophor A 6 Ceteareth-6, Stearyl Alcohol 1.0 Cremophor A 25 Ceteareth-25 12.0 Tegin G Glycol Stearate SE 10.0 Miglyol 812 Caprylic/Capric Triglyceride 10.0 Witconol APM PPG-3 Myristyl Ether 1.0 Cetiol SB 45 Butyrosperum Parkii (Shea Butter) Phase B 3.0 Glycerin 87% Glycerin 1.5 Triethanolamine Care Triethanolamine 3.0 Uvinul MS 40 Benzophenone-4 to 100 Water dem. Aqua dem. Phase C 2.0 UV filter capsule Aqua (water), Ethylhexyl (16.6% of Ethylhexyl Triazone, Dimethyl Triazone in Spectrasolv Capramide, Silica, PVP, DMDA) corresponds to Chlorphenesin 2% of Uvinul T 150 Phase D 0.5 Euxyl K300 Phenoxyethanol, Methylparaben, Butylparaben, Ethylparaben, Propylparaben, Isobutylparaben

[0375] Preparation:

[0376] The components of phases A and B are each heated to 80 C. separately from one another, subsequently combined and briefly homogenised.

[0377] The components of phase C are added to the mixture of phases A and B, and everything is homogenised together.

[0378] The mixture is cooled to 40 C. and homogenised again.

[0379] The components of phase D are added to the mixture of phases A+B+C, and everything is homogenised together.

[0380] Viscosity (Brookfield SP6): 7450 mPas

[0381] pH: 7.3

[0382] SPF in vivo COLIPA 6.4.

[0383] Formulation 5: O/W cream

TABLE-US-00015 % Ingredient Batch (400 g) INCI Phase A 1.8 Stearic acid Stearic Acid 1.8 Sodium hydroxide 97% Sodium Hydroxide 10.0 Water dem. Aqua dem. Phase B 1.0 Uvinul MC80 Ethylhexyl Methoxycinnamate 1.0 Cetiol OE Dicaprylyl Ether 1.0 Finsolv TN C12-15 Alkyl Benzoate 1.0 Cetiol SN Cetearyl Isononanoate 1.0 Abil K 4 Cyclomethicone 0.5 Lanette O Cetearyl Alcohol 1.0 Uvinul T150 Ethylhexyl Triazone 3.5 Glycerol monostearate Glyceryl Stearate 1.0 Softisan 100 Hydrogenated Coco-Glycerides 2.5 Uvinul A Plus Granular Diethylamino Hydroxybenzoyl Hexyl Benzoate Phase C 1.0 UV filter capsule Aqua (water), Ethylhexyl Triazone, (16.6% of Ethylhexyl Dimethyl Capramide, Silica, PVP, Triazone in Spectrasolv Chlorphenesin DMDA) 5.0 1,2-Propylene glycol Care Propylene Glycol 3.0 Glycerin 87% Glycerin 1.0 Carbopol 934 Carbomer 0.3 Disodium EDTA Disodium EDTA to 100 Water dem. Aqua dem. Phase D 1.9 Citric acid Citric Acid Phase E 0.5 Vitamin E acetate Tocopheryl Acetate 4.0 Ethanol 96% Alcohol 1.0 Euxyl K 300 Phenoxyethanol and Methylparaben and Butylparaben and Ethylparaben and Propylparaben and Isobutylparaben

[0384] Preparation:

[0385] Saponification of phase A for 1 h at 80 C.

[0386] Melting and mixing of phase B at 80 C.

[0387] Mixing of the components of phase C and heating to 80 C. (without capsules).

[0388] Admixing of the capsules according to the invention with phase C and homogenising.

[0389] Admixing of phases A+B with C and homogenising.

[0390] Addition of phase D.

[0391] Cooling to room temperature with stirring and addition of phase E with subsequent homogenisation.

[0392] SPF in vivo COLIPA 12

[0393] (UV)APF 4

[0394] Formulation 6: O/W cream

TABLE-US-00016 % Ingredient Batch (400 g) INCI Phase A 1.8 Stearic acid Stearic Acid 1.8 Sodium hydroxide 97% Sodium Hydroxide 10.0 Water dem. Aqua dem. Phase B 1.0 Uvinul MC80 Ethylhexyl Methoxycinnamate 1.0 Cetiol OE Dicaprylyl Ether 1.0 Finsolv TN C12-15 Alkyl Benzoate 1.0 Cetiol SN Cetearyl Isononanoate 1.0 Abil K 4 Cyclomethicone 0.5 Lanette O Cetearyl Alcohol 1.0 Uvinul T150 Ethylhexyl Triazone 3.5 Glycerol monostearate Glyceryl Stearate 1.0 Softisan 100 Hydrogenated Coco-Glycerides 2.5 Uvinul A Plus Granular Diethylamino Hydroxybenzoyl Hexyl Benzoate Phase C 1.0 Eusolex 232 Phenylbenzimidazole Sulfonic Acid 1.0 Sodium hydroxide 97% Sodium Hydroxide 5.0 1,2-Propylene glycol Care Propylene Glycol 3.0 Glycerin 87% Glycerin 1.0 Carbopol 934 Carbomer 0.3 Disodium EDTA Disodium EDTA to 100 Water dem. Aqua dem. Phase D 2.6 Citric acid Citric Acid Phase E 0.5 Vitamin E acetate Tocopheryl Acetate 4.0 Ethanol 96% Alcohol 1.0 Euxyl K 300 Phenoxyethanol and Methylparaben and Butylparaben and Ethylparaben and Propylparaben and Isobutylparaben

[0395] Preparation:

[0396] Saponification of phase A for 1 h at 80 C.

[0397] Melting and mixing of phase B at 80 C.

[0398] Mixing of the components of phase C and heating to 80 C.

[0399] Admixing of phases A+B with C and homogenising.

[0400] Addition of phase D.

[0401] Cooling to room temperature with stirring and addition of phase E with subsequent homogenisation.

[0402] SPF in vivo COLIPA 8

[0403] (UV)APF 3.8

[0404] Formulation 7: O/W emulsion

TABLE-US-00017 % Ingredient INCI Phase A 1.0 Cremophor A 6 Ceteareth-6, Stearyl Alcohol 1.0 Cremophor A 25 Ceteareth-25 12.0 Tegin Glyceryl Stearate SE 10.0 Miglyol 812 Caprylic/Capric Triglyceride 10.0 Witconol APM PPG-3 Myristyl Ether 1.0 Cetiol SB 45 Butrosperum Parkii (Shea Butter) 2.0 Uvinul T150 Ethylhexyl Triazone Phase B 3.0 Glycerin 87% Glycerin 1.5 Triethanolamine Care Triethanolamine 3.0 Uvinul MS 40 Benzophenone-4 to 100 Water dem. Aqua dem. Phase C 0.5 Euxyl K300 Phenoxyethanol, Methylparaben, Butylparaben, Ethylparaben, Propylparaben, Isobutylparaben

[0405] Preparation:

[0406] Heating of phases A and B separately to 80 C.

[0407] Add phase B to phase A with stirring and briefly homogenise.

[0408] Addition of phase C to combined phases A+B and homogenisation.

[0409] Cooling to 40 C. and homogenisation.

[0410] Addition of phase C and homogenisation.

[0411] Viscosity (Brookfield SP6): 3350 mPas

[0412] pH value: 7.0

[0413] SPF in vivo COLIPA 6

[0414] Formulation 8: O/W emulsion

TABLE-US-00018 % Ingredient INCI Phase A 1.0 Cremophor A 6 Ceteareth-6, Stearyl Alcohol 1.0 Cremophor A 25 Ceteareth-25 12.0 Tegin G Glycol Stearate SE 10.0 Miglyol 812 Caprylic/Capric Triglyceride 10.0 Witconol APM PPG-3 Myristyl Ether 1.0 Cetiol SB 45 Butyrosperum Parkii (Shea Butter) Phase B 3.0 Glycerin 87% Glycerin 1.5 Triethanolamine Care Triethanolamine 3.0 Uvinul MS 40 Benzophenone-4 to 100 Water dem. Aqua dem. 2.0 UV filter capsule Aqua (water), Ethylhexyl Triazone, (16.6% of Ethylhexyl Dimethyl Capramide, Silica, PVP, Triazone in Spectrasolv Chlorphenesin DMDA) Phase C 0.5 Euxyl K300 Phenoxyethanol, Methylparaben, Butylparaben, Ethylparaben, Propylparaben, Isobutylparaben

[0415] Preparation:

[0416] Heat phase A and phase B to 80 C. each separately from one another.

[0417] Addition of phase B to phase A with stirring and brief homogenisation.

[0418] Cool to 40 C. with stirring, and add phase C and homogenise.

[0419] Viscosity (Brookfield SP6): 7450 mPas

[0420] pH value: 7.3

[0421] SPF in vivo COLIPA 6

[0422] Formulation 9:

TABLE-US-00019 % Ingredient INCI Phase A 10.0 Miglyol 812 Caprylic/Capric Triglycerides 1.5 Abil350 Dimethicone 3.0 Finsolv TN C12.15 alkyl Benzoate 1.0 Cremophor CO 40 PEG-40 Hydrogenated Castor Oil Phase B to 100 Water Water 2.0 UV filter capsule (16.6% Aqua (water), Ethylhexyl Triazone, of Ethylhexyl Triazone I Dimethyl Capramide, Silica, PVP, Spectrasolv DMDA) Chlorphenesin 5.0 Propylene glycol Propylene Glycol Phase C 5.0 Ethanol Alcohol 0.5 Cremophor A 25 Ceteareth-25 Phase D 2.0 Sepigel 305 Polyacrylamide, C13-14 Isoparaffin, Laureth-7 Phase E 1.0 Euxyl K300 Phenoxyethanol and Methylparaben and Butylparaben and Ethylparaben and Propylparaben and Isobutylparaben

[0423] Preparation:

[0424] Heating of phase A to 80 C.

[0425] Dispersion of phase B at room temperature with stirring.

[0426] Homogenisation of phase B in phase A.

[0427] Addition of phase C to phases A+B and homogenisation.

[0428] After addition of phases D and E, homogenise again.

[0429] SPF in vitro 6.

[0430] Formulation 10:

TABLE-US-00020 % Ingredient INCI Phase A 10.0 Miglyol 812 Caprylic/Capric Triglycerides 1.5 Abil350 Dimethicone 3.0 Finsolv TN C12.15 Alkyl Benzoate 1.0 Cremophor CO 40 PEG-40 Hydrogenated Castor Oil 2.0 Uvinul T150 Ethylhexyl Triazone Phase B to 100 Water Water 5.0 Propylene glycol Propylene Glycol Phase C 5.0 Ethanol Alcohol 0.5 Cremophor A 25 Ceteareth-25 Phase D 2.0 Sepigel 305 Polyacrylamide, C13-14 Isoparaffin, Laureth-7 Phase E 1.0 Euxyl K300 Phenoxyethanol and Methylparaben and Butylparaben and Ethylparaben and Propylparaben and Isobutylparaben

[0431] Preparation:

[0432] Heating of phase A to 80 C.

[0433] Dispersion of phase B at room temperature with stirring.

[0434] Homogenisation of phase B in phase A.

[0435] Addition of phase C to phases A+B and homogenisation.

[0436] After addition of phases D and E, homogenise again.

[0437] SPF in vitro 6

[0438] Formulation 11:

TABLE-US-00021 % Ingredient Batch (400 g) INCI Phase A 3.0 Uvinul T 150 Ethylhexyl Triazone 10.0 Uvinul A-Plus Granular Diethylamino Hydroxybenzoyl Hexyl Benzoate 3.0 Tinosorb S Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 1.0 Cutina GMS Glyceryl Stearate 2.0 Axol C 62 Glyceryl Stearate Citrate 7.0 Finsolv TN C12-15 Alkyl Benzoate 7.0 Cetiol B Dibutyl Adipate 4.0 Cosmacol ETI Di-C12-13 Alkyl Tartrate 1.0 Lanette O Cetearyl Alcohol 2.0 Unimer U-6 Triacontanyl PVP 3.0 Luvitol Lite Hydrogenated Polyisobutene Phase B 6.0 T-Lite SF-S Titanium Dioxide and Hydrated Silica and Dimethicone/Methicone Copolymer and Aluminum Hydroxide Phase C 2.0 Glycerin 86% Glycerin 2.0 Panthenol 50 P Panthenol 0.2 Edeta BD Disodium EDTA to 100 Water, demin. Water 0.15 Keltrol [E] Xanthan Gum 0.15 Polysurf 67 CS Cetyl Hydroxyethylcellulose 4.8 Tris Amino Ultra PC(20% in Tromethamine water) 2.0 Eusolex 232 Phenylbenzimidazole Sulfonic Acid Phase D 0.5 Vitamin E acetate Tocopheryl Acetate 1.0 Euxyl K 300 Phenoxyethanol and Methylparaben and Butylparaben and Ethylparaben and Propylparaben and Isobutylparaben

[0439] Preparation:

[0440] Heating of phase A to 80 C.

[0441] Addition of phase B to the molten phase A and homogenisation.

[0442] Homogenisation of phase C until clear.

[0443] Addition of phase C to phases A+B and homogenisation.

[0444] Cooling to 40 C. with stirring.

[0445] Addition of phase D, brief homogenisation and cooling to room temperature with stirring.

[0446] SPF in vivo COLIPA 30

[0447] Formulation 12:

TABLE-US-00022 % Ingredient INCI Phase A 3.0 Uvinul T 150 Ethylhexyl Triazone 10.0 Uvinul A-Plus Granular Diethylamino Hydroxybenzoyl Hexyl Benzoate 3.0 Tinosorb S Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 1.0 Cutina GMS Glyceryl Stearate 2.0 Axol C 62 Glyceryl Stearate Citrate 7.0 Finsolv TN C12-15 Alkyl Benzoate 7.0 Cetiol B Dibutyl Adipate 4.0 Cosmacol ETI Di-C12-13 Alkyl Tartrate 1.0 Lanette O Cetearyl Alcohol 2.0 Unimer U-6 Triacontanyl PVP 3.0 Luvitol Lite Hydrogenated Polyisobutene Phase B 6.0 T-Lite SF-S Titanium Dioxide and Hydrated Silica and Dimethicone/Methicone Copolymer and Aluminum Hydroxide Phase C 2.0 Glycerin 86% Glycerin 2.0 Panthenol 50 P Panthenol 0.2 Edeta BD Disodium EDTA to 100 Water, demin. Water 0.15 Keltrol [E] Xanthan Gum 0.15 Polysurf 67 CS Cetyl Hydroxyethylcellulose 4.8 Tris Amino Ultra Tromethamine PC(20% in water) 12.05 UV filter capsule (16.6% Aqua (water), Ethylhexyl Triazone, of Ethylhexyl Triazone in Dimethyl Capramide, Silica, PVP, Spectrasolv DMDA) Chlorphenesin Phase D 0.5 Vitamin E acetate Tocopheryl Acetate 1.0 Euxyl K 300 Phenoxyethanol and Methylparaben and Butylparaben and Ethylparaben and Propylparaben and Isobutylparaben

[0448] Preparation:

[0449] Heating of phase A to 80 C.

[0450] Addition of phase B to the molten phase A and homogenisation.

[0451] Homogenisation of phase C until clear. Addition of phase C to phases A+B and homogenisation.

[0452] Cooling to 40 C. with stirring.

[0453] Addition of phase D, brief homogenisation and cooling to room temperature with stirring.

[0454] SPF in vivo COLIPA 33

[0455] (UV)APF in vitro 11.