Water based concentrated product forms of oil-soluble organic UV absorbers

Abstract

The instant invention refers to the use of a concentrated aqueous polymer dispersion with an average particle size of less than 1000 nm comprising (a) a polymer carrier prepared by heterophase radical polymerization of at least one ethylenically unsaturated monomer in the presence of (b) an oil-soluble organic UV absorber selected from the class of p-aminobenzoic acid derivatives; salicylic acid derivatives; benzophenone derivatives; diphenyl acrylate derivatives; benzofuran derivatives; polymeric UV absorbers, comprising one or more organosilicon radicals; cinnamic acid derivatives; camphor derivatives; s-triazine derivatives; trianilino-s-triazine derivatives; menthyl anthranilates; and benzotriazole derivatives; wherein the weight ratio of the oil-soluble organic UV absorber (b) to polymer carrier (a) is greater than 50 parts UV absorber per 100 parts of carrier; for the protection of human and animal hair and skin against the damaging effect of UV radiation. The concentrated aqueous polymer dispersions show unexpectedly high sunscreen effects and a positive skin feeling.

Claims

1. A cosmetic composition comprising a concentrated aqueous polymer dispersion for the protection of human or animal hair or skin against the damaging effects of UV radiation comprising particles with an average particle size of less than 1000 nm; and a cosmetically acceptable carrier, wherein the particles of the concentrated aqueous polymer dispersion comprise: (a) a polymer carrier prepared by heterophase radical polymerization of at least one ethylenically unsaturated monomer in the presence of (b) at least one oil-soluble organic UV absorber of (b.sub.2); wherein (b.sub.2) is Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine of formula (2); ##STR00042## wherein the at least one ethylenically unsaturated monomer is selected from the group consisting of C.sub.1-C.sub.18 acrylates, C.sub.1-C.sub.18 methacrylates, acrylic acid, (meth)acrylic acid, styrene, vinyltoluene, hydroxy-functional acrylates or (meth)acrylates, acrylates or (meth)acrylates derived from alkoxylated alcohols, multifunctional acrylates or (meth)acrylates, and mixtures thereof; wherein the weight ratio of the oil-soluble organic UV absorber (b) to polymer carrier (a) in the particles is equal to or greater than 80 parts UV absorber per 100 parts of polymer carrier; wherein the concentration of the particles of the polymer carrier with the oil-soluble organic UV absorber in the dispersion is more than 50% and up to 60% b.w.; and wherein the at least one oil-soluble organic UV absorber (b) is dissolved in the at least one ethylenically unsaturated monomer before the heterophase radical polymerization.

2. The composition according to claim 1 wherein the average particle size is less than 500 nm.

3. The composition according to claim 1 comprising additionally a non-ionic, cationic or anionic surfactant.

4. The composition according to claim 1 wherein the oil-soluble organic UV absorber (b) has a water solubility of less than 1% by weight at room temperature and atmospheric pressure.

5. The cosmetic composition according to claim 1 in which is an aqueous environment/media/formulation.

6. The cosmetic composition according to claim 1, further comprising from 1 to 60% by weight, based on the total weight of the composition, of at least one oil component, from 0 to 30% by weight, based on the total weight of the composition, of at least one emulsifier, from 10 to 90% by weight, based on the total weight of the composition, of water, and from 0 to 88.9% by weight of further cosmetically acceptable adjuvants.

7. The cosmetic composition according to claim 1, wherein the heterophase radical polymerization for preparation of the polymer carrier comprises: (i) dissolving the oil-soluble organic UV absorber (b) in at least one ethylenically unsaturated monomer (a); (ii) preparing a conventional o/w emulsion of said UV absorber (b) dissolved in at least one ethylenically unsaturated monomer (a); (iii) homogenizing the conventional emulsion to a miniemulsion wherein the droplets of the organic phase have an average diameter below 1000 nm; and (iv) polymerizing the miniemulsion by adding a polymerization initiator.

8. The composition according to claim 1 wherein the polymer carrier consists of a polymerization reaction product of (i) the at least one ethylenically unsaturated monomer and (ii) optionally 0.5 to 20 wt. % ethylenically unsaturated multifunctional crosslinking monomers based on the total weight of monomers forming the polymerization reaction product.

Description

A. PREPARATION EXAMPLES

(1) The following oil-soluble UV absorbers are tested concerning their efficiency in sunscreen products:

(2) TABLE-US-00002 Compound of formula Structure (101) (102) (103) (104) (105) 0 (106)

Example A1

(3) For the preparation of a stable oil/water emulsion a mixture (UV-Mix 1) consisting of

(4) 65 parts of the compound (101),

(5) 10 parts of the compound (102) and

(6) 25 parts of the compound (103)

(7) is dissolved in 20 g methyl methacrylate (MMA), 1.6 g stearyl methacrylate (SMA) and 0.06 g butandioldiacrylate (BDDA). The oil phase is added dropwise to a stirred solution of 1.6 g sodium dodecylsulphate in 56.5 g deionised water. After stirring for 30 min and ultrasonically converting a kinetically stable emulsion is obtained with an average droplet size below 250 nm. The emulsion is heated up to 55° C. and the redox initiator (0.06 g ascorbic acid dissolved in 3 g deionised water; 0.25 ml H.sub.2O.sub.2 (35%) diluted in 0.5 g deionised water) is subsequently added to the reaction mixture.

(8) The reaction mixture is continuously stirred by a mechanical stirrer and is maintained at 55° C. for three hours, then cooled to room temperature (RT) and filtered via a 20 μm filter.

(9) The resulting particle size D.sub.INT is 141 nm.

(10) The active content of the oil soluble UV absorber mixture of the compounds (101), (102) and (103) is 20 wt %, based on the total weight of the emulsion.

Example A2

(11) For the preparation of a stable oil/water emulsion a mixture (UV-Mix 1) consisting of

(12) 65 parts of the compound (101),

(13) 10 parts of the compound (102) and

(14) 25 parts of the compound (103)

(15) is dissolved in 16 g methyl methacrylate (MMA), 1.6 g stearyl methacrylate (SMA) and 0.05 g butandioldiacrylate (BDDA). The oil phase is added dropwise to a stirred solution of 1.6 g sodium dodecylsulphate in 56.5 g deionised water. After stirring for 30 min and ultrasonically converting a kinetically stable emulsion is obtained with an average droplet size below 250 nm. The emulsion is heated up to 55° C. and the redox initiator (0.08 g ascorbic acid dissolved in 3 g deionised water; 0.32 ml H.sub.2O.sub.2 (35%) diluted in 0.5 g deionised water) is subsequently added to the reaction mixture.

(16) The reaction mixture is continuously stirred by a mechanical stirrer and is maintained at 55° C. for three hours, then cooled to RT and filtered via a 20 μm filter. The resulting particle size D.sub.INT is 182 nm.

(17) The active content of the oil soluble UV absorber mixture of the compounds (101), (102) and (103) is 24 wt %, based on the total weight of the emulsion.

Example A3

(18) For the preparation of a stable oil/water emulsion a mixture (UV-Mix 1) consisting of

(19) 65 parts of the compound (101),

(20) 10 parts of the compound (102) and

(21) 25 parts of the compound (103)

(22) is dissolved in 20 g ethyl acrylate (EA), 1.6 g stearyl methacrylate (SMA) and 0.06 g butandioldiacrylate (BDDA).

(23) The oil phase is added dropwise to a stirred solution of 1.6 g sodium dodecylsulphate in 56.5 g deionised water.

(24) After stirring for 30 min and ultrasonically converting a kinetically stable emulsion is obtained with an average droplet size below 250 nm. The emulsion is heated up to 55 C and the redox initiator (0.06 g ascorbic acid dissolved in 3 g deionised water; 0.25 ml H.sub.2O.sub.2 (35%) diluted in 0.5 g deionised water) is subsequently added to the reaction mixture.

(25) The reaction mixture is continuously stirred by a mechanical stirrer and is maintained at 55° C. for three hours, then cooled to RT and filtered via a 20 μm filter. The resulting particle size D.sub.INT is 156 nm.

(26) The active content of the oil soluble UV absorber mixture of the compounds (101), (102) and (103) is 20 wt %, based on the total weight of the emulsion.

Example A4

(27) For the preparation of a stable oil/water a mixture (UV-Mix 1) consisting of

(28) 65 parts of the compound (101),

(29) 10 parts of the compound (102) and

(30) 25 parts of the compound (103)

(31) is dissolved in 16 g ethyl acrylate (EA), 1.6 g stearyl methacrylate (SMA) and 0.05 g butandioldiacrylate (BDDA). The oil phase is added dropwise to a stirred solution of 1.6 g sodium dodecylsulphate in 56.5 g deionised water. After stirring for 30 min and ultrasonically converting a kinetically stable emulsion is obtained with an average droplet size below 250 nm. The emulsion is heated up to 55° C. and the redox initiator (0.08 g ascorbic acid dissolved in 3 g deionised water; 0.32 ml H.sub.2O.sub.2 (35%) diluted in 0.5 g deionised water) is subsequently added to the reaction mixture. The reaction mixture is continuously stirred by a mechanical stirrer and is maintained at 55° C. for three hours, then cooled to RT and filtered via a 20 μm filter.

(32) The resulting particle size D.sub.INT is 199 nm.

(33) The active content of the oil soluble UV absorber mixture of the compounds (101), (102) and (103) is 24 wt %, based on the total weight of the emulsion.

Example A5

(34) For the preparation of a stable oil/water emulsion a mixture (UV-Mix 1) consisting of

(35) 65 parts of the compound (101),

(36) 10 parts of the compound (102) and

(37) 25 parts of the compound (103)

(38) Is dissolved in 40 g methyl methacrylate (MMA), 4.8 g stearyl methacrylate (SMA) and 0.12 g butandioldiacrylate (BDDA). The oil phase is added dropwise to a stirred solution of 10.3 g Disponil® FES 32 IS (31 wt % active, Cognis Deutschland GmbH&Co.KG) in 115 g deionised water. After stirring for 30 min and ultrasonically converting a kinetically stable emulsion is obtained with an average droplet size below 250 nm.

(39) The emulsion is heated up to 55° C. and the redox initiator (0.2 g ascorbic acid dissolved in 3 g deionised water; 0.81 ml H.sub.2O.sub.2 (35%) diluted in 2.0 g deionised water) is subsequently added to the reaction mixture. The reaction mixture is continuously stirred by a mechanical stirrer and is maintained at 55° C. for three hours, then cooled to RT and filtered via a 20 μm filter.

(40) The resulting particle size D.sub.INT is 170 nm.

(41) The active content of the oil soluble UV absorber mixture of the compounds (101), (102) and (103) is 20 wt %, based on the total weight of the emulsion.

Example A6

(42) The following samples were prepared with a monomer mixture (Mix I), containing 11% hydroxyethyl methacrylate, 15% vinyl toluol, 15% cyclohexyl methacrylate, 28% methyl methacrylate and 31% iso-butyl methacrylate.

(43) For the preparation of a stable oil/water emulsion a mixture (UV-Mix1) consisting of

(44) 65 parts of the compound (101),

(45) 10 parts of the compound (102) and

(46) 25 parts of the compound (103)

(47) Is dissolved in 40 g of Mix I, 3.2 g stearyl methacrylate (SMA) and 0.12 g butandioldiacrylate (BDDA). The oil phase is added dropwise to a stirred solution of 10.3 g Disponil® FES 32 IS (31 wt % active, Cognis Deutschland GmbH&Co.KG) in 110 g deionised water. After stirring for 30 min and ultrasonically converting a kinetically stable emulsion is obtained with an average droplet size below 250 nm. The emulsion is heated up to 55° C. and the redox initiator (0.2 g ascorbic acid dissolved in 5 g deionised water; 0.81 ml H.sub.2O.sub.2 (35%) diluted in 5.0 g deionised water) is subsequently added to the reaction mixture. The reaction mixture is continuously stirred by a mechanical stirrer and is maintained at 55° C. for three hours, then cooled to RT and filtered via a 20 μm filter. The resulting particle size D.sub.INT is 198 nm. The final active content of the oil soluble UV absorber mixture of the compounds (101), (102) and (103) is 20 wt %, based on the total weight of the emulsion.

Example A7

(48) For the preparation of a stable oil/water emulsion a mixture (UV-Mix1) consisting of

(49) 65 parts of the compound (101),

(50) 10 parts of the compound (102) and

(51) 25 parts of the compound (103)

(52) Is dissolved in 40 g of Mix I and 3.2 g stearyl methacrylate (SMA). The oil phase is added dropwise to a stirred solution of 10.3 g Disponil® FES 32 IS (31 wt % active, Cognis Deutschland GmbH&Co.KG) in 110 g deionised water. After stirring for 30 min and ultrasonically converting a kinetically stable emulsion is obtained with an average droplet size below 250 nm. The emulsion is heated up to 55° C. and the redox initiator (0.2 g ascorbic acid dissolved in 5 g deionised water; 0.81 ml H.sub.2O.sub.2 (35%) diluted in 5.0 g deionised water) is subsequently added to the reaction mixture. The reaction mixture is continuously stirred by a mechanical stirrer and is maintained at 55° C. for three hours, then cooled to RT and filtered via a 20 μm filter. The resulting particle size D.sub.INT is 198 nm.

(53) The final active content of the oil soluble UV absorber mixture of the compounds (101), (102) and (103) is 20 wt %, based on the total weight of the emulsion.

Example A8

(54) For the preparation of a stable oil/water emulsion a mixture (UV-Mix1) consisting of

(55) 65 parts of the compound (101),

(56) 10 parts of the compound (102) and

(57) 25 parts of the compound (103)

(58) is dissolved in 40 g of Mix I, 3.2 g stearyl methacrylate (SMA) and 0.06 g dodecyl mercaptane (DDM). The oil phase is added dropwise to a stirred solution of 10.3 g Disponil® FES 32 IS (31 wt % active, Cognis Deutschland GmbH&Co.KG) in 110 g deionised water. After stirring for 30 min and ultrasonically converting a kinetically stable emulsion is obtained with an average droplet size below 250 nm. The emulsion is heated up to 55° C. and the redox initiator (0.2 g ascorbic acid dissolved in 5 g deionised water; 0.81 ml H.sub.2O.sub.2 (35%) diluted in 5.0 g deionised water) is subsequently added to the reaction mixture.

(59) The reaction mixture is continuously stirred by a mechanical stirrer and is maintained at 55° C. for three hours, then cooled to RT and filtered via a 20 μm filter.

(60) The resulting particle size D.sub.INT is 198 nm.

(61) The final active content of the oil soluble UV absorber mixture of the compounds (101), (102) and (103) is 20 wt %, based on the total weight of the emulsion.

(62) In analogy to examples A1 to A8 the following oil soluble UV filters or mixtures of oil soluble UV filters are used for the preparation of stable emulsions as described above:

(63) TABLE-US-00003 Example A9 to A16: Example A17 to A24: A mixture (UV-Mix2) consisting of A mixture (UV-Mix3) 97 parts of the compound (101), consisting of 1 part of the compound (102) and 90 parts of the 2 parts of the compound (103) compound (101) and 10 parts of the compound (102) Example A25 to A32: Example A33 to A40: Compound (101) Compound (102) Example A41 to A48: Example A49 to A56: A mixture (UV-Mix4) consisting of A mixture (UV-Mix5) 33.3 parts of the compound (104), consisting of 66.6 parts of the compound (105) 30 parts of the compound (104), 70 parts of the compound (105) Examples A57 to A64: Examples A 65 to A72: A mixture (UV-Mix6) consisting of A mixture (UV-Mix7) 90 parts of the compound (102), consisting of 10 parts of the compound (106) 99 parts of the compound (102), 1 part of the compound (106) Examples A73 to A80: Examples A81 to A88: A mixture (UV-Mix8) consisting of A mixture (UV-Mix9) 80 parts of the compound (102), consisting of 20 parts of the compound (103) 77 parts of the compound (102), 33 parts of the compound (103) Examples A89 to A96: A mixture (UV-Mix10) consisting of 75 parts of the compound (102), 20 parts of the compound (103) 5 parts of the compound (106)

(64) In analogy to examples A1 to A104 the above mentioned oil soluble UV filters [compound (101) to (106)] as well as their mixtures [(UV-Mix 1) to (UV-Mix10)] can be used for the preparation of stable emulsions as described in the following preparation examples:

Example A97 to A112

(65) For the preparation of a stable oil/water emulsion

(66) an oil soluble UV filter selected from [compound (101) to (106)]

(67) or a mixture of oil soluble UV filters selected from [(UV-Mix 1) to (UV-Mix10)]

(68) is dissolved in 34.2 g of methyl methacrylate (MMA), 3.04 g stearyl methacrylate (SMA), 0.76 g methyl acrylic acid (MAA) and 0.11 g butandiol diacrylate (BDDA). The oil phase is added dropwise to a stirred solution of 10.3 g Disponil® FES 32 IS (31 wt % active, Cognis Deutschland GmbH&Co.KG) in 110 g deionised water. After stirring for 30 min and ultrasonically converting a kinetically stable emulsion is obtained with an average droplet size below 250 nm. The emulsion is heated up to 55° C. and the redox initiator (0.2 g ascorbic acid dissolved in 5 g deionised water; 0.81 ml H.sub.2O.sub.2 (35%) diluted in 5.0 g deionised water) is subsequently added to the reaction mixture.

(69) The reaction mixture is continuously stirred by a mechanical stirrer and is maintained at 55° C. for three hours, then cooled to RT and filtered via a 20 μm filter.

(70) The resulting particle size D.sub.INT is 198 nm.

(71) The final active content of the oil soluble UV absorber is 20 wt %, based on the total weight of the emulsion.

Example A113 to A128

(72) For the preparation of a stable oil/water emulsion

(73) an oil soluble UV filter selected from [compound (101) to (106)]

(74) or a mixture of oil soluble UV filters selected from [(UV-Mix 1) to (UV-Mix10)]

(75) is dissolved in 76 g of methyl methacrylate (MMA) and 0.11 g butandiol diacrylate (BDDA). The oil phase is added dropwise to a stirred solution of 10.3 g Disponil® FES 32 IS (31 wt % active, Cognis Deutschland GmbH&Co.KG) in 110 g deionised water. After stirring for 30 min and ultrasonically converting a kinetically stable emulsion is obtained with an average droplet size below 250 nm. The emulsion is heated up to 55° C. and the redox initiator (0.2 g ascorbic acid dissolved in 5 g deionised water; 0.81 ml H.sub.2O.sub.2 (35%) diluted in 5.0 g deionised water) is subsequently added to the reaction mixture.

(76) The reaction mixture is continuously stirred by a mechanical stirrer and is maintained at 55° C. for three hours, then cooled to RT and filtered via a 20 μm filter.

(77) The resulting particle size D.sub.INT is 198 nm.

(78) The final active content of the oil soluble UV absorber is 20 wt %, based on the total weight of the emulsion.

Example A129 to A144

(79) For the preparation of a stable oil/water emulsion

(80) an oil soluble UV filter selected from [compound (101) to (106)]

(81) or a mixture of oil soluble UV filters selected from [(UV-Mix 1) to (UV-Mix10)]

(82) is dissolved in 76 g of methyl methacrylate (MMA) and 1.14 g butandiol diacrylate (BDDA). The oil phase is added dropwise to a stirred solution of 10.3 g Disponil® FES 32 IS (31 wt % active, Cognis Deutschland GmbH&Co.KG) in 110 g deionised water. After stirring for 30 min and ultrasonically converting a kinetically stable emulsion is obtained with an average droplet size below 250 nm. The emulsion is heated up to 55° C. and the redox initiator (0.2 g ascorbic acid dissolved in 5 g deionised water; 0.81 ml H.sub.2O.sub.2 (35%) diluted in 5.0 g deionised water) is subsequently added to the reaction mixture.

(83) The reaction mixture is continuously stirred by a mechanical stirrer and is maintained at 55° C. for three hours, then cooled to RT and filtered via a 20 μm filter.

(84) The resulting particle size D.sub.INT is 198 nm.

(85) The final active content of the oil soluble UV absorber is 20 wt %, based on the total weight of the emulsion.

Example A145 to A160

(86) or the preparation of a stable oil/water emulsion

(87) an oil soluble UV filter selected from [compound (101) to (106)]

(88) or a mixture of oil soluble UV filters selected from [(UV-Mix 1) to (UV-Mix10)]

(89) is dissolved in 76 g of methyl methacrylate (MMA) and 1.14 g trimethylolpropane triacrylate (TMPTA). The oil phase is added dropwise to a stirred solution of 10.3 g Disponil® FES 32 IS (31 wt % active, Cognis Deutschland GmbH&Co.KG) in 110 g deionised water. After stirring for 30 min and ultrasonically converting a kinetically stable emulsion is obtained with an average droplet size below 250 nm. The emulsion is heated up to 55° C. and the redox initiator (0.2 g ascorbic acid dissolved in 5 g deionised water; 0.81 ml H.sub.2O.sub.2 (35%) diluted in 5.0 g deionised water) is subsequently added to the reaction mixture.

(90) The reaction mixture is continuously stirred by a mechanical stirrer and is maintained at 55° C. for three hours, then cooled to RT and filtered via a 20 μm filter.

(91) The resulting particle size D.sub.INT is 198 nm.

(92) The final active content of the oil soluble UV absorber is 20 wt %, based on the total weight of the emulsion.

B. APPLICATION EXAMPLES

(93) The UV absorbing PMMA polymerisates are incorporated under stirring in the aqueous phase of cosmetic formulations:

(94) Basis Formulation 1:

(95) SPF8 (5% OCR; 0.9% BMDBM, 0.8% Tinosorb S)

(96) TABLE-US-00004 % w/w (as INCI-Name supplied) Part A Butylene Glycol Dicaprylate/Dicaprate 8.00 Dicaprylyl Ether 6.00 Octyldodecanol 5.00 Cyclomethicone 3.00 Glyceryl Stearate Citrate 2.50 Stearyl Alcohol 2.30 Butyl Methoxydibenzoylmethane 0.90 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 0.80 Hydrogenated Coco-Glycerides 1.50 Octocrylene 5.00 PVP/Hexadecene Copolymer 0.80 Part B Aqua Qs to 100 Glycerin 7.00 Xanthan Gum 0.10 Acrylates/C10-30 Alkyl Acrylate Crosspolymer 0.05 Disodium EDTA 0.05 Part C DMDM Hydantoin 0.30 Phenoxyethanol 0.70

(97) TABLE-US-00005 Example B1: Addition of 10% PMMA polymerisate according to Preparation Example A1 in the water phase of base formation 1 Example B2: Addition of 1.3% Ethylhexyl Methoxycinnnamate, 0.5% Benzotriazolyl Dodecyl p-Cresol and 0.2% Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine in the oil phase of the Base formulation 1 as comparative example Example B3: Base formulation 1 without further additives as reference example

(98) The additions from base Formulation 1 are incorporated in the base formulation 1 at 30 to 40° C. with stirring.

(99) The samples are applied on sand blasted PMMA plates (delivered by Helioscience, Marseille, France) with a concentration of 1.4 mg/cm.sup.2, irradiated with an Atlas CPS+ Irradiator and tested in an Optometrics SPF 290 analyzer. The testing procedure is carried out according to DIN 67502. The calculation of the in vitro SPF is done according to M. Wloka et al., Proceedings of the 8.sup.th International Conference, The Royal Society, London, Paper12.

(100) TABLE-US-00006 Results Example B1 Example B2 Example B3 In vitro SPF 6.3 5.0 3.3

(101) Basis Formulation 2:

(102) O/W anionic SPF10 (5% OCR; 2.5% BMDBM, 1.7% Tinosorb S)

(103) TABLE-US-00007 % w/w (as INCI-Name supplied) Part A Phenethyl Benzoate 5.50 Cetearyl Ethylhexanoate 4.00 Glyceryl Stearate 4.00 Cetearyl Alcohol (and) PEG-20 Stearate 2.50 Potassium Cetyl Phosphate 2.00 Butyl Methoxydibenzoylmethane 2.50 Octocrylene 5.00 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 1.70 Part B Aqua Qs to 100 Propylene Glycol 3.50 Sodium EDTA 0.20 Xanthan Gum 0.15 Part C Propylene Glycol (and) Diazolidinyl Urea 0.70 (and) Methylparaben (and) Propylparaben Part D Triethanolamine qs

(104) TABLE-US-00008 Example B4: Addition of 10% PMMA polymerisate according to Preparation Example A1 in the water phase of base formation 2 Example B5: Addition of 1.3% Ethylhexyl Methoxycinnnamate, 0.5% Benzotriazolyl Dodecyl p-Cresol and 0.2% Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine in the oil phase of the Base formulation 2 as comparative example Example B6: Base formulation 2 without further additives as reference example

(105) The components of B4, B5 and B6 respectively are incorporated in the base formulation 2 at 50 to 60° C. with stirring.

(106) The samples are applied on sand blasted PMMA plates (delivered by Helioscience, Marseille, France) with a concentration of 1.4 mg/cm.sup.2, irradiated with an Atlas CPS+ Irradiator and tested in an Optometrics SPF 290 analyzer. The testing procedure is carried out according to DIN 67502. The calculation of the in vitro SPF is done according to M. Wloka et al., Proceedings of the 8.sup.th International Conference, The Royal Society, London, Paper12.

(107) TABLE-US-00009 Results Example B4 Example B5 Example B6 In vitro SPF 12.4 11.7 8.4

(108) Basis Formulation 3:

(109) O/W anionic SPF25 (10% OCR; 2.6% BMDBM, 2.5% Tinosorb S, 1.6% TiO.sub.2)

(110) TABLE-US-00010 % w/w (as INCI-Name supplied) Part A Phenethyl Benzoate 6.00 Cetearyl Ethylhexanoate 2.00 Glyceryl Stearate 4.00 Cetearyl Alcohol (and) PEG-20 Stearate 3.00 Potassium Cetyl Phosphate 2.00 Butyl Methoxydibenzoylmethane 2.60 Octocrylene 10.00  Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 2.50 Titanium Dioxide (and) Aluminum Hydroxide (and) 1.60 Stearic Acid Part B Aqua Qs to 100 Propylene Glycol 3.50 Sodium EDTA 0.20 Xanthan Gum 0.15 Part C Propylene Glycol (and) Diazolidinyl Urea (and) 0.70 Methylparaben (and) Propylparaben Part D Triethanolamine qs

(111) TABLE-US-00011 Example B7: Addition of 10% PMMA polymerisate according to Preparation Example A1 in the water phase of base formation 3 Example B8: Addition of 1.3% Ethylhexyl Methoxycinnnamate, 0.5% Benzotriazolyl Dodecyl p-Cresol and 0.2% Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine in the oil phase of the Base formulation 3 as comparative example Example B9: Base formulation 3 without further additives as reference example

(112) The components of B7, B85 and B9 respectively are incorporated in the base formulation 3 at 50 to 60° C. with stirring.

(113) The samples are applied on sand blasted PMMA plates (delivered by Helioscience, Marseille, France) with a concentration of 1.4 mg/cm.sup.2, irradiated with an Atlas CPS+ Irradiator and tested in an Optometrics SPF 290 analyzer. The testing procedure is carried out according to DIN 67502. The calculation of the in vitro SPF is done according to M. Wloka et al., Proceedings of the 8.sup.th International Conference, The Royal Society, London, Paper12.

(114) TABLE-US-00012 Results Example B7 Example B8 Example B9 In vitro SPF 27 25 18

(115) The in-vitro SPF Very Water Resistance (VWR) Evaluations Were Conducted Using VITRO-SKIN® N-19 as the Substrate According to the IMS, Inc. in vitro Very Water Resistant Test Protocol.

(116) TABLE-US-00013 Results Example B7 Example B8 % SPF remainingg 98 87

(117) Basis Formulation 4:

(118) W/O SPF10 (5% OCR; 2.5% BMDBM, 1.7% Tinosorb S)

(119) TABLE-US-00014 % w/w (as INCI-Name supplied) Part A Phenethyl Benzoate 7.00 Microcrystalline Wax 1.50 Mineral Oil 3.50 Isohexadecane 3.50 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 1.70 Octocrylene 5.00 Cetyl Alcohol 0.50 Butyl Methoxydibenzoylmethane 2.50 Hydrogenated Castor Oil 0.80 PEG-30 Dipolyhydroxystearate 3.50 PEG-22/Dodecyl Glycol Copolymer 1.50 Part B Aqua Qs to 100 Propylene Glycol 4.00 Hydrated Magnesium Sulfate 0.70 Sodium EDTA 0.20 Glycerin 2.00 Part C Diazolidinyl Urea (and) Methyl paraben (and) 0.50 Propyl paraben (and) Propylene Glycol

(120) TABLE-US-00015 Example B10: Addition of 10% PMMA polymerisate according to Preparation Example A1 in the water phase of base formation 4 Example B11: Addition of 1.3% Ethylhexyl Methoxycinnnamate, 0.5% Benzotriazolyl Dodecyl p-Cresol and 0.2% Bis- Ethylhexyloxyphenol Methoxyphenyl Triazine in the oil phase of the Base formulation 4 as comparative example Example B12: Base formulation 4 without further additives as reference example

(121) The components of B10, B11 and B12 respectively are incorporated in the base formulation 4 at 50 to 60° C. with stirring.

(122) The samples are applied on sand blasted PMMA plates (delivered by Helioscience, Marseille, France) with a concentration of 1.4 mg/cm.sup.2, irradiated with an Atlas CPS+ Irradiator and tested in an Optometrics SPF 290 analyzer. The testing procedure is carried out according to DIN 67502. The calculation of the in vitro SPF is done according to M. Wloka et al., Proceedings of the 8.sup.th International Conference, The Royal Society, London, Paper12.

(123) TABLE-US-00016 Results Example B10 Example B11 Example B12 In vitro SPF 19 17 11

(124) Basis Formulation 5:

(125) W/O SPF25 (10% OCR; 2.6% BMDBM, 2.5% Tinosorb S, 1.6% TiO.sub.2)

(126) TABLE-US-00017 % w/w (as INCI-Name supplied) Part A Phenethyl Benzoate 5.00 Microcrystalline Wax 1.50 Mineral Oil 3.50 Isohexadecane 3.50 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 2.50 Octocrylene 10.00  Cetyl Alcohol 1.50 Butyl Methoxydibenzoylmethane 2.60 Titanium Dioxide (and) Stearic Acid (and) Alumina 1.60 Hydrogenated Castor Oil 1.00 PEG-30 Dipolyhydroxystearate 3.50 PEG-22/Dodecyl Glycol Copolymer 1.80 Part B Aqua Qs to 100 Propylene Glycol 4.00 Hydrated Magnesium Sulfate 0.70 Sodium EDTA 0.20 Glycerin 2.00 Part C Diazolidinyl Urea (and) Methyl paraben (and) 0.50 Propyl paraben (and) Propylene Glycol

(127) TABLE-US-00018 Example B13: Addition of 10% PMMA polymerisate according to Preparation Example A1 in the water phase of base formation 5 Example B14: Addition of 1.3% Ethylhexyl Methoxycinnnamate, 0.5% Benzotriazolyl Dodecyl p-Cresol and 0.2% Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine in the oil phase of the Base formulation 5 as comparative example Example B15: Base formulation 5 without further additives as reference example

(128) The components of B13, B14 and B15 respectively are incorporated in the base formulation 5 at 50 to 60° C. with stirring.

(129) The samples are applied on sand blasted PMMA plates (delivered by Helioscience, Marseille, France) with a concentration of 1.4 mg/cm.sup.2, irradiated with an Atlas CPS+ Irradiator and tested in an Optometrics SPF 290 analyzer. The testing procedure is carried out according to DIN 67502. The calculation of the in vitro SPF is done according to M. Wloka et al., Proceedings of the 8.sup.th International Conference, The Royal Society, London, Paper12.

(130) TABLE-US-00019 Results Example B13 Example B14 Example B15 In vitro SPF 49 30 36

(131) The samples were tested in vivo according to the International Sun Protection Factor (SPF) Test Method, COLIPA, May 2006 (screening) and Colipa Recommendation No. 11—SPF Classification/upper limit, COLIPA, June 2002.

(132) TABLE-US-00020 Results Example B13 Example B14 In vivo SPF 47.7 32.5

(133) Basis Formulation 6:

(134) O/W non-ionic SPF10 (5% OCR; 2.5% BMDBM, 1.7% Tinosorb S)

(135) TABLE-US-00021 % w/w (as INCI-Name supplied) Part A Polyglyceryl-3 Methylglucose Distearate 2.00 Steareth-2 2.50 Steareth-21 1.00 Caprylic/Capric Triglyceride 6.50 Isopropyl Palmitate 5.80 Decyl Oleate 5.70 Cetyl Alcohol 0.70 Butyl Methoxydibenzoylmethane 2.50 Octocrylene 5.00 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 1.70 Part B Aqua Qs to 100 Glycerin 3.00 Disodium EDTA 0.20 Xanthan Gum 0.30 Part C Phenoxyethanol (and) Methylparaben (and) 1.00 Ethylparaben (and) Butylparaben (and) Propylparaben (and) Isobutylparaben Part D Water (and) Sodium Hydroxide qs

(136) TABLE-US-00022 Example B16: Addition of 10% PMMA polymerisate according to Preparation Example A1 in the water phase of base formation 6 Example B17: Addition of 1.3% Ethylhexyl Methoxycinnnamate, 0.5% Benzotriazolyl Dodecyl p-Cresol and 0.2% Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine in the oil phase of the Base formulation 6 as comparative example Example B18: Base formulation 6 without further additives as reference example

(137) The components of B16, B17 and B18 respectively are incorporated in the base formulation 6 at 50 to 60° C. with stirring.

(138) The samples are applied on sand blasted PMMA plates (delivered by Helioscience, Marseille, France) with a concentration of 1.4 mg/cm.sup.2, irradiated with an Atlas CPS+ Irradiator and tested in an Optometrics SPF 290 analyzer. The testing procedure is carried out according to DIN 67502. The calculation of the in vitro SPF is done according to M. Wloka et al., Proceedings of the 8.sup.th International Conference, The Royal Society, London, Paper12.

(139) TABLE-US-00023 Results Example B16 Example B17 Example B18 In vitro SPF 18.5 14.0 11.7

(140) Basis Formulation 7:

(141) O/W non-ionic SPF25 (10% OCR; 2.6% BMDBM, 2.5% Tinosorb S, 1.6% TiO.sub.2)

(142) TABLE-US-00024 % w/w (as INCI-Name supplied) Part A Polyglyceryl-3 Methylglucose Distearate 2.00 Steareth-2 2.50 Steareth-21 1.00 Caprylic/Capric Triglyceride 6.50 Isopropyl Palmitate 5.80 Decyl Oleate 5.70 Cetyl Alcohol 1.50 Butyl Methoxydibenzoylmethane 2.60 Octocrylene 10.00  Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 2.50 Titanium Dioxide (and) Stearic Acid (and) Alumina 1.60 Part B Aqua Qs to 100 Glycerin 3.00 Disodium EDTA 0.20 Xanthan Gum 0.30 Part C Phenoxyethanol (and) Methylparaben (and) 1.00 Ethylparaben (and) Butylparaben (and) Propylparaben (and) Isobutylparaben Part D Water (and) Sodium Hydroxide qs

(143) TABLE-US-00025 Example B19: Addition of 10% PMMA polymerisate according to Preparation Example A1 in the water phase of base formation 7 Example B20: Addition of 1.3% Ethylhexyl Methoxycinnnamate, 0.5% Benzotriazolyl Dodecyl p-Cresol and 0.2% Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine in the oil phase of the Base formulation 7 as comparative example Example B21: Base formulation 7 without further additives as reference example

(144) The components of B19, B20 and B21 respectively are incorporated in the base formulation 7 at 50 to 60° C. with stirring.

(145) The samples are applied on sand blasted PMMA plates (delivered by Helioscience, Marseille, France) with a concentration of 1.4 mg/cm.sup.2, irradiated with an Atlas CPS+ Irradiator and tested in an Optometrics SPF 290 analyzer. The testing procedure is carried out according to DIN 67502. The calculation of the in vitro SPF is done according to M. Wloka et al., Proceedings of the 8.sup.th International Conference, The Royal Society, London, Paper12.

(146) TABLE-US-00026 Results Example B19 Example B20 Example B21 In vitro SPF 33.0 27.5 25.4

(147) Basis Formulation 8:

(148) O/W gel SPF10 (5% OCR; 2.5% BMDBM, 1.7% Tinosorb S)

(149) TABLE-US-00027 % w/w (as INCI-Name supplied) Part A Stearyl Dimethicone 6.00 Octyldodecanol 4.00 C12-15 Alkyl Benzoate 13.80  Octocrylene 5.00 Butyl Methoxydibenzoylmethane 2.50 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 1.70 Part B Aqua Qs to 100 Acrylates/C10-30 Alkyl Acrylate Crosspolymer 0.35 Glycerin 6.00 Disodium EDTA 0.10 Part C Tocopheryl Acetate 0.50 Phenoxyethanol (and) Methylparaben (and) 1.00 Ethylparaben (and) Butylparaben (and) Propylparaben (and) Isobutylparaben

(150) TABLE-US-00028 Example B22: Addition of 10% PMMA polymerisate according to Preparation Example A1 in the water phase of base formation 8 Example B23: Addition of 1.3% Ethylhexyl Methoxycinnnamate. 0.5% Benzotriazolyl Dodecyl p-Cresol and 0.2% Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine in the oil phase of the Base formulation 8 as comparative example Example B24: Base formulation 8 without further additives as reference example

(151) The components of B22, B23 and B24 respectively are incorporated in the base formulation 8 at 50 to 60° C. with stirring.

(152) The samples are applied on sand blasted PMMA plates (delivered by Helioscience, Marseille, France) with a concentration of 1.4 mg/cm.sup.2, irradiated with an Atlas CPS+ Irradiator and tested in an Optometrics SPF 290 analyzer. The testing procedure is carried out according to DIN 67502. The calculation of the in vitro SPF is done according to M. Wloka et al., Proceedings of the 8.sup.th International Conference, The Royal Society, London, Paper12.

(153) TABLE-US-00029 Results Example B22 Example B23 Example B24 In vitro SPF 14.5 11.2 8.6

(154) Basis Formulation 9: Water/Silicon

(155) TABLE-US-00030 % w/w INCI-Name (as supplied) Part A Lauryl PEG/PPG-18/18 Methicone 3.00 C30-45 Alkyl Methicone (and) C30-45 Olefin 2.00 Ethylhexyl Methoxycinnamate 7.50 Isoamyl p-Methoxycinnamate 3.50 Part B Cyclohexasiloxane (and) Cyclopentasiloxane 8.50 Part C Water Qs to 100 Glycerin 4.00 Sodium Chloride 1.00

(156) TABLE-US-00031 Example B25: Addition of 10% PMMA polymerisate according to Preparation Example A106 in the water phase of base formation 9 Example B26: Addition of 2% Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine in the oil phase of the Base formulation 9 as comparative example

(157) The components of B25, and B26 respectively are incorporated in the base formulation 9 at 50 to 60° C. with stirring.

(158) The samples are applied on sand blasted PMMA plates (delivered by Helioscience, Marseille, France) with a concentration of 1.4 mg/cm.sup.2, irradiated with an Atlas CPS+ Irradiator and tested in an Optometrics SPF 290 analyzer. The testing procedure is carried out according to DIN 67502. The calculation of the in vitro SPF is done according to M. Wloka et al., Proceedings of the 8.sup.th International Conference, The Royal Society, London, Paper12.

(159) TABLE-US-00032 Results: Example B25 Example B26 In vitro SPF 16 15

(160) Basis Formulation 10: O/W Anionic (10% OCR; 2.6% BMDBM, 0.5% Tinosorb S. 1.6% TiO.sub.2)

(161) TABLE-US-00033 % w/w (as INCI-Name supplied) Part A Phenethyl Benzoate 6.00 Cetearyl Ethylhexanoate 2.00 Glyceryl Stearate 4.00 Cetearyl Alcohol (and) PEG-20 Stearate 3.00 Potassium Cetyl Phosphate 2.00 Butyl Methoxydibenzoylmethane 2.60 Octocrylene 10.00  Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 0.50 Titanium Dioxide (and) Aluminum Hydroxide (and) 1.60 Stearic Acid Part B Aqua Qs to 100 Propylene Glycol 3.50 Sodium EDTA 0.20 Xanthan Gum 0.15 Part C Propylene Glycol (and) Diazolidinyl Urea (and) 0.70 Methylparaben (and) Propylparaben Part D Triethanolamine qs

(162) TABLE-US-00034 Example B27: Addition of 10% PMMA polymerisate according to Preparation Example A106 in the water phase of base formation 10 Example B28: Addition of 2% Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine in the oil phase of the Base formulation 10 as comparative example

(163) The components of B27 and B28 respectively are incorporated in the base formulation 10 at 50 to 60° C. with stirring.

(164) The samples are applied on sand blasted PMMA plates (delivered by Helioscience, Marseille, France) with a concentration of 1.4 mg/cm.sup.2, irradiated with an Atlas CPS+ Irradiator and tested in an Optometrics SPF 290 analyzer. The testing procedure is carried out according to DIN 67502. The calculation of the in vitro SPF is done according to M. Wloka et al., Proceedings of the 8.sup.th International Conference, The Royal Society, London, Paper12.

(165) TABLE-US-00035 Results Example B27 Example B28 In vitro SPF 25.1 18.1

(166) Basis Formulation 11: W/O (10% OCR: 2.6% BMDBM, 0.5% Tinosorb S 1.6% TiO.sub.2)

(167) TABLE-US-00036 % w/w (as INCI-Name supplied) Part A Phenethyl Benzoate 5.00 Microcrystalline Wax 1.50 Mineral Oil 3.50 Isohexadecane 3.50 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 0.50 Octocrylene 10.00  Cetyl Alcohol 1.50 Butyl Methoxydibenzoylmethane 2.60 Titanium Dioxide (and) Stearic Acid (and) Alumina 1.60 Hydrogenated Castor Oil 1.00 PEG-30 Dipolyhydroxystearate 3.50 PEG-22/Dodecyl Glycol Copolymer 1.80 Part B Aqua Qs to 100 Propylene Glycol 4.00 Hydrated Magnesium Sulfate 0.70 Sodium EDTA 0.20 Glycerin 2.00 Part C Diazolidinyl Urea (and) Methyl paraben (and) 0.50 Propyl paraben (and) Propylene Glycol

(168) TABLE-US-00037 Example B29: Addition of 10% PMMA polymerisate according to Preparation Example A106 in the water phase of base formation 11 Example B30: Addition of 2% Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine in the oil phase of the Base formulation 11 as comparative example

(169) The components of B29 and B30 respectively are incorporated in the base formulation 11 at 50 to 60° C. with stirring.

(170) The samples are applied on sand blasted PMMA plates (delivered by Helioscience, Marseille, France) with a concentration of 1.4 mg/cm.sup.2, irradiated with an Atlas CPS+ Irradiator and tested in an Optometrics SPF 290 analyzer. The testing procedure is carried out according to DIN 67502. The calculation of the in vitro SPF is done according to M. Wloka et al., Proceedings of the 8.sup.th International Conference, The Royal Society, London, Paper12.

(171) TABLE-US-00038 Results Example B29 Example B30 In vitro SPF 48.3 36.0

(172) Basis Formulation 12:

(173) TABLE-US-00039 Examples B31 B32 B33 B34 B35 B36 B37 B38 % w/w % w/w % w/w % w/w % w/w % w/w % w/w % w/w (as (as (as (as (as (as (as (as INCI-Name supplied) supplied) supplied) supplied) supplied) supplied) supplied) supplied) Part Phenethyl Benzoate 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 A Cetearyl Ethylhexanoate 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Glyceryl Stearate 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Cetearyl Alcohol (and) PEG-20 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 Stearate Potassium Cetyl Phosphate 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Butyl Methoxydibenzoylmethane 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Octocrylene 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 Bis-Ethylhexyloxyphenol 2.00 2.00 2.00 2.00 Methoxyphenyl Triazine Part Water 58.40 49.60 66.72 57.92 68.92 60.12 65.51 56.71 B Propylene Glycol 3.50 3.50 3.50 3.50 3.50 3.50 3.50 3.50 Sodium EDTA 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 Xanthan Gum 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 Part Water 10.00 10.00 C Phenylbenzimidazole Sulfonic 2.30 2.30 Acid Triethanolamine 1.26 1.26 Titanium Dioxide (and) Hydrated 7.10 7.10 Silica (and) Aluminum Hydroxide (and) Alginic Acid Methylene Bis-Benzotriazolyl 6.00 6.00 Tetramethylbutylphenol (and) Aqua (and) Decyl Glucoside (and) Propylene Glycol (and) Xanthan Gum Tris-Biphenyl Triazine 4.00 4.00 Preparation Example A106 10.00 10.00 10.00 10.00 Part Propylene Glycol (and) Diazoli- 0.70 0.70 0.70 0.70 0.70 0.70 0.70 0.70 C dinyl Urea (and) Methylparaben (and) Propylparaben Part Triethanolamine qs qs qs qs qs qs qs E

(174) Basis Formulation 13:

(175) TABLE-US-00040 Example INCI B39 B40 Lauryl PEG-9 Polydimethylsiloxyethyl 3.00 3.00 Dimethicone Ethylhexyl Benzoate 13.00 8.00 Dimethicone (and) 1.00 1.00 Trimethylsiloxysilicate Cyclopentasiloxane 11.00 11.00 Caprylyl Methicone 11.00 11.00 Ethylhexyl Methoxycinnamate 7.00 7.00 Zinc Oxide (and) Dimethicone/Methicone 8.30 8.30 Copolymer Cyclomethicone (and) Titanium Dioxide 5.00 5.00 (and) Bis-PEG/PPG-14/14 Di- methicone Bis-Ethylhexyloxyphenol Methoxy- 3.00 0.00 phenyl Triazine Water 16.10 13.10 Tocopheryl Acetate 3.00 3.00 Butylene Glycol 3.00 3.00 Sodium Chloride 1.00 1.00 Disodium EDTA 0.20 0.20 Alcohol 7.00 7.00 Preparation Example A106 0.00 10.00 Polymethylsilsesquioxane 4.00 4.00 Silica 3.00 3.00 Phenonip 0.40 0.40