Crosslinked partial polyglycerol esters

Abstract

The present invention provides partial polyglycerol esters based on mono- and dicarboxylic acids, as well as their production and use, particularly in cosmetics.

Description

Field of the invention

[0001] The invention provides polyglycerol partial esters based on mono- and dicarboxylic acids, the production and use thereof, in cosmetics in particular.Prior art

[0002] Commercially available cosmetic film formers for sun protection and make-up formulations are mostly high-molecular-weight synthetic / petrochemically based, non-biodegradable polymers such as polyurethanes, polyacrylates, polyolefins, polyvinylpyrrolidones or the corresponding copolymers thereof. Examples thereof are products with the Antaron / Ganex (Ashland), Baycusan (Covestro) or Tego SP (Evonik) trade names.

[0003] Reasonably hydrophilic and thus reasonably readily water-soluble / water-swellable film formers based on natural polymers have likewise been described and are based for example on polysaccharides such as starch, cellulose and derivatives thereof or polypeptides. However, these do not exhibit good water resistance and often also show inadequate sun protection factor (SPF) boosting properties in sun protection or make-up formulations.

[0004] Products based on renewable raw materials are of ever-increasing interest to consumers not just from an environmental perspective, but from a toxicological perspective too. For instance, partial esters of polyols with fatty acids have already made inroads into diverse fields of use in cosmetics and other areas. Corresponding products having "film-forming properties" are already on the market. Examples of these include: Syncrowax ™< ORM (Croda; INCI: Sorbitol / Sebacic Acid Copolymer Behenate), Cera Bellina #106 (Koster Keunen; INCI: Polyglyceryl-3 Beeswax), CosmoSurf ®< PG1-IS (Surfatech Corp.; INCI: Polyglyceryl-3 Stearate / Isostearate Dimer Dilinoleate Copolymer), SurfaCare S (Surfatech Corp.; INCI: Oleic / Linoleic / Linolenic Polyglycerides), LexFilm Sun natural (Inolex; INCI: Capryloyl Glycerin / Sebacic Acid Copolymer), SolAmaze ™< Natural polymer (Nouryon; INCI: Diisostearoyl Polyglyceryl-3 Dimer Dilinoleate (and) Caprylic / Capric Triglyceride), Pelemol 6GPR (Phoenix Chem; INCI: Polyglyceryl-6 Polyricinoleate) and Nomcort HK-G (INCI: Glyceryl Behenate / Eicosadioate), Nomcort HK-P (INCI: Polyglyceryl-10 Behenate / Eicosadioate) and Nomcort SG (INCI: Glyceryl Tribehenate / Isostearate / Eicosadioate) from Nisshin Oillio Group.

[0005] However, all these products have inadequate film-forming properties compared to the abovementioned synthetic / petrochemically based polymers.

[0006] Partial esters of polyglycerols are a particularly interesting group of products on account of the diverse possibilities for variation: EP0835862 describes polyglycerol partial esters of saturated or unsaturated, linear or branched fatty acids and polyfunctional carboxylic acids, obtainable by esterification of a polyglycerol mixture with saturated or unsaturated, linear or branched fatty acids having 12 to 22 carbon atoms and polyfunctional carboxylic acids having 4 to 54 carbon atoms and an average functionality of 2 to 2.4, the degree of esterification of the polyglycerol mixture being between 30 and 75%, and the use thereof as W / O emulsifiers and dispersion aids.

[0007] A disadvantage of the specific polyglycerol partial esters disclosed in the prior art is that they are liquid at room temperature, albeit highly viscous, and are thus unsuitable as film formers at body temperature.

[0008] EP1500427 describes polyglycerol partial esters of polyhydroxystearic acid and polyfunctional carboxylic acids, obtainable by esterification of a polyglycerol mixture with polyhydroxystearic acid and dimer fatty acid and / or di- and / or tricarboxylic acids and fatty acids having 6 to 22 carbon atoms. The polyglycerol partial esters are used for low-viscosity W / O emulsions and as dispersion aids.

[0009] A disadvantage of the method described in the prior art is that the products obtained are always highly viscous, i.e. but liquid at room temperature, even the product obtained at the end of the first step when the polyhydroxystearic acid is not added until the second step. Such products are unsuitable as film formers at body temperature.

[0010] EP1683781 describes polyglycerol partial esters of polyricinoleic acid and polyfunctional carboxylic acids, obtainable by esterification a) of a polyglycerol mixture with b) at least one particular polyricinoleic acid and optionally b1) polyhydroxystearic acid and c) at least one di- and / or tricarboxylic acid and d) at least one fatty acid according to methods known per se. The polyglycerol preferably has an average degree of condensation n of 1 to 11, preferably 2 to 6.

[0011] A disadvantage of the method described in the prior art is that the products obtained are always highly viscous, i.e. but liquid at room temperature, even the product obtained at the end of the first step when the polyhydroxystearic acid is not added until the second step. Such products are unsuitable as film formers at body temperature.

[0012] EP3500550 describes polyglycerol partial esters obtainable by esterification of a polyglycerol with a carboxylic acid mixture comprising at least one polyhydroxycarboxylic acid of a hydroxycarboxylic acid having 8 to 32 carbon atoms, at least one short-chain dicarboxylic acid having 2 to 16 carbon atoms, at least one long-chain dicarboxylic acid having 24 to 44 carbon atoms and at least one linear or branched, saturated or unsaturated fatty acid having 14 to 24 carbon atoms. These are used as W / O emulsifiers.

[0013] Reactions of monocarboxylic acid (oleic acid or isostearic acid) with polyglycerol and sebacic acid or dimer acid (examples 6a, 12 and 13) with a degree of esterification of 38.7-48.3% are described here. The products are liquids that are highly viscous at room temperature. Reactions of monocarboxylic acids (oleic acid, isostearic acid or palmitic / stearic acid) with polyglycerol and a combination of sebacic acid and dimer acid (examples 4, 6b and 14) with a degree of esterification of 48.7-61.6% are additionally described. With the exception of example 14, the products are highly viscous liquids at room temperature.

[0014] EP2593076 describes polyglycerol oligoesters obtainable by reacting polyglycerol having 3 to 20 glycerol units with a dicarboxylic acid or a cyclic anhydride of such a dicarboxylic acid having 4 to 22 carbon atoms and a monocarboxylic acid having 4 to 24 carbon atoms in a molar ratio of from 1.5:1.0:0.1 to 3.0:1.0:3.0. The products can be used as emulsifiers, solubilizing agents and / or thickeners.

[0015] The described examples have a degree of esterification of only 12.5-25.1%; according to the claims a degree of esterification of 66.6% is possible if using polyglycerol-3 in the ratio 1.5:1.0:3.0. The described examples have max. 2 equiv. of monocarboxylic acid (ex. E10) and always 2 equiv. of polyol (to 1 equiv. of dicarboxylic acid).

[0016] EP2363387 describes (poly)glycerol partial esters containing an average (numerical average) of 0.75 to 2.25 acid residues of one or more carboxylic acids having 10 to 24 carbon atoms and containing an average (numerical average) of 0.005 to 0.5 residues of a polyfunctional carboxylic acid. The use as O / W emulsifiers is described.

[0017] The reaction of polyglycerols having a degree of polymerization of 2.8-5.3 with fatty acids (C16, C18 and C22) and citric acid is described in the examples. The esters obtained have a degree of esterification of 27-43% of the hydroxyl groups of the polyglycerol used; no melting point data are given. The molar ratio of monocarboxylic acid to citric acid is 3.5-21.5.

[0018] EP1417955 describes a "humectant" consisting of (A) a glycerol / glycerol condensate ester with saturated linear fatty acids having 16-28 carbon atoms and a saturated aliphatic dicarboxylic acid having 16-28 carbon atoms, wherein at least half of the available hydroxyl groups of the glycerol / glycerol condensate remain free (unesterified), (B) a water-soluble diol and (C) a water-soluble tri- or polyol.

[0019] WO2015013951 describes a water-free cosmetic composition comprising (a) an ester of polyglycerol having an average degree of polymerization of 2-12, a linear saturated C16-28 fatty acid and an aliphatic saturated C16-28 dicarboxylic acid, (b) a polyol having at least 3 hydroxy groups and (c) a glyceryl ester surfactant.

[0020] All known products of the prior art exhibit only very minimal film-forming properties or none at all. They likewise exhibit little or no SPF-boosting properties. The water resistance, especially in sun protection formulations, is also inadequate.

[0021] Although synthetic polymers such as polyacrylates deliver significant effects, they are not based on natural raw materials and are also not biodegradable.

[0022] The skin feel of the known products of the prior art is unappealing, since corresponding cosmetic formulations that contain them are very tacky and / or are absorbed only slowly into the skin.

[0023] It was an object of the invention to provide a composition that is able to overcome at least one disadvantage of the products of the prior art.Description of the invention

[0024] It has surprisingly been found that the polyglycerol partial esters described hereinbelow achieve the object of the invention.

[0025] The present invention accordingly provides polyglycerol partial esters that are characterized by a particular choice of polyglycerol and by specific ratios of the different carboxylic acids that have undergone esterification.

[0026] The invention further provides a method for preparing the polyglycerol partial esters of the invention and for the use of the polyglycerol partial esters in cosmetic applications.

[0027] An advantage of the present invention is that the polyglycerol partial esters described herein may be prepared from exclusively renewable raw materials, unlike the polyacrylates described above. A further advantage is that the polyglycerol partial esters described herein can be prepared on the basis of principles of green chemistry.

[0028] Another advantage of the present invention is that formulations can be provided that are polyglycol ether-free.

[0029] A further advantage is that the polyglycerol partial esters described herein are biodegradable, unlike the polyacrylates described above.

[0030] A further advantage is that the polyglycerol partial esters described herein have a good ecotoxicological profile.

[0031] A further advantage of the polyglycerol partial esters described herein is that they are very mild on the skin, not irritating and non-toxic.

[0032] Another advantage of the polyglycerol partial esters described herein is that they have improved sensory properties in formulations. The tackiness of sun protection formulations is reduced after application. The formulations undergo rapid absorption into the skin, since absorption is increased during application and for 5 min thereafter on the skin.

[0033] Another advantage of the polyglycerol partial esters described herein is that they give rise to enhancement of "velvety-silkiness" in formulations.

[0034] A further advantage is that the polyglycerol partial esters described herein have a good skin-moisturizing effect.

[0035] Another advantage is that the polyglycerol partial esters described herein impart an increased sun protection factor to the sun protection formulations.

[0036] Another advantage is that the polyglycerol partial esters described herein are very well suited to be used in sun protection formulations having very high concentrations of UV light protection filters.

[0037] A further advantage of the polyglycerol partial esters described herein is that they impart very high water resistance to the formulations. In sun protection formulations this results in the formulations ensuring prolonged UV protection in the water or after bathing.

[0038] Another advantage of the polyglycerol partial esters according to the invention is that they impart increased wear resistance to the colour pigments when used in make-up applications.

[0039] In the context of pigment-containing formulations, a further advantage of the polyglycerol partial esters according to the invention is that they permit good dispersion of pigments in the formulations.

[0040] A further advantage of the polyglycerol partial esters described herein is that they have good compatibility with formulations containing UV protection filters or pigments.

[0041] In general, the polyglycerol partial esters described herein impart good stability to the formulations. Another advantage of the polyglycerol partial esters according to the invention is that they are easily processable, since they mix readily with typical cosmetic oils and can be rapidly incorporated into corresponding emulsions.

[0042] A further advantage of the polyglycerol partial esters described herein is that they impart high gloss to solid or waxy formulations such as lipsticks.

[0043] Yet another advantage of the polyglycerol partial esters according to the invention is that they are particularly tolerant to electrolytes, which means that, for example, formulations containing large amounts of salt remain stable.

[0044] A further advantage of the polyglycerol partial esters according to the invention is that they have a structuring and viscosity-increasing effect in formulations having high oil contents or even pure oils.

[0045] The present invention thus provides a polyglycerol partial ester obtainable by esterification a) of a polyglycerol having an average degree of condensation N of 2.4 to 15.0, preferably 2.6 to 10.0, especially 2.8 to 6.0, with a carboxylic acid mixture comprising: b1) at least one short-chain dicarboxylic acid having 4 to 18, preferably 4 to 14, more preferably 6 to 10, carbon atoms, b2) at least one long-chain dicarboxylic acid having 24 to 44, preferably 30 to 40, more preferably 34 to 38, carbon atoms and c) at least one long-chain, saturated and linear monocarboxylic acid having 18 to 32, preferably 18 to 26, more preferably 20 to 22, carbon atoms, wherein the sum total of all short-chain and long-chain dicarboxylic acids present in the carboxylic acid mixture comes to at least 75% by weight, preferably at least 85% by weight, more preferably at least 95% by weight, based on all the dicarboxylic acids present in the carboxylic acid mixture, wherein the sum total of all long-chain, saturated and linear monocarboxylic acids present in the carboxylic acid mixture comes to at least 86% by weight, preferably at least 90% by weight, more preferably at least 95% by weight, based on all the monocarboxylic acids present in the carboxylic acid mixture, wherein the molar ratio of all carboxyl groups present in the carboxylic acid mixture to all hydroxyl groups present in the polyglycerol used is at least 35 to 100, preferably at least 50 to 98, more preferably at least 68 to 95, characterized in that the molar ratio of polyglycerol a) to the sum total of the dicarboxylic acid components b1) and b2) to monocarboxylic acid component c) is from 1.0:1.0:1.0 to 4.0:1.0:10.0, preferably from 1.0:1.0:1.5 to 3.0:1.0:8.0.

[0046] The polyglycerol partial esters according to the invention are mixtures of different substances; it is therefore clear to those skilled in the art that the numerical values specified are average values across the mixture.

[0047] The term "polyglycerol" is for the purpose of the present invention to be understood as meaning a polyglycerol that may also contain glycerol. Consequently, for the purposes of calculating amounts, masses and the like, any glycerol fraction should also be taken into consideration.

[0048] Because of its polymeric character, the polyglycerol is a statistical mixture of various compounds. Polyglycerol may have ether bonds formed between two primary, one primary and one secondary, and two secondary positions of the glycerol monomers. For this reason, the polyglycerol base framework does not usually consist exclusively of linearly linked glycerol units, but may also comprise branchings and rings. For details see for example "Original synthesis of linear, branched and cyclic oligoglycerol standards", Cassel et al., J. Org. Chem. 2001, 875-896.

[0049] The same applies to the term "polyglycerol partial ester" in the context of the present invention.

[0050] The term "short-chain dicarboxylic acid" is in the context of the present invention to be understood as meaning dicarboxylic acids having 4 to 18, preferably 4 to 14, more preferably 6 to 10, carbon atoms.

[0051] The term "long-chain dicarboxylic acid" is in the context of the present invention to be understood as meaning dicarboxylic acids having 24 to 44, preferably 30 to 40, more preferably 34 to 38, carbon atoms.

[0052] The term "long-chain" monocarboxylic acid is in the context of the present invention to be understood as meaning monocarboxylic acids having 18 to 32, preferably 18 to 26, more preferably 20 to 22, carbon atoms.

[0053] The polyglycerol partial ester obtainable by esterification of carboxylic acids according to the invention can of course also be obtained by esterification of the corresponding carboxylic acid derivatives, for example the anhydrides or carboxylic esters thereof (such as methyl or ethyl esters). If the polyglycerol partial esters are obtained by (trans)esterification of a polyol ester of the di- and / or monocarboxylic acids, it will be apparent to those skilled in the art that the molar ratio of polyglycerol a) to the sum total of dicarboxylic acid components b1) and b2) to carboxylic acid component c) relates not to the number of molecules of the respective polyol ester, but to the number of acyl residues of the di- and / or monocarboxylic acid provided by the respective polyol ester.

[0054] For the present invention, it is important that the polyglycerol used has an average degree of condensation N of 2.4 to 15.0, preferably 2.6 to 10.0, especially 2.8 to 6.0.

[0055] The average degree of condensation of the polyglycerol N is calculated via its hydroxyl value (OHV, in mg KOH / g) according to the following formula: N = 112200 − 18 ⋅ OHV 74 ⋅ OHV − 56100

[0056] Suitable detection methods for determining the hydroxyl value are in particular those according to DGF C-V 17 a (53), Ph. Eur. 2.5.3 Method A and DIN 53240.

[0057] Unless otherwise stated, all stated percentages (%) are percentages by weight.

[0058] Polyglycerol partial esters preferred in accordance with the invention are characterized in that the polyglycerol used has a glycerol content of 0.05% by weight to 25.0% by weight, preferably of 0.1% by weight to 15.0% by weight, more preferably of 0.1% by weight to 10.0% by weight, where the percentages by weight are based on the total amount of polyglycerol used. The stated percentages by weight are determined here by the GC method described hereinbelow.

[0059] Polyglycerol partial esters preferred in accordance with the invention are characterized in that the polyglycerol used has a diglycerol content of 0.1% by weight to 45.0% by weight, preferably of 0.5% by weight to 35.0% by weight, more preferably of 3.0% by weight to 30.0% by weight, where the percentages by weight are based on the total amount of polyglycerol used.

[0060] The stated percentages by weight are determined here by the GC method described hereinbelow.

[0061] It is advantageous when the polyglycerol used has a polydispersity index of more than 0.6, preferably of more than 1.0, more preferably of more than 1.2.

[0062] For the purposes of the present invention, the polydispersity index is calculated as ∑ i n i − N ⋅ x i where n i is the degree of condensation of the individual oligomer i, N the average degree of condensation of the polyglycerol [already described above and how to determine] and x i the proportion of the oligomer i in the polyglycerol mixture, as determined in the GC method described hereinbelow.

[0063] A suitable method for determining the oligomer distribution of the polyglycerol in a given polyglycerol partial ester comprises the hydrolysis or alcoholysis of the partial ester, separation of the resulting polyglycerol from the carboxylic acid compounds formed and analysis by gas chromatography after derivatization.

[0064] For this purpose, 0.6 g of polyglycerol ester is boiled under reflux in 25 ml of 0.5 N ethanolic KOH for 30 minutes and adjusted to pH 2-3 with sulfuric acid. The carboxylic acids are separated by extracting with three portions of petroleum ether of equivalent volume. The combined extracts are evaporated to a volume of approx. 10 ml. A 0.5 ml aliquot is transferred to an autosampler vial and, after addition of 0.5 ml of MTBE and 1 ml of TMPAH solution (trimethylanilinium hydroxide in methanol) as derivatization agent, analysed by GC.

[0065] The fatty acid analysis by GC is carried out using a gas chromatograph equipped with a split / splitless injector, a capillary column and a flame ionization detector. Conditions:Injector:290°C, split 30 mlInjected volume:1 µlColumn:30 m * 0.32 mm HP1 0.25 µmCarrier gas:Helium, inlet pressure 70 kPaTemp. program:80°C to 300°C at 8°C / min;Detector:FID at320°CHydrogen35 ml / minAir240 ml / minMake-up gas (purge gas)35 ml / min

[0066] When using these conditions, the methyl carboxylate esters are separated according to their chain length.

[0067] The relative content of the individual carboxylic acids (chain-length distribution) is evaluated as a percentage of the peak area.

[0068] The residue after extraction with petroleum ether is adjusted to pH 7-8 by addition of barium hydroxide solution. The precipitated barium sulfate is removed by centrifugation. The supernatant is drawn off and the residue extracted with three 20 ml portions of ethanol. The combined supernatants are evaporated at 80°C / 50 mbar. The residue is dissolved in pyridine. 500 µl of the solution is transferred to an autosampler vial and 1 ml of MSTFA (N-methyl-N-trifluoroacetamide) added. The vial is closed and heated to 80°C for 30 minutes.

[0069] The GC analysis of the polyglycerol component (as the trimethylsilyl derivative) is carried out using a gas-liquid chromatograph equipped with an on-column injector and an FID detector. Conditions:Injector:On-column injection (direct injection onto column)Injected volume:0.1 µlCarrier gas:3 ml / min hydrogen (constant flow)Column:SimDist 12 m x 0.32 mm x 0.1 µm (Varian)Temperature program:65°C to 365°C, 10°C / minDetector (FID):375°C

[0070] Under these conditions, the polyglycerols are separated according to their degree of condensation. In addition, cyclic isomers are separated from linear isomers up to a degree of condensation of four.

[0071] The peak areas of the individual oligomers are separated by a perpendicular line applied at the lowest point of the trough between peaks.

[0072] Since the resolution of oligomers higher than hexaglycerol is poor, the peaks of heptaglycerol and higher oligomers are combined as "heptaglycerol and higher" and treated as heptaglycerol for the purposes of calculating the polydispersity index. Linear and cyclic isomers are likewise combined in the calculation of the polydispersity index.

[0073] The relative ratio of the individual polyglycerol oligomers and isomers is calculated from the GC peak area obtained as described above.

[0074] The described GC analyses of the carboxylic acid and polyglycerol components can of course also be performed on the raw materials used for the preparation of the polyglycerol partial esters of the invention.

[0075] Polyglycerol partial esters preferred in accordance with the invention are characterized in that the polyglycerol used has a content of cyclic isomers of 1% by weight to 50% by weight, preferably of 2% by weight to 40% by weight, more preferably of 3% by weight to 30% by weight.

[0076] The stated percentages by weight are determined by the GC method described above and are based on the amount of the overall polyglycerol used.

[0077] It is preferable in accordance with the invention when the employed short-chain dicarboxylic acid in the polyglycerol partial ester of the invention is selected from aliphatic, linear dicarboxylic acids, especially succinic acid, maleic acid, tartaric acid, malic acid, fumaric acid, sorbic acid, α-ketoglutaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid and brassylic acid, with particular preference given to adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.

[0078] It is preferable in accordance with the invention when the employed long-chain dicarboxylic acid in the polyglycerol partial ester of the invention is selected from the group comprising dimer fatty acids that are oligomeric forms of various unsaturated monomeric fatty acids. Dimer fatty acids are a mixture of acyclic and cyclic dicarboxylic acids obtained by catalytic dimerization of unsaturated fatty acids having 12 to 22 carbon atoms. For the preparation and use of dimer acids and the physical and chemical properties thereof, reference is made to the publication "The Dimer Acids: The chemical and physical properties, reactions and applications", ed. E.C. Leonard; Humko Sheffield Chemical, 1975, Memphis, Tenn..

[0079] The dicarboxylic acids may also contain tri- and polyfunctional carboxylic acids to a minor extent. The functionality of the mixture should not exceed, on molar average, a value of 2.4. Particularly suitable as the long-chain dicarboxylic acid for the end use in accordance with the invention is dimer acid or a mixture of dimer and trimer acid (for example Radiacid 0977 from Oleon) obtained from vegetable oils having a high content of unsaturated C18 fatty acids (oleic, linoleic, linolenic acid).

[0080] Polyglycerol partial esters preferred in accordance with the invention are characterized in that the long-chain, saturated and linear monocarboxylic acids used are selected from hydroxy-substituted and unsubstituted fatty acids.

[0081] When mixtures of hydroxy-substituted and unsubstituted fatty acids are in accordance with the invention used as long-chain, saturated and linear monocarboxylic acids, these fatty acid mixtures preferably have a content of hydroxy-substituted fatty acids within a range of from 0.1% by weight to 25% by weight, preferably from 1% by weight to 10% by weight, where the percentages by weight are based on all long-chain, saturated and linear monocarboxylic acids.

[0082] Polyglycerol partial esters particularly preferred in accordance with the invention are characterized in that the long-chain, saturated and linear monocarboxylic acids used are selected from unsubstituted fatty acids.

[0083] In this connection, the long-chain, saturated and linear monocarboxylic acids used are selected in particular from stearic acid, arachidic acid and behenic acid. Typical commercially available products are: technical-grade stearic acid containing at least 92% C18 (for example Mascid 1892 from Musim Mas, Palmac 90-18 from IOI, Radiacid 0152 from Oleon, Wilfarin SA-1892 from Wilmar), technical-grade stearic acid containing at least 98% C18 (for example Edenor C18-98 MY from Emery, Palmac 98-18 from IOI), technical-grade arachidic acid (for example Palmera A5020 from KLK, Nouracid RE07 from Oleon, Nouracid RD3030 from Oleon), technical-grade behenic acid containing at least 60% C22 (for example Palmera A6022 from KLK), technical-grade behenic acid containing at least 85% C22 (for example Palmera A8522 from KLK, Radiacid 0560 from Oleon) and technical-grade behenic acid containing at least 92% C22 (for example Palmera A9322 from KLK).

[0084] Polyglycerol partial esters preferred in accordance with the invention are characterized in that the total content of aromatic mono- and dicarboxylic acids based on all mono- and dicarboxylic acids used is from 0% by weight to 35% by weight, preferably from 0.1% by weight to 25% by weight. Polyglycerol partial esters particularly preferred in accordance with the invention are characterized in that the total content of aromatic mono- and dicarboxylic acids based on all mono- and dicarboxylic acids used is 0% by weight.

[0085] Polyglycerol partial esters alternatively particularly preferred are characterized in that the total content of aromatic mono- and dicarboxylic acids based on all mono- and dicarboxylic acids used is from 5% by weight to 35% by weight, preferably from 11% by weight to 25% by weight.

[0086] From the amounts of the various components used in the esterification, it is clearly evident that it is preferable in accordance with the invention when the polyglycerol partial ester of the invention has a degree of esterification of 35% to 100%, preferably of 50% to 98%, more preferably of 68% to 95%. The determination of the degree of esterification of the polyglycerol partial esters of the invention is described hereinbelow in the examples.

[0087] In this connection, it is particularly preferable that the polyglycerol partial ester of the invention has an acid value of less than 25, preferably less than 15, especially within a range from 0.1 to 10, more preferably within a range from 0.5 to 10.

[0088] For the present invention it is advantageous and thus preferable that the value for the hydrophilic-lipophilic balance (HLB value) of the polyglycerol partial ester is from 2.0 to 8.0, preferably from 2.5 to 7.5 and more preferably from 3 to 5.2. The HLB value is a measure of the degree of hydrophilicity or lipophilicity of the molecule determined through the calculation of values for the different regions of the molecule. For the purposes of the present invention, the HLB value of the polyglycerol partial esters is calculated as follows: HLB = mp / ( mp + ma * 20 , where mp is the mass of the polyglycerol and ma the mass of the carboxylic acid mixture used in the synthesis of the polyglycerol ester (comprising mono- and dicarboxylic acids). For example, the esterification of 100 g of polyglycerol with 90 g of monocarboxylic acid and 10 g of dicarboxylic acid would result in an HLB value of (100 g / (90 g + 10 g + 100 g))*20 = 10, irrespective of the degree of polymerization of the polyglycerol and the nature of the carboxylic acids used.

[0089] Polyglycerol partial esters preferred in accordance with the invention are characterized in that they have an iodine value of less than 20, preferably less than 12, particularly preferably less than 5. A suitable method for determining the iodine value in the context of the present invention is EN 14111:2003.

[0090] It is preferable in accordance with the invention that the polyglycerol partial ester of the invention has a melting point of greater than 35°C, preferably greater than 40°C, in particular greater than 50°C, more preferably within a range from 51°C to 100°C.

[0091] The polyglycerol partial esters of the present invention can be prepared by classical esterification methods; in place of the carboxylic acids it is of course also possible to use the corresponding carboxylic acid derivatives, for example the anhydrides or carboxylic esters thereof (such as methyl or ethyl esters). It is also possible to use triglycerides, especially in the form of natural fats and oils, so long as they provide the carboxylic acids required according to the invention.

[0092] Polyglycerol partial esters according to the invention are preferably obtained by the method described hereinbelow; the present invention thus further provides a method for preparing a polyglycerol partial ester, said method comprising the method steps of A) providing a polyglycerol having an average degree of condensation N of 2.4 to 15.0, preferably 2.6 to 10.0, especially 2.8 to 6.0, B) providing a carboxylic acid mixture comprising: at least one short-chain dicarboxylic acid having 4 to 18, preferably 4 to 14, more preferably 6 to 10, carbon atoms, at least one long-chain dicarboxylic acid having 24 to 44, preferably 30 to 40, more preferably 34 to 38, carbon atoms, and at least one long-chain, saturated and linear monocarboxylic acid having 18 to 32, preferably 18 to 26, more preferably 20 to 22, carbon atoms, wherein the sum total of all short-chain and long-chain dicarboxylic acids present in the carboxylic acid mixture comes to at least 75% by weight, preferably at least 85% by weight, more preferably at least 95% by weight, based on all the dicarboxylic acids present in the carboxylic acid mixture, wherein the sum total of all long-chain, saturated and linear monocarboxylic acids present in the carboxylic acid mixture comes to at least 86% by weight, preferably at least 90% by weight, more preferably at least 95% by weight, based on all the monocarboxylic acids present in the carboxylic acid mixture, C) esterifying the polyglycerol with the carboxylic acid mixture, wherein the molar ratio of all carboxyl groups present in the carboxylic acid mixture to all hydroxyl groups present in the polyglycerol used is at least 35 to 100, preferably at least 50 to 98, more preferably at least 68 to 95, characterized in that the molar ratio of polyglycerol a) to the sum total of the dicarboxylic acid components b1) and b2) to carboxylic acid component c) is from 1.0:1.0:1.0 to 4.0:1.0:10.0, preferably from 1.0:1.0:1.5 to 3.0:1.0:8.0.

[0093] In the method according to the invention, preference is given to using those polyglycerols, monocarboxylic acids and dicarboxylic acids that are cited above as used with preference for the polyglycerol partial ester according to the invention. Correspondingly graduated preferences can be applied by analogy.

[0094] In the method according to the invention, method step C) can be carried out as a one-pot reaction or else as a stepwise process.

[0095] If method step C) is carried out as a one-pot reaction, the carboxylic acid mixture is esterified with the polyglycerol.

[0096] If method step C) is carried out as a stepwise process, the monocarboxylic acid and the dicarboxylic acids are added sequentially and esterified with the polyglycerol; strictly speaking, the monocarboxylic acid and the dicarboxylic acids are not provided as a carboxylic acid mixture, but this process is equivalent. In this connection it is possible for the polyglycerol to first undergo reaction with the monocarboxylic acid before then undergoing crosslinking with the dicarboxylic acids in a second step. However, the reverse stepwise synthetic sequence comprising an initial reaction of the polyglycerol with the dicarboxylic acids and then a subsequent reaction with the monocarboxylic acid is possible too. Splitting the individual reactants into several portions and multistage reactions is another possible application.

[0097] Since the polyglycerol partial esters according to the invention have an excellent use profile in cosmetic formulations, the present invention further provides a formulation, especially a cosmetic formulation, comprising 1) the polyglycerol partial ester according to the invention or a polyglycerol partial ester obtainable by the method according to the invention.

[0098] Preferably, the formulation according to the invention comprises a further component 2) at least one substance selected from the group comprising UV light protection filter substances and pigments, especially UV light protection filter substances, which are preferably organic.

[0099] The UV light protection filter substances present may for example be organic substances that are capable of absorbing ultraviolet rays and re-emitting the absorbed energy in the form of longer-wavelength radiation, for example heat.

[0100] UVB filters can be oil-soluble or water-soluble. Examples of oil-soluble UVB light protection filters include: 3-benzylidenecamphor derivatives, for example 3-(4-methylbenzylidene)camphor (INCI: 4-Methylbenzylidene Camphor), 4-aminobenzoic acid derivatives, for example 2-ethylhexyl 4-(dimethylamino)benzoate (INCI: Ethylhexyl Dimethyl PABA), 2-hydroxyethyl 4-{bis[2-(2-hydroxyethoxy)ethyl]amino}benzoate (INCI: PEG-25 PABA), cinnamic esters, for example 2-ethylhexyl 4-methoxycinnamate (INCI: Ethylhexyl Methoxycinnamate), isopentyl 4-methoxycinnamate (INCI: Isoamyl p-Methoxycinnamate), 2-ethylhexyl 2-cyano-3,3-diphenylacrylate (INCI: Octocrylene), salicylic esters, for example 2-ethylhexyl salicylate (INCI: Ethylhexyl Salicylate), homomenthyl salicylate (INCI: Menthyl Salicylate), 3,3,5-trimethylcyclohexyl salicylate (INCI: Homosalate), 2-hydroxybenzoic acid - 2,2',2"-nitrilotriethanol (1:1) (INCI: TEA-Salicylate), benzophenone derivatives, for example 2-hydroxy-4-methoxybenzophenone (INCI: Benzophenone-3), 2,2'-dihydroxy-4-methoxybenzophenone (INCI: Benzophenone-8), 2-hydroxy-4-methoxy-4'-methylbenzophenone (INCI: Benzophenone-10), triazine derivatives, for example tris(2-ethylhexyl) 4,4',4"-(1,3,5-triazine-2,4,6-triyltriimino)tribenzoate (INCI: Ethylhexyl Triazone, obtainable for example under the trade name Uvinul T 150 from BASF), iscotrizinol (INCI: Diethylhexyl Butamido Triazone) and 2,4,6-tri(4-biphenylyl)-1,3,5-triazine (INCI: Tris-Biphenyl Triazine).

[0101] An additional UVB filter is the (3-(4-(2,2-bis(ethoxycarbonyl)vinyl)phenoxy)propenyl)methoxysiloxane / dimethylsiloxane copolymer (INCI: Polysilicone-15) obtainable for example under the trade name Parsol SLX.

[0102] Useful water-soluble UVB sun protection filters include for example: salts of 2-phenylbenzimidazole-5-sulfonic acid, such as its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts, and also the sulfonic acid itself having the INCI name Phenylbenzimidazole Sulfonic Acid, sulfonic acid derivatives of benzophenone, for example 5-benzoyl-4-hydroxy-2-methoxybenzenesulfonic acid (INCI: Benzophenone-4) and salts thereof, benzenesulfonic acid derivatives of 3-benzylidenecamphor, for example 4-[(E)-(4,7,7-trimethyl-3-oxobicyclo[2.2.1]hept-2-ylidene)methyl]benzenesulfonic acid (INCI: Benzylidene Camphor Sulfonic Acid) and salts thereof.

[0103] Examples of typical oil-soluble UVA / broadband light protection filters that may be used include derivatives of benzoylmethane, for example 1-(4-methoxyphenyl)-3-[4-(2-methyl-2-propanyl)phenyl]-1,3-propanedione (INCI: Butyl Methoxydibenzoylmethane) or 1-(4-isopropylphenyl)-3-phenyl-1,3-propanedione (INCI: Isopropyl Dibenzoylmethane), triazine derivatives, for example 2,2'-[6-(4-methoxyphenyl)-1,3,5-triazine-2,4-diyl]bis{5-[(2-ethylhexyl)oxy]phenol} (INCI: Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine, obtainable for example under the trade name Tinosorb S from BASF), N,N'-bis[4-[5-(1, 1-dimethylpropyl)-2-benzoxazolyl]phenyl]-N"-(2-ethylhexyl)-1,3,5-triazine-2,4,6-triamine (INCI: Ethylhexyl Bis-Isopentylbenzoxazolylphenyl Melamine, obtainable under the trade name Uvasorb K2A from 3V Sigma), and derivatives of benzophenone, for example hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate (INCI: Diethylamino Hydroxybenzoyl Hexyl Benzoate).

[0104] Useful water-soluble UVA / broadband light protection filters include, for example: 3,3'-(1,4-phenylenedimethylene)-bis(7,7-dimethyl-2-oxobicyclo[2.2.1]hept-1-ylmethanesulfonic acid) and salts thereof, especially the corresponding sodium, potassium or triethanolammonium salt, which is also described as benzene-1,4-di(2-oxo-3-bornylidenemethyl-10-sulfonic acid) and has the INCI name Terephthalylidene Dicamphor Sulfonic Acid (obtainable under the trade name Mexoryl SX), 2,2'-(1,4-phenylene)-bis(6-sulfo-1H-benzimidazole-4-sulfonic acid) and salts thereof, the corresponding sodium, potassium or triethanolammonium salts, for example disodium 2,2'-(1,4-phenylene)-bis(6-sulfo-1H-benzimidazole-4-sulfonate) having the INCI name Disodium Phenyl Dibenzimidazole Tetrasulfonate, trade name for example Neo Heliopan AP.

[0105] Examples of other UVA / broadband filters are 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(2,4,4-trimethyl-2-pentanyl)phenol] (INCI: Methylene Bis-Benzotriazolyl Tetramethylbutylphenol, obtainable for example under the trade name Tinosorb M from BASF), 2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]phenol (INCI: Drometrizole Trisiloxane, trade name: Mexoryl XL), (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl 2-aminobenzoate (INCI: Menthyl Anthranilate) and 2-ethoxyethyl (2E)-3-(4-methoxyphenyl)acrylate (INCI: Cinoxate).

[0106] The UV filters may of course also be present in mixtures in the compositions according to the invention.

[0107] In addition to the soluble UV light protection filter substances mentioned, insoluble pigments may also be used for this purpose, namely finely dispersed metal oxides or salts, for example titanium dioxide, zinc oxide, iron oxide, aluminium oxide, cerium oxide, zirconium oxide, silicates (talc), barium sulfate and zinc stearate. The particles should here have an average diameter of less than 100 nm, for example of between 5 and 50 nm and especially between 15 and 30 nm. They may be spherical in shape, but it is also possible to use particles that are ellipsoidal in shape or have a shape that deviates in another way from spherical. Also possible however are micronized organic pigments, for example 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(2,4,4-trimethyl-2-pentanyl)phenol] (INCI: Methylene Bis-Benzotriazolyl Tetramethylbutylphenol, obtainable for example under the trade name Tinosorb M from BASF), having a particle size of < 200 nm, which is obtainable for example as a 50% aqueous dispersion.

[0108] In addition, further suitable UV light protection filters are given in the review by P. Finkel in SOFW Journal, 122, 543 (1996) or in the chapter "The Chemistry of Ultraviolet Filters" by N.A. Shaath in "Principles and Practice of Photoprotection", S.Q. Wang, H.W. Lim (eds.), Springer International Publishing, Switzerland, 2016.

[0109] It is preferable in accordance with the invention that component 2) of the formulation according to the invention is selected from at least two, preferably at least three, more preferably at least four, substances selected from the group of UV light protection filter substances.

[0110] It is preferable in accordance with the invention that component 2) of the formulation according to the invention is selected from the group comprising organic UV light protection filter substances, especially from the group of triazine derivatives.

[0111] It is in addition preferable in accordance with the invention that component 2) of the formulation according to the invention is selected from the group of UV light protection filter substances comprising, preferably consisting of, butyl methoxydibenzoylmethane, ethylhexyl triazone, bis-ethylhexyloxyphenol methoxyphenyl triazine, diethylhexyl butamido triazone, diethylamino hydroxybenzoyl hexyl benzoate, benzophenone-3, benzophenone-4, 4-methylbenzylidene camphor, octocrylene, ethylhexyl methoxycinnamate, ethylhexyl salicylate, homomenthyl salicylate, phenylbenzimidazole sulfonic acid, methylene bis-benzotriazolyl tetramethylbutylphenol, disodium phenyl dibenzimidazole tetrasulfonate, isoamyl p-methoxycinnamate, ethylhexyl dimethyl PABA.

[0112] It is in addition preferable in accordance with the invention that component 2) of the formulation according to the invention is selected from the group of pigments comprising unmodified or surface-modified, inorganic or organic pigments, preferably inorganic pigments such as activated carbon, talc, iron oxide pigments, titanium dioxide, zinc oxide, silica, cerium oxides, zirconium oxides, aluminium oxides, calcium carbonate, barium sulfate, chromium oxides, manganese oxides, bismuth oxychloride, ultramarine, calcium sulfate, alkali magnesium silicates or mixtures thereof.

[0113] Examples of organic pigments may be: carotenoids, chlorophylls, xanthophylls, caramel and the salts of the recited examples and also dyes obtained from fruits of plants or other plant parts, for example from orange, cacao, turmeric, shea, sandalwood, onion, carob tree fruit, paprika, maize, tomato, beetroot, peanut, grape, red cabbage, red rice, radish, elderberry, lingonberry, blueberry, raspberry, blackberry, boysenberry, gooseberry, cranberry, saffron, strawberry, cherry, tea, hibiscus, plum, blueberry or mulberry. Also employable as dye pigments are the substances approved and suitable for cosmetic purposes, as listed for example in the publication "Kosmetische Färbemittel" [Cosmetic colorants] of the Dyes Committee of the Deutsche Forschungsgemeinschaft [German Research Foundation], Verlag Chemie, Weinheim, 1984, pages 81 to 106.

[0114] It is in addition preferable in accordance with the invention that, when component 2) of the formulation according to the invention is selected from the group of UV light protection filter substances, pigments selected from titanium dioxide and zinc oxide are additionally present as component 2. In this connection too, the UV light protection filter substances that are preferably present correspond to the preferred UV light protection filter substances mentioned above.

[0115] A preferred formulation according to the invention is characterized in that component 1) is present in an amount of 0.1% by weight to 20% by weight, preferably of 0.25% by weight to 12% by weight, more preferably of 0.5% by weight to 6% by weight, and component 2) is present in an amount of 0.1% by weight to 60% by weight, preferably of 1% by weight to 50% by weight, more preferably of 3% by weight to 40% by weight.

[0116] The formulations according to the invention can comprise for example at least one further additional component selected from the group comprising emollients, emulsifiers, co-emulsifiers, thickeners / viscosity regulators / stabilizers, antioxidants, hydrotropes (or polyols), solids and fillers, pearlescent additives and opacifiers, insect repellents, self-tanning agents, preservatives, conditioning agents, perfumes, colorants, cosmetic active substances, care additives, refatting agents, solvents.

[0117] Substances that can be used as exemplary representatives of the individual groups are known to those skilled in the art and can for example be taken from German application DE102008001788.4.

[0118] As regards further optional components and also the amounts used of these components, reference is expressly made to the relevant handbooks known to those skilled in the art, for example K. Schrader, "Grundlagen und Rezepturen der Kosmetika" [Fundamentals and formulations of cosmetics], 2nd edition, pages 329 to 341, Hüthig Buch Verlag, Heidelberg.

[0119] The amounts of the respective additives depend on the intended use.

[0120] Typical starting formulations for the relevant applications are known prior art and are contained for example in the brochures of the manufacturers of the relevant base materials and active substances. These existing formulations can generally be adopted unchanged. However, any desired modifications necessary for adjustment and optimization can be made in a straightforward manner through simple tests.

[0121] Formulations according to the invention may for example be used in the form of an emulsion, a suspension, a solution, a cream, a salve, a paste, a gel, an oil, a powder, an aerosol, a stick, a spray, a cleansing product, a make-up product or a sun protection product.

[0122] The present invention further provides for the use of the polyglycerol partial esters of the invention, or of the polyglycerol partial esters obtainable by the method of the invention, as film formers.

[0123] The present invention further provides for the use of the polyglycerol partial esters of the invention, or of the polyglycerol partial esters obtainable by the method of the invention, to boost the sun protection factor of UV light protection filter substances.

[0124] The present invention further provides for the use of the polyglycerol partial esters of the invention, or of the polyglycerol partial esters obtainable by the method of the invention, to reduce the rinseability and / or the wear of a formulation from a surface.

[0125] In the use according to the invention, preference is given to using the components mentioned above as components that are preferably present in the context of the formulations according to the invention.

[0126] The examples that follow describe the present invention by way of example without any intention to limit the invention, the scope of application of which is apparent from the entirety of the description and the claims, to the embodiments specified in the examples.Examples:Melting point determination by the capillary method:

[0127] Melting points were determined using the capillary method based on DIN 53181, DIN EN ISO 3146, DGF C-IV 3a and Ph. Eur. 2.2.14.Degree of esterification:

[0128] The degree of esterification of all OH groups can be determined via the hydroxyl value, the acid value and the saponification value according to the following formula: Degree of esterification = 100 SV − AV / SV − AV + OHV where SV = saponification value, AV = acid value and OHV = hydroxyl value.

[0129] Suitable detection methods for determining the saponification value are in particular those according to DGF C-V 3, DIN EN ISO 3681 and Ph. Eur. 2.5.6.

[0130] Suitable methods for determining the acid value are in particular those according to DGF C-V 2, DIN EN ISO 2114, Ph. Eur. 2.5.1, ISO 3682 and ASTM D 974.

[0131] Suitable detection methods for determining the hydroxyl value are in particular those according to DGF C-V 17 a (53), Ph. Eur. 2.5.3 Method A and DIN 53240.Ratio of the raw materials:

[0132] The molar ratio of polyglycerol a) to the sum total of dicarboxylic acid components b1) and b2) to carboxylic acid component c) is abbreviated to PG:Di:Mono.Example 1, inventive: Polyglycerol partial ester (PGE), inventive

[0133] A mixture of polyglycerol (OHV = 1100 mg KOH / g, 42.24 g, 0.176 mol), behenic acid (92%, 340 g / mol, 86.16 g, 0.253 mol), sebacic acid (202 g / mol, 13.88 g, 0.068 mol) and dimer acid (Radiacid 0977 from Oleon having approx. 36 carbon atoms, functionality = 2.0, AV = 192 mg KOH / g, 560 g / mol, 37.31 g, 0.066 mol) was heated to 240°C with stirring and the water that formed was continuously distilled off until an acid value of < 5 mg KOH / g was attained. After cooling, a yellowish, brittle, solid product was obtained.

[0134] Acid value: 1.9 mg KOH / g; saponification value: 176 mg KOH / g; hydroxyl value: 110 mg KOH / g; degree of esterification: 61.3%; melting point: 62°C; HLB: 4.7. PG:Di:Mono = 1.3:1:1.9Example 2, inventive: PGE, inventive

[0135] A mixture of polyglycerol (OHV = 972 mg KOH / g, 80.86 g, 0.179 mol), behenic acid (92%, 340 g / mol, 86.16 g, 0.253 mol), sebacic acid (202 g / mol, 13.88 g, 0.068 mol) and dimer acid (Radiacid 0977 from Oleon having approx. 36 carbon atoms, functionality = 2.0, AV = 192 mg KOH / g, 560 g / mol, 37.31 g, 0.066 mol) was heated to 240°C with stirring and the water that formed was continuously distilled off until an acid value of < 5 mg KOH / g was attained. After cooling, a yellowish, brittle, solid product was obtained.

[0136] Acid value: 2.8 mg KOH / g; saponification value: 136 mg KOH / g; hydroxyl value: 246 mg KOH / g; degree of esterification: 35.1%; melting point: 66°C; HLB: 7.4.

[0137] PG:Di:Mono = 1.3:1:1.9.Example 3, inventive: PGE, inventive

[0138] A mixture of polyglycerol (OHV = 1100 mg KOH / g, 42.24 g, 0.176 mol), behenic acid (92%, 340 g / mol, 94.77 g, 0.279 mol), sebacic acid (202 g / mol, 13.88 g, 0.068 mol) and dimer acid (Radiacid 0977 from Oleon having approx. 36 carbon atoms, functionality = 2.0, AV = 192 mg KOH / g, 560 g / mol, 37.31 g, 0.066 mol) was heated to 240°C with stirring and the water that formed was continuously distilled off until an acid value of < 5 mg KOH / g was attained. After cooling, a yellowish, brittle, solid product was obtained.

[0139] Acid value: 2.1 mg KOH / g; saponification value: 188 mg KOH / g; hydroxyl value: 82 mg KOH / g; degree of esterification: 69.4%; melting point: 64°C; HLB: 4.5.

[0140] PG:Di:Mono = 1.3:1:2.1.Example 4, inventive: PGE, inventive

[0141] A mixture of polyglycerol (OHV = 1100 mg KOH / g, 42.24 g, 0.176 mol), behenic acid (92%, 340 g / mol, 77.54 g, 0.228 mol), sebacic acid (202 g / mol, 13.88 g, 0.068 mol) and dimer acid (Radiacid 0977 from Oleon having approx. 36 carbon atoms, functionality = 2.0, AV = 192 mg KOH / g, 560 g / mol, 37.31 g, 0.066 mol) was heated to 240°C with stirring and the water that formed was continuously distilled off until an acid value of < 5 mg KOH / g was attained. After cooling, a yellowish, brittle, solid product was obtained.

[0142] Acid value: 3.3 mg KOH / g; saponification value: 168 mg KOH / g; hydroxyl value: 80 mg KOH / g; degree of esterification: 67.3%; melting point: 63°C; HLB: 4.9.

[0143] PG:Di:Mono = 1.3:1:1.7.Example 5, inventive: PGE, inventive

[0144] A mixture of polyglycerol (OHV = 1100 mg KOH / g, 42.24 g, 0.176 mol), behenic acid (92%, 340 g / mol, 86.16 g, 0.253 mol), adipic acid (146 g / mol, 10.02 g, 0.068 mol) and dimer acid (Radiacid 0977 from Oleon having approx. 36 carbon atoms, functionality = 2.0, AV = 192 mg KOH / g, 560 g / mol, 37.31 g, 0.066 mol) was heated to 240°C with stirring and the water that formed was continuously distilled off until an acid value of < 5 mg KOH / g was attained. After cooling, a yellowish, brittle, solid product was obtained.

[0145] Acid value: 4 mg KOH / g; saponification value: 172 mg KOH / g; hydroxyl value: 96 mg KOH / g; degree of esterification: 63.6%; melting point: 64°C; HLB: 4.8.

[0146] PG:Di:Mono = 1.3:1:1.9.Example 6, inventive: PGE, inventive

[0147] A mixture of polyglycerol (OHV = 1100 mg KOH / g, 42.24 g, 0.176 mol), behenic acid (92%, 340 g / mol, 130.0 g, 0.382 mol), sebacic acid (202 g / mol, 13.88 g, 0.068 mol) and dimer acid (Radiacid 0977 from Oleon having approx. 36 carbon atoms, functionality = 2.0, AV = 192 mg KOH / g, 560 g / mol, 37.31 g, 0.066 mol) was heated to 240°C with stirring and the water that formed was continuously distilled off until an acid value of approx. 5 mg KOH / g was attained. After cooling, a yellowish, brittle, solid product was obtained.

[0148] Acid value: 6.2 mg KOH / g; saponification value: 171 mg KOH / g; hydroxyl value: 85 mg KOH / g; degree of esterification: 66.0%; melting point: 65°C; HLB: 3.8.

[0149] PG:Di:Mono = 1.3:1:2.9.Example 7, inventive: PGE, inventive

[0150] A mixture of polyglycerol (OHV = 1100 mg KOH / g, 42.24 g, 0.176 mol), behenic acid (92%, 340 g / mol, 131.3 g, 0.386 mol), sebacic acid (202 g / mol, 6.94 g, 0.034 mol) and dimer acid (Radiacid 0977 from Oleon having approx. 36 carbon atoms, functionality = 2.0, AV = 192 mg KOH / g, 560 g / mol, 18.65 g, 0.033 mol) was heated to 240°C with stirring and the water that formed was continuously distilled off until an acid value of < 5 mg KOH / g was attained. After cooling, a yellowish, brittle, solid product was obtained.

[0151] Acid value: 1.4 mg KOH / g; saponification value: 161 mg KOH / g; hydroxyl value: 117 mg KOH / g; degree of esterification: 57.7%; melting point: 68°C; HLB: 4.2.

[0152] PG:Di:Mono = 2.6:1:5.8.Example 8, inventive: PGE, inventive

[0153] A mixture of polyglycerol (OHV = 1100 mg KOH / g, 42.24 g, 0.176 mol) and stearic acid (92%, 284 g / mol, 136.7 g, 0.481 mol) was heated to 240°C with stirring and the water that formed was continuously distilled off until an acid value of < 15 mg KOH / g was attained. After addition of sebacic acid (202 g / mol, 13.88 g, 0,068 mol) and dimer acid (Radiacid 0977 from Oleon having about 36 carbon atoms, functionality = 2.0, AV = 192 mg KOH / g, 560 g / mol, 37.31 g, 0.066 mol), the mixture was further heated to 240°C with stirring and the water that formed was continuously distilled off until an acid value of < 5 mg KOH / g was attained. After cooling, a yellowish, brittle, solid product was obtained.

[0154] Acid value: 3.1 mg KOH / g; saponification value: 198 mg KOH / g; hydroxyl value: 36 mg KOH / g; degree of esterification: 84.4%; melting point: 51°C; HLB: 3.7.

[0155] PG:Di:Mono = 1.3:1:3.6.Example 9, inventive: PGE, inventive

[0156] A mixture of polyglycerol (OHV = 1100 mg KOH / g, 42.24 g, 0.176 mol), behenic acid (92%, 340 g / mol, 77.52 g, 0.227 mol), oleic acid (> 72%, iodine value: 94 mg l 2 / g, 281 g / mol, 7.1 g, 0.025 mol), sebacic acid (202 g / mol, 13.88 g, 0.068 mol) and dimer acid (Radiacid 0977 from Oleon having approx. 36 carbon atoms, functionality = 2.0, AV = 192 mg KOH / g, 560 g / mol, 37.31 g, 0.066 mol) was heated to 240°C with stirring and the water that formed was continuously distilled off until an acid value of < 5 mg KOH / g was attained. After cooling, a yellowish, brittle, solid product was obtained.

[0157] Acid value: 2 mg KOH / g; saponification value: 179 mg KOH / g; hydroxyl value: 115 mg KOH / g; degree of esterification: 60.6%; melting point: 61°C; HLB: 4.7.

[0158] PG:Di:Mono = 1.3:1:1.9.Example 10, noninventive: PGE without dicarboxylic acid

[0159] A mixture of polyglycerol (OHV = 1100 mg KOH / g, 50.0 g, 0.208 mol) and stearic acid (92%, 284 g / mol, AV = 199 mg KOH / g, 254.3 g, 0.895 mol) was heated to 240°C with stirring and the water that formed was continuously distilled off until an acid value of < 5 mg KOH / g was attained. After cooling, a yellowish, brittle, solid product was obtained.

[0160] Acid value: 3.8 mg KOH / g; saponification value: 176 mg KOH / g; hydroxyl value: 24 mg KOH / g; degree of esterification: 87.8%; melting point: 58°C; HLB: 3.3.Example 11, noninventive: PGE palmitate

[0161] A mixture of polyglycerol (OHV = 1100 mg KOH / g, 42.2 g, 0.176 mol), palmitic acid (256 g / mol, 64.8 g, 0.253 mol), sebacic acid (202 g / mol, 13.9 g, 0.068 mol) and dimer acid (Radiacid 0977 from Oleon having approx. 36 carbon atoms, functionality = 2.0, AV = 192 mg KOH / g, 560 g / mol, 37.3 g, 0.066 mol) was heated to 240°C with stirring and the water that formed was continuously distilled off until an acid value of < 5 mg KOH / g was attained.

[0162] Acid value: 1.9 mg KOH / g; saponification value: 197 mg KOH / g; hydroxyl value: 121 mg KOH / g; degree of esterification: 61.7%; melting point: 34°C; HLB: 5.3.

[0163] PG:Di:Mono = 1.3:1:1.9.Example 12, noninventive: Reworking of example E10 from EP2593076, low degree of esterification

[0164] A mixture of polyglycerol (462 g / mol, 160.0 g, 0.346 mol) and succinic acid (118 g / mol, 20.4 g, 0.173 mol) with addition of catalyst KOH (0.67 g) was heated to 240°C with stirring and the water that formed was continuously distilled off until an acid value of < 5 mg KOH / g was attained. After addition of palmitic acid (256 g / mol, 88.7 g, 0.346 mol), the mixture was further heated to 240°C with stirring and the water that formed was continuously distilled off until an acid value of less than 5 mg KOH / g was attained. After cooling, a yellowish, soft / waxy, solid product was obtained.

[0165] Acid value: 3.1 mg KOH / g; saponification value: 149 mg KOH / g; hydroxyl value: 658 mg KOH / g; degree of esterification: 18.2%; HLB: 11.9.

[0166] PG:Di:Mono = 2.0:1:2.0.Example 13, noninventive: Reworking of example 6B from EP3500550, isostearic acid

[0167] A mixture of polyglycerol (315 g / mol, 99.0 g, 0.314 mol), sebacic acid (202 g / mol, 26.0 g, 0.129 mol) and isostearic acid (285 g / mol, 135.5 g, 0.475 mol) was heated to 240°C with stirring and the water that formed was continuously distilled off until an acid value of < 1 mg KOH / g was attained. After addition of dimer acid (575 g / mol, 54.5 g, 0.095 mol), the mixture was further heated to 240°C with stirring and the water that formed was continuously distilled off until an acid value of less than 2 mg KOH / g was attained. After cooling, a clear, yellow, liquid product was obtained. Acid value: 0.3 mg KOH / g; saponification value: 174 mg KOH / g; hydroxyl value: 177 mg KOH / g; degree of esterification: 49.5%; HLB: 6.3.

[0168] PG:Di:Mono = 1.4:1:2.1.Example 14, noninventive: Reworking of example 14 from EP3500550, C16 / 18 fatty acid

[0169] A mixture of polyglycerol (240 g / mol, 74.8 g, 0.312 mol), sebacic acid (202 g / mol, 21.9 g, 0.108 mol), dimer acid (575 g / mol, 84.1 g, 0.146 mol) and C16 / 18 fatty acid (C16 / C18 = approx. 50:50, 270 g / mol, 134.8 g, 0.499 mol) was heated to 240°C with stirring and the water that formed was continuously distilled off until an acid value of < 5 mg KOH / g was attained. After cooling, a light yellow, solid product was obtained.

[0170] Acid value: 2.9 mg KOH / g; saponification value: 191 mg KOH / g; hydroxyl value: 111 mg KOH / g; degree of esterification: 62.9%; melting point: 86°C; HLB: 4.7.

[0171] PG:Di:Mono = 1.2:1:2.0.

[0172] Example 15 a-g, further noninventive commercial products a. Tego SP 13 Sun Up MB (Evonik, INCI: Poly C10-30 Alkyl Acrylate) b. Antaron V-220 (Ashland, INCI: VP / Eicosene Copolymer) c. Isolan PDI (Evonik, INCI: Diisostearoyl Polyglyceryl-3 Dimer Dilinoleate) d. Isolan GPS (Evonik, INCI: Polyglyceryl-4 Diisostearate / Polyhydroxystearate / Sebacate) e. Cera Bellina #106 (Koster Keunen; INCI: Polyglyceryl-3 Beeswax) f. CosmoSurf PG1-IS (Surfatech Corp.; INCI: Polyglyceryl-3 Stearate / Isostearate Dimer Dilinoleate Copolymer) g. LexFilm ™< Sun Natural MB (Inolex, INCI: Capryloyl Glycerin / Sebacic Acid Copolymer) Application example 1: In-vitro SPF-boosting test of cosmetic formulations

[0173] Polyglycerol partial esters (PGEs) according to the invention have the characteristic feature of a strong tendency to film formation compared to noninventive polyglycerol partial esters or noninventive commercial products. The film-forming properties in sun protection formulations can be quantitatively demonstrated by means of in-vitro SPF tests.

[0174] This was done by preparing O / W sun protection emulsions on a 200 g laboratory scale into which were incorporated the various film formers in an each time identical manner according to the recipes hereinbelow (Table 1). The emulsions were prepared according to the method known to those skilled in the art commonly used in the production of lotions. Table 1: Composition of the O / W sun protection emulsions for in-vitro determination of the SPFPhase Ingredient Formulation A (reference) Formulation B ATego ®< Care PBS 6 MB (Polyglyceryl-6 Stearate, Polyglyceryl-6 Behenate)3.00%3.00%Tegin ®< M Pellets MB (Glyceryl Stearate)0.50%0.50%Tego ®< Alkanol 1618 (Cetearyl Alcohol)0.50%0.50%Tegosoft ®< XC MB (Phenoxyethyl Caprylate)5.00%3.50%Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine3.00%3.00%Butyl Methoxydibenzoylmethane2.00%2.00%Ethylhexyl Salicylate3.00%3.00%Octocrylene8.00%8.00%Homosalate3.00%3.00%Ethylhexyl Triazone1.50%1.50%dermofeel ®< Toco 70 non GMO (Tocopherol, Helianthus Annuus (Sunflower) Seed Oil)0.70%0.70%PGE inventive / noninventive / commercial product -1.50% BGlycerin3.00%3.00%Disodium EDTA0.05%0.05%Waterto 100%to 100%CXanthan Gum (Keltrol CG-SFT, CP Kelco)0.50%0.50%DVerstatil ®< PC (Phenoxyethanol, Caprylyl Glycol)1.20%1.20%

[0175] 24.5 mg of reference formulation A and of test formulations B were respectively evenly applied to and spread over polymethyl methacrylate plates (PMMA; 7.0 cm x 3.5 cm, 2 µm roughness, Schönberg GmbH & Co. KG) (1 mg / cm 2< ). For each measurement, six replicate determinations were carried out, i.e. each formulation was applied to 6 individual PMMA plates. These were left in a drying cabinet at 30°C for 30 min, after which the SPF of the plates was determined using a Labsphere UV2000S Ultraviolet Transmittance Analyzer in accordance with Colipa Guideline (2011) with in each case 4 measurement points per PMMA plate. The individual SPF values for each PMMA plate / formulation were noted and the mean value determined. The mean SPF values for each formulation with film former were divided by the mean SPF value of formulation A without film former. The results are listed below in Table 2. Table 2: Relative in-vitro SPF values of the example products in formulation BFormulation B Product examples present in formulation B SPF boost (relative to reference formulation A) B1Tego ®< SP 13 Sun Up (Poly C10-30 Alkyl Acrylate)1.94B2VP / Eicosene Copolymer Antaron V-220 (Antaron V-220, Ashland))1.55B3Isolan ®< PDI (Diisostearoyl Polyglyceryl-3 Dimer Dilinoleate)1.15B4Isolan ®< GPS (Polyglyceryl-4 Diisostearate / Polyhydroxystearate / Sebacate)1.16B5Polyglyceryl-3 Beeswax (Cera Bellina, Koster Keunen)1.39B6Polyglyceryl-3 Stearate / Isostearate / Dimer Dilinoleate Crosspolymer (CosmoSurf PG1-IS, SurfaTech Corp.)1.01B7Capryloyl Glycerin / Sebacic Acid Copolymer (LexFilm Sun Natural MB, Inolex Inc.)1.00B8Ex. 101.06B9Ex. 111.27B10Ex. 12 (= example E10 from EP2593076)1.02B11Ex. 13 (= example 6B from EP3500550)1.00B12Ex. 14 (= example 14 from EP3500550)1.02B13*Ex. 11.94B14*Ex. 21.47B15*Ex. 31.78B16*Ex. 41.65B17*Ex. 51.77B18*Ex. 61.56B19*Ex. 71.94B20*Ex. 81.62B21*Ex. 91.61* inventive examples

[0176] For the inventive examples, the results in Table 2 in all cases show SPF-boost values of over 1.4 (relative to reference formulation A without film former). Indeed, values comparable with the polyacrylate Tego ®< SP 13 Sun Up and better than with the synthetic VP / Eicosene Copolymer were achieved by the best polyglycerol partial esters according to the invention. Significantly better values compared to plant-based reference substance of the prior art were obtained.Application example 2: In-vivo SPF water resistance test of cosmetic formulations

[0177] To determine the water resistance of sun protection formulations and sun protection factors (SPF) thereof, screening studies in accordance with Colipa 2005 (Cosmetics Europe: Guidelines For Evaluating Sun Product Water Resistance, 2005) were carried out at an external, accredited test institute.

[0178] The sun protection factor of a test person (SPFi) before and after water-bath treatment is calculated as the ratio of the minimum erythema dose on protected skin (MEDp) and the minimum erythema dose on unprotected skin (MEDu) on the same test person: SPFi = MEDp / MEDu. The minimum erythema dose is defined here as the amount of energy necessary to produce the first clearly perceptible redness within a clearly defined area, the redness being assessed 16 h to 24 h after exposure to light using a sunlight simulator (6 increasing UV doses with 15% progression). The sun protection factor is determined after application of 2 ± 0.05 mg of the test formulation on 1 cm 2< of skin before and after two periods of immersion in a water bath at 30 ± 2°C for 20 min each time. The water resistance is then obtained as the ratio of the sun protection factor after and before the water bath: WR = SPF(after water bath) / SPF(before water bath). For further retails, reference is made to the method description of the Colipa (The European Cosmetic and Perfumery Association). Table 3: Composition of the O / W sun protection emulsions for in-vivo measurement of the SPF water resistancePhase Ingredient Formulation C (reference) % w / w Formulation D % w / w Formulation E % w / w Tego ®< Care PBS 6 MB (Polyglyceryl-6 Stearate, Polyglyceryl-6 Behenate)3.003.003.00Tegin ®< M Pellets MB (Glyceryl Stearate)0.500.500.50Tego ®< Alkanol 1618 (Cetearyl Alcohol)0.500.500.50Tegosoft ®< XC MB (Phenoxyethyl Caprylate)6.004.504.50AAntaron V-220 (Ashland, INCI: VP / Eicosene Copolymer)-1.50-Polyglycerol partial ester (PGE) Ex. 1 --1.50 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (Tinosorb S, BASF)3.003.003.00Butyl Methoxydibenzoylmethane2.002.002.00Ethylhexyl Salicylate3.003.003.00Octocrylene8.008.008.00Homosalate3.003.003.00Ethylhexyl Triazone1.501.501.50BWaterto 100to 100to 100Glycerin3.003.003.00CAcrylates / C10-30 Alkyl Acrylate Crosspolymer (Carbomer Copolymer C)0.200.200.20Tegosoft ®< XC MB (Phenoxyethyl Caprylate)0.800.800.80DSodium hydroxide (10% in water)0.600.600.60EVerstatil ®< PC (Phenoxyethanol, Caprylyl Glycol)1.001.001.00 Table 4: In-vivo SPF water resistance values for formulation C, D and E Formulation C D E Film-former product example in formulation - Antaron V-220 (Ashland, INCI: VP / Eicosene Copolymer)PGE Ex. 1In-vivo water resistance (WR, in %) 34.658.863.6

[0179] Table 4 details the results of the in-vivo water resistance measurements with formulations C, D and E from Table 3. The vehicle formulation C (without film former) showed a WR value of only 34.6% and cannot therefore be considered a water-resistant sun protection formulation in cosmetics. By contrast, formulation E with inventive example 1 provided good water resistance, with a WR value of 63.6%, and could be declared "water resistant" (i.e. WR of min. 50%). The addition of the inventive product example 1 thus brought about a significant and very good improvement in the water resistance of formulation C and is even better than the comparative formulation D with the synthetic comparative example VP / Eicosene Copolymer.Application example 3: Sensory properties test of cosmetic formulations

[0180] The test formulations V1, V2, V3, V4, V5, V6 and V7 were investigated by a group of volunteer subjects trained in the assessment of sensory properties (N = 13). The skin feel of the cosmetic formulations described in the examples in Tables 5a and 5b was determined by a so-called panel. In these tests, a defined amount of the test lotions was applied to a clearly defined area of the forearm. The volunteer subjects compared the sensory properties of the cosmetic formulations and of the respective comparative formulation without knowing the composition. Assessment was on a scale from 0 (little) to 10 (much).

[0181] Inventive examples are marked with an *. Table 5a: Composition of the sun protection formulations for the sensory properties testV1 V2* V3 Phase Raw material % w / w % w / w % w / w A Tegin ®< M Pellets MB (Glyceryl Stearate)0.50.50.5Tego ®< Alkanol 1618 (Cetearyl Alcohol)0.50.50.5Tegosoft ®< XC MB (Phenoxyethyl Caprylate)4.04.04.0Polyglycerol partial ester (PGE) Ex. 1 - 1.5 -LexFilm ™< Sun Natural MB (Inolex, INCI: Capryloyl Glycerin / Sebacic Acid Copolymer)--1.5Bis-ethylhexyloxyphenol Methoxyphenyl Triazine333Butyl Methoxy Dibenzoylmethane222Ethylhexyl Salicylate333Octrocrylene888Homosalate333Ethylhexyl Triazone1.51.51.5dermofeel ®< Toco 70 non-GMO (Tocopherol, Helianthus Annuus (Sunflower) Seed Oil)0.20.20.2B Potassium Cetyl Phosphate1.51.51.5Glycerin2.52.52.5Waterto 100to 100to 100Disodium EDTA0.050.050.05C Tegosoft ®< XC MB (Phenoxyethyl Caprylate)0.30.30.3Tego Carbomer 341 ER (Carbomer)0.30.30.3NaOH 10% soln. in water0.30.30.3D Verstatil ®< PC Phenoxyethanol, Caprylyl Glycol111 Table 5b: Composition of the sun protection formulations for the sensory properties test V4* V5 V6* V7 Phase Raw material % w / w % w / w % w / w % w / w A Tego ®< Care PBS 6 MB (Polyglyceryl-6 Stearate, Polyglyceryl-6 Behenate)3333Tegin ®< M Pellets MB0.50.50.50.5(Glyceryl Stearate)Tego ®< Alkanol 1618 (Cetearyl Alcohol)0.50.50.50.5dermofeel ®< sensolv MB (Isoamyl Laurate)4.34.34.34.3Polyglycerol partial ester (PGE) Ex. 1 1.5-1.5-Antaron ™< V-220 (VP / Eicosene Copolymer, Ashland)-1.5-1.5Bis-ethylhexyloxyphenol Methoxyphenyl Triazine3333Butyl Methoxy Dibenzoylmethane2222Ethylhexyl Salicylate3333Octrocrylene8888Homosalate3333Ethylhexyl Triazone1.51.51.51.5dermofeel ®< Toco 70 non-GMO (Tocopherol, Helianthus Annuus (Sunflower) Seed Oil)0.20.20.20.2B Glycerin2222Waterto 100to 100to 100to 100EDTA0.050.050.050.05C Xanthan Gum (Keltrol CG-SFT, CP Kelco)0.30.30.30.3dermofeel ®< sensolv MB (Isoamyl Laurate)0.30.3--Tego Carbomer 341 ER (Carbomer)0.30.3--NaOH 10% soln. in water0.30.3--D Verstatil ®< PC (Phenoxyethanol, Caprylyl Glycol)1111

[0182] With regard to the use properties of the polyglycerol partial esters (PGEs) of the present invention, there were differences in sensory properties compared to the blank formulation without film former and compared to a likewise natural film former of the prior art that result in an improved skin feel during and after application. The results are collated in Table 6. Compared to the blank formulation V1, in V2 the polyglycerol partial ester (PGE) of the present invention brought about a significant increase in "velvety-silkiness" skin feel during and 5 min after application. The "velvety-silkiness" during application and after 5 min is also highest compared to the natural film former counterpart in V3. The polyglycerol partial ester (PGE) of the present invention is likewise able to achieve higher spreadability and reduced tackiness after 5 min compared to the blank formulation and to the formulation comprising the natural film former counterpart. The reduced tackiness is of particular interest in sun protection formulations, because the UV filters are generally associated with high tackiness.

[0183] Both in a test formulation based on a carbomer thickener (V4) and with a natural thickener (V6), the polyglycerol partial ester (PGE) of the present invention exhibits increased "velvety-silkiness" during application and after 5 min compared to a synthetic, non-biodegradable film former (V5 and V7 respectively). Here too, reduced "tackiness" after 5 min was observed in both thickener systems. The absorption during application and after 5 min is higher with the polyglycerol partial ester (PGE) of the present invention in both thickener systems. Table 6: Results of the sensory properties testsSpreadabilityAbsorptionVelvety-silkyAbsorption after 5 minVelvety-silky after 5 minTackiness after 5 minV1661614V2*773842V3560615V4*762722V5540614V6*771821V7550704 Further formulation examples

[0184] The following formulation examples demonstrate the usability of the inventive polyglycerol partial esters in cosmetic emulsions by way of example and do not limit the subject matter of the invention.

[0185] All percent values are unless otherwise stated percentages by weight. Production and homogenization steps are carried out according to usual methods.

[0186] If necessary, the pH is adjusted with acids or bases, this being noted accordingly in the formulation. Since the amount of acid or base needed can depend on the batches of the other ingredients, it is in the examples here often entered as q.s. (= quantum satis). It is also necessary to adjust to different pH values depending on the preservative used. Customary pH values that were used and adjusted to here in the example formulations are in the range from pH 3.5 to 8.0.

[0187] The example recipes listed hereinbelow were respectively produced with each of the inventive PGEs from examples 1 to 9.Fun in the Sun SPF 30 Spray

[0188] Phase Raw material % w / w % w / w % w / w % w / w ATEGO ®< Care PBS 6 MB (Polyglyceryl-6 Stearate, Polyglyceryl-6 Behenate)3.003.003.003.00dermofeel ®< sensolv MB (Isoamyl Laurate)3.003.003.003.00Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (Tinosorb S, BASF)3.003.003.003.00Butyl Methoxydibenzoylmethane2.002.002.002.00Homosalate4.004.004.004.00Ethylhexyl Salicylate4.004.004.004.00Octocrylene4.004.004.004.00Polyglycerol partial ester (PGE) 0.50 1.50 0.75 0.75 VP / Eicosene Copolymer (Antaron V-220, Ashland)0.50--0.5TEGO ®< Filmstar One MB (INCI: Polyglyceryl-3 Stearate / Sebacate Crosspolymer)--0.750.5TEGO ®< Feel C 10 (Cellulose)1.001.001.001.00BWaterto 100to 100to 100to 100Gellan Gum (Kelcogel CG-HA, CP Kelco)0.030.030.030.03EDTA0.050.050.050.05Glycerin3.003.003.003.00Acrylates / C10-30 Alkyl Acrylate Crosspolymer0.200.200.200.20CPhenylbenzimidazole Sulfonic Acid2.002.002.002.00Tromethamine0.880.880.880.88Water7.127.127.127.12DTromethamine (Trisaminomethane, 30% in water)q.s.q.s.q.s.q.s.Edermofeel ®< OMP (Methylpropanediol, Caprylyl Glycol, Phenylpropanol)3.003.003.003.00 Oil Release Sun Care Lotion SPF 50

[0189] Phase Raw material % w / w % w / w ATego ®< Care PBS 6 MB (Polyglyceryl-6 Stearate, Polyglyceryl-6 Behenate)3.003.00Tegosoft ®< XC (Phenoxyethyl Caprylate)15.0015.00Tegosoft ®< DC MB (Decyl Cocoate)10.0010.00Tegosoft ®< CT (Caprylic / Capric Triglyceride)10.0010.00Polyglycerol partial ester (PGE) 1.50 2.50 Diethylamino Hydroxybenzoyl Hexyl Benzoate (Uvinul A plus, BASF)10.0010.00Ethylhexyl Methoxycinnamate10.0010.00Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (Tinosorb S, BASF)5.005.00Ethylhexyl Salicylate5.005.00Homosalate5.005.00Tego ®< Feel C 10 (Cellulose)1.00-Dimethicone Crosspolymer-0.50BWaterto 100to 100Glycerin3.003.00CVerstatil ®< TBO (Triethyl Citrate; Caprylyl Glycol; Benzoic Acid)1.201.20DCitric Acid (10% in water)q.s. to pH 5.2q.s. to pH 5.2 Alcoholic Sun Care Spray SPF 30

[0190] Phase Raw material % w / w % w / w % w / w ATEGOSOFT ®< CT (Caprylic / Capric Triglyceride)20.0020.0020.00TEGOSOFT ®< TN (C12-15 Alkyl Benzoate)8.008.008.00TEGOSOFT ®< APM (PPG-3 Myristyl Ether)8.008.008.00Polyglycerol partial ester (PGE) 3.00 1.80 2.00 VP / Hexadecene Copolymer (Antaron V-216, Ashland)-0.70-TEGO ®< Filmstar One MB (INCI: Polyglyceryl-3 Stearate / Sebacate Crosspolymer)--1.00TEGO ®< Xymenynic (Caprylic / Capric Triglyceride; Xymenynic Acid)2.002.002.00Octocrylene6.806.806.80Ethylhexyl Salicylate2.502.502.50Butyl Methoxydibenzoylmethane5.005.005.00Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (Tinosorb S, BASF SE)3.003.003.00Diethylhexyl Butamido Triazone1.201.201.20BAlcoholto 100to 100to 100 Alcoholic Sun Care Spray SPF 30

[0191] Phase Raw material % w / w % w / w % w / w ATEGOSOFT ®< CT (Caprylic / Capric Triglyceride)20.0020.0020.00dermofeel ®< sensolv MB (Isoamyl Laurate)8.008.008.00TEGOSOFT ®< APM (PPG-3 Myristyl Ether)8.008.008.00Polyglycerol partial ester (PGE) 3.00 1.80 3.00 VP / Hexadecene Copolymer (Antaron V-216, Ashland)-0.70-TEGO ®< Filmstar One MB (INCI: Polyglyceryl-3 Stearate / Sebacate Crosspolymer)--1.00TEGO ®< Xymenynic (Caprylic / Capric Triglyceride; Xymenynic Acid)2.002.002.00Octocrylene6.806.806.80Ethylhexyl Salicylate2.502.502.50Butyl Methoxydibenzoylmethane5.005.005.00Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (Tinosorb S, BASF SE)3.003.003.00Diethylhexyl Butamido Triazone1.201.201.20BAlcoholto 100to 100to 100 Transparent Sun Care Spray SPF 25

[0192] Phase Raw material % w / w ATegosoft ®< P (Isopropyl Palmitate)12.00Polyglycerol partial ester (PGE) 1.00 Tegosoft ®< APM (PPG-3 Myristyl Ether)3.00Tegosoft ®< GC (PEG-7 Glyceryl Cocoate)1.50Tego ®< Turmerone (Curcuma Longa (Turmeric) Root Extract)0.50Prunus Amygdalus Dulcis (Sweet Almond) Oil2.00Dimethicone5.00Homosalate10.00Octocrylene9.40Ethylhexyl Salicylate4.50Butyl Methoxydibenzoylmethane3.00Tocopheryl Acetate0.50BDenat. Alcoholto 100 Water Resistant Aerosol Spray SPF 30

[0193] Phase Raw material % w / w % w / w % w / w % w / w ADenat. Alcoholto 100to 100to 100to 100Polyester-10 (and) Propylene Glycol Dibenzoate1.501.501.501.50Polyglycerol partial ester (PGE) 0.75 3.00 1.00 1.50 TEGO ®< SP 13 Sun Up MB (Poly C10-30 Alkyl Acrylate)0.90--0.50TEGO ®< Filmstar One MB (INCI: Polyglyceryl-3 Stearate / Sebacate Crosspolymer)--2.001.00Benzophenone-35.005.005.005.00Ethylhexyl Salicylate5.005.005.005.00Ethylhexyl Methoxycinnamate7.507.507.507.50Homosalate10.0010.0010.0010.00Butyl Methoxydibenzoylmethane2.002.002.002.00TEGOSOFT ®< M (Isopropyl Myristate)4.004.004.004.00BDRIVOSOL ®< 27D60 (Butane; Propane; Isobutane)10.0020.0020.0020.00 Water Resistant Aerosol Spray SPF 30

[0194] Phase Raw material % w / w % w / w % w / w ADenat. Alcoholto 100to 100to 100Polyester-10 (and) Propylene Glycol Dibenzoate1.501.501.50Polyglycerol partial ester (PGE) 0.75 3.00 1.50 TEGO ®< SP 13 Sun Up MB (Poly C10-30 Alkyl Acrylate)0.90-TEGO ®< Filmstar One MB (INCI: Polyglyceryl-3 Stearate / Sebacate Crosspolymer)--1.50Benzophenone-35.005.005.00Ethylhexyl Salicylate5.005.005.00Ethylhexyl Methoxycinnamate7.507.507.50Homosalate10.0010.0010.00Butyl Methoxydibenzoylmethane2.002.002.00dermofeel ®< sensolv MB (Isoamyl Laurate)6.006.006.00BDRIVOSOL ®< 27D60 (Butane; Propane; Isobutane)10.0020.0020.00 Light O / W Sun Care Lotion

[0195] Phase Raw material % w / w % w / w % w / w % w / w AAxol ®< C 62 Pellets MB (Glyceryl Stearate Citrate)2.502.500.502.50Glyceryl Stearate SE-1.004.001.00Cetearyl Alcohol1.001.00-1.00Glyceryl Stearate--1.20-Tegosoft ®< CT (Caprylic / Capric Triglyceride)8.002.00-2.00Tegosoft ®< TN (C12-15 Alkyl Benzoate)-6.007.006.00Diisopropyl Adipate1.001.001.001.00Polyglycerol partial ester (PGE) 2.00 2.00 2.00 1.50 Butyloctyl Salicylate (HallBrite BHB, The HallStar Company)2.002.002.002.00Tocopheryl Acetate0.200.200.200.20Dimethicone (5 mPas)1.00--0.50Tapioca Starch-1.00--Hydroxyethyl Acrylate / Sodium Acryloyldimethyl Taurate Copolymer1.20-Triacontanyl PVP (Antaron WP-660, Ashland)1.00Butyl Methoxydibenzoylmethane1.501.501.501.50Diethylamino Hydroxybenzoyl Hexyl Benzoate (Uvinul A Plus, BASF)4.004.004.004.00Ethylhexyl Triazone2.002.002.002.00Ethylhexyl Salicylate5.005.005.005.00Octocrylene8.008.008.008.00Ethylhexyl Methoxycrylene1.501.501.501.50BTitanium Dioxide; Trimethoxycaprylylsilane1.001.001.001.00CGlycerin3.203.203.203.20Propanediol2.502.502.502.50EDTA0.020.020.020.02Waterto 100to 100to 100to 100DAcrylates / C10-30 Alkyl Acrylate Crosspolymer0.100.100.100.10Tegosoft ®< CT (Caprylic / Capric Triglyceride)0.900.900.900.90ESodium Hydroxide (10% in water)q.s.q.s.q.s.q.s.ZPreservative, Perfumeq.s.q.s.q.s.q.s. Dry Touch Hand Moisturizing Cream

[0196] Phase Raw material % w / w % w / w % w / w AVarisoft ®< TA 100 (Distearyldimonium Chloride)3.003.00-Tego ®< Care Eco CAT MB (Distearoylisopropyl Dimonium Methosulfate; Stearyl Alcohol)--4.50Stearyl Alcohol1.001.001.00Tegin ®< M Pellets MB (Glyceryl Stearate)1.001.002.00Tegosoft ®< SH (Stearyl Heptanoate)1.001.001.00Tegosoft ®< P (Isopropyl Palmitate)5.005.005.00Polyglycerol partial ester (PGE) 1.50 2.00 2.00 Triacontanyl PVP (Antaron WP-660, Ashland)0.50--Diethylamino Hydroxybenzoyl Hexyl Benzoate (Uvinul A plus, BASF)3.003.003.00Ethylhexyl Salicylate3.003.003.00Ethylhexyl Methoxycinnamate5.005.005.00Tocopheryl Acetate0.500.500.50Tego ®< Feel C 10 (Cellulose)1.00-1.00BWaterto 100to 100to 100Glycerin3.003.003.00CTego ®< Natural Betaine (Betaine)2.002.002.00Water2.002.002.00DPhenoxyethanol, Ethylhexylglycerin (Euxyl PE 9010, Schülke & Mayr GmbH)0.700.700.70 Age Defense BB Cream SPF 15

[0197] Phase Raw material % w / w % w / w % w / w AC14-22 Alcohols; C12-20 Alkyl Glucoside 4.50 -3.50 Cetearyl Alcohol; Cetearyl Glucoside-5.20-Potassium Cetyl Phosphate0.80--Sodium Stearoyl Glutamate-1.102.00Glyceryl Stearate1.001.001.00Stearic Acid0.500.500.50Stearyl Alcohol1.001.001.00Butylene Glycol Dicaprylate / Dicaprate5.002.005.50Tegosoft ®< DEC (Diethylhexyl Carbonate)1.904.901.40Capryloyl Glycerin / Sebacic Acid Copolymer (LexFilm Sun Natural MB, Inolex Inc.)1.50--Polyglycerol partial ester (PGE) 1.50 3.00 3.00 HyaCare ®< Filler CL (Water; Ethylhexyl Stearate; Sodium Hyaluronate Crosspolymer; Polyglyceryl-4 Diisostearate / Polyhydroxystearate / Sebacate; Sodium Isostearate)2.002.002.00Phytosphingosine0.100.100.10Ethylhexyl Methoxycinnamate5.005.005.00Diethylamino Hydroxybenzoyl Hexyl Benzoate3.003.003.00BTitanium Dioxide (Hombitan AC 360, Sachtleben)3.003.003.00Talc (Micro Talc IT Extra-AW, Mondo Minerals B.V.)2.002.002.00Unipure Yellow LC 1820.360.360.36Unipure Red LC 3810.120.120.12Unipure Black LC 9890.080.080.08Tegosoft ®< AC MB (Isoamyl Cocoate)4.404.404.40Tegosoft ®< CT (Caprylic / Capric Triglyceride)4.004.004.00Polymethyl Methacrylate (Sepimat P, Seppic)3.003.003.00Polyhydroxystearic Acid0.500.50-CWaterto 100to 100to 100Glycerin3.003.003.00HyaCare ®< 50 (Hydrolysed Hyaluronic Acid)0.100.100.10Tego ®< Pep 4-17 (Tetrapeptide-21; Glycerin; Butylene Glycol; Water)2.002.002.00DAlcohol3.003.003.00EPreservativeq.s.q.s.q.s. Moisture Caring BB Cream SPF 15

[0198] Phase Raw material % w / w % w / w AAbil ®< EM 180 (Cetyl PEG / PPG-10 / 1 Dimethicone)2.002.00Abil ®< Wax 9801 (Cetyl Dimethicone)2.002.00Diethylamino Hydroxybenzoyl Hexyl Benzoate; Ethylhexyl Methoxycinnamate10.0010.00Dicaprylyl Carbonate2.002.00Polyglycerol partial ester (PGE) 0.50 1.50 Dimethicone (and) Trimethylsiloxysilicate3.003.00HyaCare ®< Filler CL (Water; Ethylhexyl Stearate; Sodium Hyaluronate Crosspolymer; Polyglyceryl-4 Diisostearate / Polyhydroxystearate / Sebacate; Sodium Isostearate)2.002.00Phytosphingosine (Phytosphingosine)0.100.10Hydrogenated Castor Oil0.500.50Microcrystalline Wax0.500.50BTalc (Micro Talc IT Extra-AW, Mondo Minerals B.V.)2.002.00Titanium Dioxide (Hombitan AC 360, Sachtleben)4.004.00Unipure Yellow LC 1820.360.36Unipure Red LC 3810.120.12Unipure Black LC 9890.080.08Aerosil ®< R 972 (Silica Dimethylsilylate)0.50-Tegosoft ®< OS (Ethylhexyl Stearate)5.005.00Tegosoft ®< DEC (Diethylhexyl Carbonate)6.006.00CWaterto 100to 100HyaCare ®< (Sodium Hyaluronate)0.050.05Glycerin5.005.00Sodium Chloride0.800.80DPhenoxyethanol; Ethylhexylglycerin (Euxyl PE 9010, Schülke & Mayr)0.700.70 Anhydrous stick

[0199] Phase Raw material % w / w dermofeel ®< viscolid MB (Hydrogenated Vegetable Oil)10.00Tego ®< SP 13 Sun Up (Poly C10-30 Alkyl Acrylate)5.00Polyglycerol partial ester (PGE) 10.00 Tegosoft ®< CT (Caprylic / Capric Triglyceride)30.00Isopropyl Palmitate15.00Ethylhexyl Methoxycinnamate7.50Octyldodecanolto 100 O / W Sun Protect & Bronze

[0200] Phase Raw material % w / w % w / w % w / w % w / w % w / w AGlyceryl Stearate Citrate2.002.002.002.002.00TEGO ®< Alkanol 1618 (Cetearyl Alcohol)1.501.501.501.501.50TEGOSOFT ®< DC MB (Decyl Cocoate)8.008.008.008.008.00TEGOSOFT ®< XC MB (Phenoxyethyl Caprylate)4.004.004.004.004.00Cera Alba (Beeswax 8104, KahlWax)0.50----Polyglycerol partial ester (PGE) 0.50 2.00 1.10 1.30 1.50 Styrene / Acrylates Copolymer (Dermacryl E, Nouryon)--1.00-0.50Acrylates / Octylacrylamide Copolymer (Dermacryl 79, Nouryon)---0.8-TEGO ®< Filmstar One MB (INCI: Polyglyceryl-3 Stearate / Sebacate Crosspolymer)----0.50Titanium Dioxide, Trimethoxycaprylylsilane1.501.501.501.501.50Dimethicone (5 cSt)3.00----Talc-1.201.201.201.20Octocrylene9.009.009.009.009.00Ethylhexyl Salicylate4.504.504.504.504.50Butyl Methoxydibenzoylmethane2.002.002.002.002.00Tocopheryl Acetate0.500.500.500.500.50Xanthan Gum (Keltrol CG-SFT, CP Kelco)0.500.500.500.500.50BWaterto 100to 100to 100to 100to 100Glycerin3.003.003.003.003.00Panthenol1.001.001.001.001.00CAcrylates / C10-30 Alkyl Acrylate Crosspolymer0.100.100.100.100.10TEGOSOFT ®< TN (C12-15 Alkyl Benzoate)0.400.400.400.400.40DSodium Hydroxide (10% in water)q.s.q.s.q.s.q.s.q.s.EButylene Glycol; Acetyl-L-Tyrosine; Hydrolyzed Vegetable Protein; Adenosin Triphosphate; Riboflavin (Unipertan VEG-2001)0.800.800.800.800.80ZPreservative, Perfumeq.s.q.s.q.s.q.s.q.s. Sun Care Foam SPF 50

[0201] Phase Raw material % w / w % w / w % w / w ATego ®< Care PBS 6 MB (Polyglyceryl-6 Stearate, Polyglyceryl-6 Behenate)2.002.002.00Tegosoft ®< AC MB (Isoamyl Cocoate)5.005.005.00dermofeel ®< viscolid MB (Hydrogenated Vegetable Oil)0.500.500.50Polyglycerol partial ester (PGE) 0.50 0.50 0.50 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine4.504.504.50Butyl Methoxydibenzoylmethane3.003.003.00Octocrylene8.008.008.00Homomenthyl Salicylate6.006.006.00Ethylhexyl Salicylate2.502.502.50Tego ®< Feel C 10 (Cellulose)2.00--Methyl Methacrylate Crosspolymer-1.50-Aluminium Starch Octenylsuccinate--1.70BWaterto 100to 100to 100Glycerin2.002.002.00EDTA Disodium0.050.050.05CC12-15 Alkyl Benzoate0.800.800.80Carbomer0.200.200.20Xanthan Gum (Keltrol CG-SFT, CP Kelco)0.200.200.20DWater11.6811.6811.68Phenylbenzimidazole Sulfonic Acid3.003.003.00Tromethamine1.321.321.32EPhenoxyethanol, Ethylhexylglycerin (Euxyl PE 9010, Schülke & Mayr GmbH)0.700.700.70Tego ®< Betain 810 (Capryl / Capramidopropyl Betaine)1.001.001.00Rewoteric ®< AM C (Sodium Cocoamphoacetate)1.001.001.00FTromethamine (30% in water)q.s.q.s.q.s. W / O Sun Protection Shake-Shake

[0202] Phase Raw material % w / w AAbil ®< EM 90 (Cetyl PEG / PPG-10 / 1 Dimethicone)1.00Tegosoft ®< CT (Caprylic / Capric Triglyceride)11.00Dicaprylyl Carbonate2.50Dimethicone (5 cSt)12.00Octocrylene6.00Ethylhexyl Salicylate2.00Butyl Methoxydibenzoylmethane0.80Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (Tinosorb S, BASF SE)1.50Titanium Dioxide, Trimethoxycaprylylsilane2.00Polyglycerol partial ester (PGE) 0.50 BWater4.43Phenylbenzimidazole Sulfonic Acid (Eusolex 232, Merck KGaA)0.50Sodium Hydroxide0.07CDistarch Phosphate (MAIS PO4 PH "B", Agrana Stärke GmbH)1.50Alcohol1.00Glycerin6.00Waterto 100ZPreservative, Perfumeq.s. Light Sun Care W / O Shake-Shake SPF30 PA+++

[0203] Phase Raw material % w / w AAbil ®< EM 90 (Cetyl PEG / PPG-10 / 1 Dimethicone)1.50Tegosoft ®< DEC (Diethylhexyl Carbonate)5.00Dimethicone (2 cSt)20.00Tegosoft ®< CT (Caprylic / Capric Triglyceride)5.00C12-15 Alkyl Benzoate; Titanium Dioxide; PEG-30 Dipolyhydroxystearate; Silica; Dimethicone (T-lique AB50Si, Uni-Powder)2.40Zinc Oxide (ZnO-NAS, Sunjin)8.00Abil ®< Wax 9801 (Cetyl Dimethicone)2.00Talc2.00Polymethylsilsesquioxane (Gransil PSQ, Grant)3.00Vinyl Dimethicone / Methicone Silsesquioxane Crosspolymer (KSP-100, ShinEtsu)1.00Polyglycerol partial ester (PGE) 2.00 Diethylamino Hydroxybenzoyl Hexyl Benzoate2.00Ethylhexyl Methoxycinnamate8.00Ethylhexyl Salicylate4.00Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (Escalol S, Ashland)0.50BWaterto 100Glycerin3.00Sodium Chloride1.00CPhenoxyethanol, Ethylhexylglycerin (Euxyl PE 9010, Schülke & Mayr GmbH)0.70 W / O Organic shake-shake SPF50+ PA++++

[0204] Phase Raw material % w / w AAbil ®< EM 90 (Cetyl PEG / PPG-10 / 1 Dimethicone)1.50Tegosoft ®< DEC (Diethylhexyl Carbonate)7.00Dimethicone (5 cSt)5.00Cyclopentasiloxane; Cyclohexasiloxane5.00Tegosoft ®< P (Isopropyl Palmitate)3.00Polyglycerol partial ester (PGE) 0.50 C12-15 Alkyl Benzoate; Titanium Dioxide; PEG-30 Dipolyhydroxystearate; Silica; Dimethicone (T-lique AB50Si, Uni-Powder)15.60Abil ®< Wax 9801 (Cetyl Dimethicone)2.00Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (Escalol S, Ashland)1.00Diethylamino Hydroxybenzoyl Hexyl Benzoate (Uvinul A plus Granular, BASF)1.50Octocrylene2.00Ethylhexyl Methoxycinnamate7.00Ethylhexyl Salicylate4.00Zinc Oxide (ZnO-NAS, Sunjin)14.40BWaterto 100Butylene Glycol3.00Sodium Chloride1.50CPhenoxyethanol, Ethylhexylglycerin (Euxyl PE 9010, Schülke & Mayr GmbH)0.70 Sun Care Cream SPF 30

[0205] Phase Raw material % w / w % w / w Adermofeel ®< GSC SG (Glyceryl Stearate Citrate)2.002.00Tegin ®< M Pellets MB (Glyceryl Stearate)0.500.50Tego ®< Alkanol 1618 (Cetearyl Alcohol)0.500.50dermofeel ®< sensolv MB (Isoamyl Laurate)4.504.50Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (Tinosorb S, BASF)3.003.00Butyl Methoxydibenzoylmethane2.002.00Ethylhexyl Salicylate3.003.00Octocrylene8.008.00Homosalate3.003.00Ethylhexyl Triazone1.501.50Polyglycerol partial ester (PGE) 1.50 1.50 BWaterto 100to 100Glycerin3.003.00EDTA0.050.05Tego ®< Feel C 10 (Cellulose)2.00-Zea Mays (Corn) Starch-2.001,2-Hexanediol2.202.20CAcrylates / C10-30 Alkyl Acrylate Crosspolymer0.200.20dermofeel ®< sensolv MB (Isoamyl Laurate)0.800.80DSodium Hydroxide (10% in water)q.s.q.s.EVerstatil ®< PC (Phenoxyethanol, Caprylyl Glycol)1.001.00 On the go UV protection stick SPF 50

[0206] Phase Raw material % w / w ATegosoft ®< M (Isopropyl Myristate)8.00Tegosoft ®< CT (Caprylic / Capric Triglyceride)7.50Tegosoft ®< DEC (Diethylhexyl Carbonate)8.60Titanium Dioxide, Silica, Dimethicone (Parsol TX, DSM)2.50BTegosoft ®< CR MB (Cetyl Ricinoleate)2.60Tegosoft ®< MM MB (Myristyl Myristate)4.00Diethylamino Hydroxybenzoyl Hexyl Benzoate8.00Ethylhexyl Salicylate5.00Ethylhexyl Methoxycinnamate10.00Homosalate5.00Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (Tinosorb S, BASF)3.50Beeswax3.50Polyglyceryl-3 Beeswax (Cera Bellina, Koster Keunen)6.00Ozokerite (1899, KahlWax)3.50Copernicia Cerifera (Carnauba) Wax (2442L, KahlWax)2.50dermofeel ®< AP MB (Ascorbyl Palmitate)0.10dermofeel ®< Toco 70 non GMO (Tocopherol, Helianthus Annuus (Sunflower) Seed Oil)0.20Tego ®< SP 13-1 (Poly C10-30 Alkyl Acrylate)2.50Polyglycerol partial ester (PGE) 5.00 CAerosil ®< 200 (Silica)2.00DTego ®< Feel C 10 (Cellulose)10.00ZPerfumeq.s. Transparent UV protection water spray SPF 30

[0207] Phase Raw material % w / w ATegosoft ®< DEC (Diethylhexyl Carbonate)15.00Isododecane7.50Tegosoft ®< P (Isopropyl Palmitate)5.00dermofeel ®< sensolv MB (Isoamyl Laurate)5.00Butyl Methoxydibenzoylmethane5.00Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (Tinosorb S, BASF)2.40Homosalate2.00Ethylhexyl Salicylate2.00Ethylhexyl Triazone1.70dermofeel ®< Toco 70 non GMO (Tocopherol, Helianthus Annuus (Sunflower) Seed Oil)0.50Polyglycerol partial ester (PGE) 0.35 BVerstatil ®< PC (Phenoxyethanol, Caprylyl Glycol)1.00Perfumeq.s.CWaterto 100Glycerin3.00Disodium EDTA0.10DWater9.65Phenylbenzimidazole Sulfonic Acid2.50Sodium Hydroxide0.35ETriethanolamineq.s. to pH 7.1 Sun Care Cream SPF 25

[0208] Phase Raw material % w / w % w / w AGlyceryl Stearate0.500.50Cetearyl Alcohol0.50-Cetyl Alcohol-0.80dermofeel ®< sensolv MB (Isoamyl Laurate)3.503.50Butyl Methoxydibenzoylmethane3.003.00Ethylhexyl Salicylate5.005.00Octocrylene10.010.0Homosalate10.010.0Polyglycerol partial ester (PGE) 1.50 1.50 BPotassium Cetyl Phosphate (Amphisol K, DSM Nutritional Products)1.501.50Waterto 100to 100Glycerin3.003.00EDTA0.050.05CAcrylates / C10-30 Alkyl Acrylate Crosspolymer0.200.20dermofeel ®< sensolv MB (Isoamyl Laurate)0.800.80DSodium Hydroxide (10% in water)0.600.60EVerstatil ®< PC (Phenoxyethanol, Caprylyl Glycol)1.001.00 Inorganic water-resistant O / W sunscreen SPF 20

[0209] Phase Raw material % w / w % w / w % w / w ATEGO ®< Care PBS 6 MB (Polyglyceryl-6 Stearate; Polyglyceryl-6 Behenate)4.004.001.50TEGO ®< SP 13-1 (Poly C10-30 Alkyl Acrylate)1.50--TEGO ®< Filmstar One MB (INCI: Polyglyceryl-3 Stearate / Sebacate Crosspolymer)--2.50TEGIN ®< M Pellets MB (Glyceryl Stearate)0.200.200.20TEGO ®< Alkanol 1618 (Cetearyl Alcohol)0.200.200.20BZinc Oxide; Triethoxycaprylylsilane (Z-Cote HP-1, BASF)7.807.807.80Titanium Dioxide, Silica, Dimethicone (Parsol TX, DSM)7.207.207.20TEGOSOFT ®< DC MB (Decyl Cocoate)3.003.003.00dermofeel ®< sensolv MB (Isoamyl Laurate)3.003.003.00TEGOSOFT ®< CT (Caprylic / Capric Triglyceride)5.005.005.00TEGOSOFT ®< DEC (Diethylhexyl Carbonate)5.005.005.00ABIL ®< 350 (Dimethicone)3.00--ABIL ®< Wax 9840 (Cetyl Dimethicone)2.00--Zea Mays (Corn) Starch-2.002.00dermosoft ®< Octiol (Caprylyl Glycol)0.500.500.50Polyglycerol partial ester (PGE) 0.50 2.50 2.50 CWaterto 100to 100to 100Glycerin3.003.003.00Xanthan Gum (Keltrol CG-SFT, CP Kelco)0.500.500.50Ddermosoft ®< Pentiol eco (Pentylene Glycol)3.003.003.00ECitric acid (50% in water)0.450.450.45 Feel the sun spray SPF 50

[0210] Phase Raw material % w / w % w / w Adermofeel ®< GSC SG (Glyceryl Stearate Citrate)2.502.50Tegin ®< M Pellets MB (Glyceryl Stearate)0.250.25Tego ®< Alkanol 1618 (Cetearyl Alcohol)0.250.25dermofeel ®< sensolv MB (Isoamyl Laurate)4.006.00Di(iso)pentyl terephthalate4.00-Polyglycerol partial ester (PGE) 1.00 1.00 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (Tinosorb S, BASF)6.006.00Diethylamino Hydroxybenzoyl Hexyl Benzoate6.006.00Ethylhexyl Salicylate5.005.00Ethylhexyl Triazone2.002.00dermofeel ®< Toco 70 non GMO (Tocopherol, Helianthus Annuus (Sunflower) Seed Oil)0.200.20Titanium Dioxide; Aluminium Hydroxide; Stearic Acid (A15-TiO 2 -ST-SA8, Kobo Products)-1.50BWaterto 100to 100Glycerin3.003.00Propylene Glycol2.002.00EDTA0.050.05CXanthan Gum (Keltrol CG-SFT, CP Kelco)0.500.50DPhenylbenzimidazole Sulfonic Acid3.003.00Tromethamine (Trisaminomethane)1.321.32Water10.6810.68EVerstatil ®< BOB (Benzyl Alcohol; Caprylyl Glycol; Benzoic Acid)1.201.20ZPerfume0.100.10 Natural Sun Protection Stick

[0211] Phase Raw material % w / w ACarthamus Tinctorius (Safflower) Seed Oil22.80Butyrospermum Parkii Butter (shea butter)7.00Hippophae Rhamnoides Fruit Oil1.00dermofeel ®< sensolv MB (Isoamyl Laurate)8.00Tegosoft ®< CT (Caprylic / Capric Triglyceride)2.00dermofeel ®< viscolid MB (Hydrogenated Vegetable Oil)2.00Tegosoft ®< DC MB (Decyl Cocoate)6.00Tegosoft ®< OER MB (Oleyl Erucate)6.00Cera Alba (Beeswax 8104, KahlWax)5.00Helianthus Annuus Seed Cera, Ascorbyl Palmitate, Tocopherol (Sunflower Seed Wax 6607L, KahlWax)3.00Euphorbia Cerifera Cera (Candelilla Wax 2039L, KahlWax)3.00Polyglycerol partial ester (PGE) 8.00 dermofeel ®< TocoBalance (Tocopherol, Helianthus Annuus (Sunflower) Seed Oil)1.50dermosoft ®< GMCY MB (Glyceryl Caprylate)1.00BDistarch Phosphate (Corn P04 PH "B", Agrana)1.00Tego ®< Feel C 10 (Cellulose)2.00Zinc Oxide (Zano 10, EverZinc)20.00CPerfume0.70 W / O Quick-Breaking Cream SPF 15

[0212] Phase Raw material % w / w AAbil ®< EM 180 (Cetyl PEG / PPG-10 / 1 Dimethicone)0.80Tegosoft ®< DEC (Diethylhexyl Carbonate)3.00Tegosoft ®< CT (Caprylic / Capric Triglyceride)2.00Dimethicone (5 cSt)3.00Polyglycerol partial ester (PGE) 1.00 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (Tinosorb S, BASF)2.00Diethylamino Hydroxybenzoyl Hexyl Benzoate2.004-Methylbenzylidene Camphor4.00Ethylhexyl Salicylate2.00Verstatil ®< BOB (Benzyl Alcohol, Caprylyl Glycol, Benzoic Acid)1.00BWaterto 100Propylene Glycol5.00Sodium Chloride1.00 W / O Sun Care Lotion SPF 8, Water Resistant

[0213] Phase Raw material % w / w % w / w % w / w % w / w AIsolan ®< GPS (Polyglyceryl-4 Diisostearate / Polyhydroxystearate / Sebacate)3.00---Polyglyceryl-3 Diisostearate-3.50--Polyglyceryl-2 Dipolyhydroxystearate--3.00-Polyglyceryl-3 Polyricinoleate---3.00Hydrogenated Castor Oil0.200.200.200.20Microcrystalline Wax0.300.300.300.30Tegosoft ®< CT (Caprylic / Capric Triglyceride)5.005.005.005.00Tegosoft ®< DEC (Diethylhexyl Carbonate)3.003.003.003.00Tegosoft ®< CR MB (Cetyl Ricinoleate)0.750.750.750.75Polyglycerol partial ester (PGE) 0.75 0.75 0.75 0.75 Triisostearin1.001.001.001.00Ethylhexyl Methoxycinnamate5.005.005.005.00Ethylhexyl Salicylate4.004.004.004.00Menthyl Anthranilate4.004.004.004.00BTego ®< Cosmo C 100 (Creatine)0.500.500.500.50Glycerin3.003.003.003.00Magnesium Sulfate Heptahydrate1.501.501.501.50Waterto 100to 100to 100to 100ZPreservative, Perfumeq.s.q.s.q.s.q.s. W / O Sun Care Lotion, Water resistant

[0214] Phase Raw material % w / w AIsolan ®< 17 MB (Polyglyceryl-4 Diisostearate / Polyhydroxystearate / Sebacate; Caprylic / Capric Triglyceride; Polyglyceryl-3 Oleate; Diisostearoyl Polyglyceryl-3 Dimer Dilinoleate)4.00Paraffin; Cera Microcristallina (Paracera W 80, Paramelt)0.25Hydrogenated Castor Oil0.25Tegosoft ®< XC MB (Phenoxyethyl Caprylate)7.00Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (Tinosorb S, BASF)7.00Homosalate10.00Diethylamino Hydroxybenzoyl Hexyl Benzoate6.00Polyglycerol partial ester (PGE) 1.00 dermofeel ®< Toco 70 non GMO (Tocopherol, Helianthus Annuus (Sunflower) Seed Oil)0.50dermosoft ®< GMC MB (Glyceryl Caprate)0.50BWaterto 100Glycerin3.00Zinc Sulfate Heptahydrate1.00 Cationic Sun Screen SPF 19, Water Resistant

[0215] Phase Raw material % w / w AVarisoft ®< TA 100 (Distearyldimonium Chloride)3.50Tegin ®< M Pellets MB (Glyceryl Stearate)2.00Stearyl Alcohol1.00Tegosoft ®< CT (Caprylic / Capric Triglyceride)5.00Tegosoft ®< DEC (Diethylhexyl Carbonate)3.50Polyglycerol partial ester (PGE) 1.50 Triisostearin1.00Titanium Dioxide, Diethylhexyl Carbonate, Polyglyceryl-6 Polyhyd roxystearate5.004-Methylbenzylidene Camphor4.00Octocrylene3.00Butyl Methoxydibenzoylmethane2.00BGlycerin3.00Waterto 100ZPreservative, Perfumeq.s. Cationic Sun Screen SPF 15, Water Resistant

[0216] Phase Raw material % w / w AVarisoft ®< TA 100 (Distearyldimonium Chloride)3.50Tegin ®< M Pellets MB (Glyceryl Stearate)1.50Stearyl Alcohol1.00Tegosoft ®< DC MB (Decyl Cocoate)8.00Dicaprylyl Carbonate5.00Tegosoft ®< MM MB (Myristyl Myristate)1.00Polyglycerol partial ester (PGE) 2.00 Tegosoft ®< OER MB (Oleyl Erucate)1.00Ethylhexyl Methoxycinnamate5.00Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine3.00BTego ®< Cosmo C 100 (Creatine)0.50Glycerin3.00Waterto 100ZPreservative, Perfumeq.s. Everyday Sunshine Cream SPF 15

[0217] Phase Raw material % w / w % w / w % w / w ATego ®< Care 165 (Glyceryl Stearate; PEG-100 Stearate)3.003.00-Polysorbate 60--4.00Stearyl Alcohol2.001.503.00Tegosoft ®< CT (Caprylic / Capric Triglyceride)4.004.004.00Propylene Glycol Dibenzoate2.002.002.00Titanium Dioxide; Trimethoxycaprylylsilane1.001.001.00Paraffinum Liquidum2.002.002.00Butyrospermum Parkii (Shea Butter)1.001.001.00Octocrylene2.002.002.00Butyl Methoxydibenzoylmethane2.002.002.00Ethylhexyl Salicylate5.005.005.00Polyglycerol partial ester (PGE) 1.50 1.50 1.50 Tocopheryl Acetate0.800.800.80BWaterto 100to 100to 100Glycerin3.003.003.00Acrylates Copolymer-1.00-Graham's salt (Sodium Hexametaphosphate)0.200.200.20Tego ®< Cosmo C 100 (Creatine)0.500.500.50HyaCare ®< 50 (Hydrolysed Hyaluronic Acid)0.100.100.10Polyacrylamide; C13-14 Isoparaffin; Laureth-7 (Sepigel 305, Seppic)2.001.202.00CWater13.2913.2913.29Phenylbenzimidazole Sulfonic Acid (Eusolex 232, Merck KGaA)1.051.051.05Sodium Hydroxideq.s.q.s.q.s.ZPreservative, perfumeq.s.q.s.q.s. High Sun Protection Lotion O / W SPF 50

[0218] Phase Raw material % w / w % w / w % w / w APolyglyceryl-3 Distearate; Glyceryl Stearate Citrate3.503.003.00Sodium Cetearyl Sulfate-0.500.50Tegosoft ®< CT (Caprylic / Capric Triglyceride)5.005.003.00Polyglycerol partial ester (PGE) 0.50 0.50 0.50 Rewopal ®< PIB 1000 (Polyisobutene)0.500.500.50Acrylates / C10-30 Alkyl Acrylate Crosspolymer0.200.20-Xanthan Gum (Keltrol CG-SFT, CP Kelco)0.200.200.05Titanium Dioxide; Trimethoxycaprylylsilane1.501.501.50Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (Tinosorb S, BASF SE)4.004.004.00Octocrylene10.0010.0010.00Butyl Methoxydibenzoylmethane4.004.004.00BGlycerin4.00to 100to 100Waterto 1005.005.00CAlcohol5.00q.s.q.s.Tegosoft ®< CT (Caprylic / Capric Triglyceride)--2.20Disteardimonium Hectorite--0.20Propylene Carbonate--0.20Preservativeq.s.q.s.q.s.DMethylene Bis-Benzotriazolyl Tetramethylbutylphenol (Tinosorb M, BASF SE)8.00q.s.q.s.ESodium Hydroxide (10% in water)q.s. to pH 6q.s. to pH 6q.s. to pH 6 Icy O / W Sun Care Lotion SPF 25

[0219] Phase Raw material % w / w % w / w % w / w % w / w APolyglyceryl-3 Distearate3.001.00--Sucrose Polystearate; Cetyl Palmitate--2.503.20Sodium Stearoyl Glutamate-1.501.00-Stearyl Alcohol1.001.001.001.00dermofeel ®< sensolv MB (Isoamyl Laurate)5.005.005.005.00Tegosoft ®< SH (Stearyl Heptanoate)1.501.501.501.50Polyglycerol partial ester (PGE) 1.50 1.80 1.80 1.80 Tego ®< Xymenynic (Caprylic / Capric Triglyceride, Xymenynic Acid)1.001.001.001.00Diethylamino Hydroxybenzoyl Hexyl Benzoate6.006.006.006.004-Methylbenzylidene Camphor4.004.004.004.00Diethylhexyl Butamido Triazone3.003.003.003.00Xanthan Gum (Keltrol CG-SFT, CP Kelco)0.500.500.500.50BWaterto 100to 100to 100to 100Glycerin3.003.003.003.00CCarbomer0.100.100.100.10Tegosoft ®< XC MB (Phenoxyethyl Caprylate)0.400.400.400.40DSodium Hydroxide (10% in water)q.s.q.s.q.s.q.s.EPreservativeq.s.q.s.q.s.q.s.ZPerfumeq.s.q.s.q.s.q.s. Low viscosity W / O sun care lotion SPF30 PA+++

[0220] Phase Raw material % w / w % w / w AAbil ®< EM 90 (Cetyl PEG / PPG-10 / 1 Dimethicone)2.502.50Tegosoft ®< TN (C12-15 Alkyl Benzoate)2.003.00Dicaprylyl Carbonate2.002.00Tegosoft ®< CT (Caprylic / Capric Triglyceride)1.00-Polyglycerol partial ester (PGE) 0.40 1.60 Dimethicone (DC 200, 5 cSt, Dow Corning)16.0016.00Titanium Dioxide (Parsol TX, DSM)10.0010.00Zinc Oxide (Sunclear-Z60CO, Sunjin)25.0025.00Hydrogenated Lecithin0.501.50Dimethicone / Vinyl Dimethicone Crosspolymer and Silica (DC 9701, DowCorning)1.001.00Nylon-121.501.50BWaterto 100to 100Butylene Glycol5.005.00Sodium Chloride1.501.50CPhenoxyethanol, Ethylhexylglycerin (Euxyl PE 9010, Schülke & Mayr GmbH)0.700.70 Sun Care Aqua Gel SPF50+,PA++++

[0221] Phase Raw material % w / w AAbil ®< Care XL 80 (Bis-PEG / PPG-20 / 5 PEG / PPG-20 / 5 Dimethicone; Methoxy PEG / PPG-25 / 4 Dimethicone; Caprylic / Capric Triglyceride)3.00Tegosoft ®< DEC (Diethylhexyl Carbonate)7.00Dimethicone (5 cSt)2.00Tegosoft ®< CT (Caprylic / Capric Triglyceride)3.00Abil ®< Wax 9801 (Cetyl Dimethicone)2.00Bis-ethylhexyloxyphenol Methoxyphenyl Triazine (Tinosorb S, BASF)3.00Diethylamino Hydroxybenzoyl Hexyl Benzoate (Uvinul A plus Granular, BASF)4.00Octocrylene5.00Avobenzone (Parsol 1789, DSM)3.00Homomenthyl Salicylate8.00Ethylhexyl Salicylate5.00Ethylhexyl Methoxycinnamate10.00Polyglycerol partial ester (PGE) 1.50 BWaterto 100Butylene Glycol3.00Xanthan Gum (Keltrol CG-SFT, CP Kelco)0.20CSodium Acrylate / Sodium Acryloyldimethyl Taurate Copolymer (and) Isohexadecane (and) Polysorbate-80 (Simulgel EG, SEPPIC)1.50DPhenoxyethanol, Ethylhexylglycerin (Euxyl PE 9010, Schülke & Mayr GmbH)0.70 O / W Sun Care Cream with high protection SPF 50+ PA+++

[0222] Phase Raw material % w / w % w / w % w / w % w / w ATego ®< Care 450 MB (Polyglyceryl-3 Methylglucose Distearate)3.003.002.502.50Potassium Cetyl Phosphate-0.50--Glyceryl Stearate Citrate--0.60-Sodium Stearoyl Glutamate---0.70Caprylic / Capric Triglyceride2.002.00--Butylene Glycol Dicaprylate / Dicaprate--1.502.00Tego ®< Alkanol 1618 (Cetearyl Alcohol)1.001.001.001.00Abil ®< Wax 9840 (Cetyl Dimethicone)0.500.500.500.50Bis-ethylhexyloxyphenol Methoxyphenyl Triazine (Tinosorb S, BASF SE)2.002.002.002.00Butyl Methoxydibenzoylmethane3.003.003.003.00Octocrylene8.008.008.008.00Ethylhexyl Salicylate5.005.005.005.00Polyglycerol partial ester (PGE) 2.60 1.90 2.80 2.30 C12-15 Alkyl Benzoate; Titanium Dioxide; PEG-30 Dipolyhydroxystearate; Silica; Dimethicone (T-lique AB50Si, Uni-Powder)8.908.908.908.90BWaterto 100to 100to 100to 100Glycerin3.003.003.003.00CPhenylbenzimidazole Sulfonic Acid3.003.003.003.00Tromethamine 78%2.002.002.002.00Water4.004.004.004.00DAcrylates / C10-30 Alkyl Acrylate Crosspolymer (2% solution in water)10.0010.0010.0010.00ESodium Hydroxide (10% in water)0.400.400.400.40FPhenoxyethanol, Ethylhexylglycerin (Euxyl PE 9010, Schülke & Mayr GmbH)0.700.700.700.70 Sun Care Cream SPF 15

[0223] Phase Raw material % w / w % w / w % w / w % w / w % w / w % w / w ATEGO ®< Care 450 MB (Polyglyceryl-3 Methylglucose Distearate)3.002.502.502.502.502.50Potassium Cetyl Phosphate-0.800.800.800.800.80TEGIN ®< M Pellets MB (Glyceryl Stearate)1.501.501.501.501.501.50TEGO ®< Alkanol 1618 (Cetearyl Alcohol)1.501.501.501.501.501.50TEGOSOFT ®< CT (Caprylic / Capric Triglyceride)2.00-----Dibutyl Adipate-5.005.005.005.005.00dermofeel ®< sensolv MB (Isoamyl Laurate)7.005.005.005.005.005.00TEGOSOFT ®< CR MB (Cetyl Ricinoleate)1.001.001.001.001.001.00Polyglycerol partial ester (PGE) 3.00 1.00 1.30 1.40 1.40 1.00 Capryloyl Glycerin / Sebacic Acid Copolymer (LexFilm Sun Natural, Inolex)-1.20---1.00Polyglyceryl-3 Stearate / Isostearate / Dimer Dilinoleate--1.00---Crosspolymer (CosmoSurf PG1-IS, SurfaTech Corp.)Diisostearoyl Polyglyceryl-3 Dimer Dilinoleate (and) Caprylic / Capric Triglyceride (SolAmaze Natural polymer, Nouryon)---0.80--Sorbitol / Sebacic Acid Copolymer Behenate (Syncrowax ORM, Croda)----1.00-TEGO ®< Filmstar One MB (INCI: Polyglyceryl-3 Stearate / Sebacate Crosspolymer)-----1.00Bis-ethylhexyloxyphenol Methoxyphenyl Triazine (Tinosorb S, BASF)1.501.501.501.501.501.50Butyl Methoxydibenzoylmethane1.001.001.001.001.001.00Ethylhexyl Triazone0.750.750.750.750.750.75Homomenthyl Salicylate1.501.501.501.501.501.50Ethylhexyl Salicylate1.501.501.501.501.501.50Octocrylene4.004.004.004.004.004.00dermofeel ®< TocoBalance (Tocopherol, Helianthus Annuus (Sunflower) Seed Oil)0.700.700.700.700.700.70TEGO ®< Feel C 10 (Cellulose)2.002.002.002.002.002.00TEGO ®< SP 13-1 (Poly C10-30 Alkyl Acrylate)1.50-----Phytosphingosine SLC (Salicyloyl Phytosphingosine)0.100.100.100.100.100.10BWaterto 100to 100to 100to 100to 100to 100Glycerin3.003.003.003.003.003.00EDTA0.050.050.050.050.050.05TEGO ®< Cosmo C 100 (Creatine)0.500.500.500.500.500.50CXanthan Gum (Ketrol CG-SFT, CP Kelco)0.500.500.500.500.500.50DTEGO ®< Pep Up (Tetrapeptide-4; Glycerin)2.002.002.002.002.002.00EVerstatil ®< PC (Phenoxyethanol, Caprylyl Glycol)1.201.201.201.201.201.20Perfumeq.s.q.s.q.s.q.s.q.s.q.s.Tromethamine (Trisaminomethane, 30% in water)q.s.q.s.q.s.q.s.q.s.q.s. W / O foundation

[0224] Phase Raw material % w / w % w / w AIsolan ®< GPS (Polyglyceryl-4 Diisostearate / Polyhydroxystearate / Sebacate)4.00-Polyglyceryl-6 Polyhydroxystearate; Polyglyceryl-6 Polyricinoleate (Emulium Illustro, Gattefossé)-3.80Tegosoft ®< AC MB (Isoamyl Cocoate)5.505.50Tegosoft ®< DC MB (Decyl Cocoate)7.507.50Tegosoft ®< CT (Caprylic / Capric Triglyceride)3.503.50CI 77891, Hydrogenated Lecithin (Unipure White LC 981 HLC, Sensient)15.0015.00CI 77492, Hydrogenated Lecithin (Unipure Yellow LC 182 HLC, Sensient)1.201.20CI 77491, Hydrogenated Lecithin (Unipure Red LC 381 HLC Sensient)0.700.70CI 77499, Hydrogenated Lecithin (Unipure Black LC 989 HLC, Sensient)0.200.20Polyglycerol partial ester (PGE) 1.50 1.50 BWaterto 100to 100Glycerin3.003.00Zinc Sulfate Heptahydrate2.002.00Verstatil ®< SL non GMO (Sodium Levulinate, Potassium Sorbate, Water)q.s.q.s.Citric Acid (10% in water)q.s. to pH 4.4q.s. to pH 4.4 W / O foundation

[0225] Phase Raw material % w / w AIsolan ®< 17 MB (Polyglyceryl-4 Diisostearate / Polyhydroxystearate / Sebacate; Caprylic / Capric Triglyceride; Polyglyceryl-3 Oleate; Diisostearoyl Polyglyceryl-3 Dimer Dilinoleate)4.00Isododecane3.33Tegosoft ®< XC MB (Phenoxyethyl Caprylate)3.33Dimethicone3.33Polyglycerol partial ester (PGE) 2.00 CI 77891, Titanium Dioxide, Alumina, Triethoxycaprylylsilane (Hombitan AC360, Sachtleben)4.00CI 77491, CI 77492, CI 77499 (Iron Oxide, Sicovit Brown 70 E 172, Rockwood Pigments)2.50Talc2.00BDicaprylyl Carbonate, Stearalkonium Hectorite, Propylene Carbonate (Cosmedia Gel CC, BASF SE)3.00Isododecane1.50Tegosoft ®< XC MB (Phenoxyethyl Caprylate)1.50Dimethicone1.50CGlycerin5.00Magnesium Sulfate Heptahydrate1.50Waterto 100DVerstatil ®< PC (Phenoxyethanol, Caprylyl Glycol)1.00Boron Nitride (Boroneige 1201, ESK)5.00 SPF 30 sun lotion with water-soluble emulsifier and natural, aqueous thickeners

[0226] Phase Raw material % w / w % w / w % w / w % w / w % w / w % w / w % w / w % w / w ATegin ®< M Pellets MB (Glyceryl Stearate)0.50.50.50.50.50.50.50.5Tego ®< Alkanol 1618 (Cetearyl Alcohol)0.50.50.50.50.50.50.50.5Tegosoft ®< XC MB (Phenoxyethyl Caprylate)4.34.34.34.34.34.34.34.3Polyglycerol partial ester (PGE) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Bis-ethylhexyloxyphenol Methoxyphenyl Triazine33333333Butyl Methoxy Dibenzoylmethane22222222Ethylhexyl Salicylate33333333Octrocrylene88888888Homosalate33333333Ethylhexyl Triazone1.51.51.51.51.51.51.51.5dermofeel ®< Toco 70 non-GMO (Tocopherol, Helianthus Annuus (Sunflower) Seed Oil)0.20.20.20.20.20.20.20.2BPotassium Cetyl Phosphate1.51.51.51.51.51.51.51.5Glycerin33333333Waterto 100to 100to 100to 100to 100to 100to 100to 100EDTA0.050.050.050.050.050.050.050.05CXanthan Gum (Keltrol CG-SFT, CP Kelco)0.3Succinoglycan (Rheozan ®< SH, Solvay)0.3Glucomannan (Rheolex ®< One-C, Nagase)0.3Sclerotium Gum (Amigel ®< , Alban Muller)0.4Gellan Gum (Kelcogel ®< Gellan Gum, CP Kelco)0.1Caesalpinia Spinosa Gum (Solagum ®< Tara, Seppic)0.45Cellulose (Exilva ®< 10 w-% active matter, Borregaard)1DPhenoxyethanol, Caprylyl Glycol11111111 SPF 30 sun lotion with oil-soluble emulsifiers and natural, aqueous thickeners

[0227] Phase Raw material % w / w % w / w % w / w % w / w % w / w % w / w % w / w % w / w % w / w % w / w % w / w % w / w ATego ®< Care PBS 6 MB (Polyglyceryl-6 Stearate, Polyglyceryl-6 Behenate)3333Axol ®< C 62 Pellets MB (Glyceryl Stearate Citrate)3333Tego ®< Care 450 MB (Polyglyceryl-3 Methylglucose Distearate)3333Tegin ®< M Pellets MB (Glyceryl Stearate)0.50.50.50.50.50.50.50.50.50.50.50.5Tego ®< Alkanol 1618 (Cetearyl Alcohol)0.50.50.50.50.50.50.50.50.50.50.5Tegosoft ®< XC MB (Phenoxyethyl Caprylate)4.34.34.34.34.34.34.34.34.34.34.34.3Polyglycerol partial ester (PGE) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 3.0 3.0 3.0 Bis-ethylhexyloxyphenol Methoxyphenyl Triazine333333333333Butyl Methoxy Dibenzoylmethane222222222222Ethylhexyl Salicylate333333333333Octrocrylene888888888888Homosalate333333333333Ethylhexyl Triazone1.51.51.51.51.51.51.51.51.51.51.51.5dermofeel ®< Toco 70 non-GMO (Tocopherol, Helianthus Annuus (Sunflower) Seed Oil)0.20.20.20.20.20.20.20.20.20.20.20.2BGlycerin333333333333Waterto 100to 100to 100to 100to 100to 100to 100to 100to 100to 100to 100to 100EDTA0.050.050.050.050.050.050.050.050.050.050.050.05CXanthan Gum (Keltrol CG-SFT, CP Kelco)0.30.30.30.30.30.3Succinoglycan (Rheozan ®< SH, Solvay)0.30.30.3Glucomannan (Rheolex ®< One-C, Nagase)0.30.30.3DPhenoxyethanol, Caprylyl Glycol111111111111 SPF 30 sun lotion, mineral UF filters and natural, aqueous thickener

[0228] Phase Raw material % w / w % w / w % w / w % w / w A 1Tego ®< Care PBS 6 MB (Polyglyceryl-6 Stearate, Polyglyceryl-6 Behenate)4Axol ®< C 62 Pellets MB (Glyceryl Stearate Citrate)2.5Tego ®< Care 450 MB (Polyglyceryl-3 Methylglucose Distearate)3Tego ®< Alkanol 1618 (Cetearyl Alcohol)0.20.20.20.2Tegin ®< M Pellets MB (Glyceryl Stearate)0.20.20.20.2Polyglycerol partial ester (PGE) 1.5 1.5 1.5 1.5 A 2Tegosoft ®< CT (Caprylic / Capric Triglyceride)5555dermofeel ®< sensolv MB (Isoamyl Laurate)6666Tegosoft ®< XC (Phenoxyethyl Caprylate)Tegosoft ®< DEC (Diethylhexyl Carbonate)5555Dimethicone3333Abil ®< Wax 9840 (Cetyl Dimethicone)2222Titanium Dioxide, Silica; Dimethicone (Parsol ®< TX, DSM)7.27.27.27.2Zinc Oxide, Triethoxycaprylylsilane (Z-Cote ®< HP 1, BASF)7.87.87.87.8dermosoft ®< Octiol (Caprylyl Glycol)0.50.50.50.5BPotassium Cetyl Phosphate1.5Waterto 100to 100to 100to 100Glycerin3333Xanthan Gum (Keltrol CG-SFT, CP Kelco)0.50.50.50.5Ddermosoft ®< Pentiol eco (Pentylene Glycol.)3333ECitric Acid 50% w-% in water0.450.450.450.45

Claims

1. Polyglycerol partial ester obtainable by esterification a) of a polyglycerol having an average degree of condensation N of 2.4 to 15.0, preferably 2.6 to 10.0, especially 2.8 to 6.0, with a carboxylic acid mixture comprising: b1) at least one short-chain dicarboxylic acid having 4 to 18, preferably 4 to 14, more preferably 6 to 10, carbon atoms, b2) at least one long-chain dicarboxylic acid having 24 to 44, preferably 30 to 40, more preferably 34 to 38, carbon atoms and c) at least one long-chain, saturated and linear monocarboxylic acid having 18 to 32, preferably 18 to 26, more preferably 20 to 22, carbon atoms, wherein the sum total of all short-chain and long-chain dicarboxylic acids present in the carboxylic acid mixture comes to at least 75% by weight, preferably at least 85% by weight, more preferably at least 95% by weight, based on all the dicarboxylic acids present in the carboxylic acid mixture, wherein the sum total of all long-chain, saturated and linear monocarboxylic acids present in the carboxylic acid mixture comes to at least 86% by weight, preferably at least 90% by weight, more preferably at least 95% by weight, based on all the monocarboxylic acids present in the carboxylic acid mixture, wherein the molar ratio of all carboxyl groups present in the carboxylic acid mixture to all hydroxyl groups present in the polyglycerol used is at least 35 to 100, preferably at least 50 to 98, more preferably at least 68 to 95, characterized in that the molar ratio of polyglycerol a) to the sum total of the dicarboxylic acid components b1) and b2) to monocarboxylic acid component c) is from 1.0:1.0:1.0 to 4.0:1.0:10.0, preferably from 1.0:1.0:1.5 to 3.0:1.0:8.0.

2. Polyglycerol partial ester according to Claim 1, characterized in that the polyglycerol used has a glycerin content of 0.05% by weight to 25.0% by weight, preferably of 0.1% by weight to 15.0% by weight, more preferably of 0.1% by weight to 10.0% by weight.

3. Polyglycerol partial ester according to Claim 1 or 2, characterized in that the polyglycerol used has a diglycerin content of 0.1% by weight to 45.0% by weight, preferably of 0.5% by weight to 35.0% by weight, more preferably of 3.0% by weight to 30.0% by weight.

4. Polyglycerol partial ester according to at least one of the preceding claims, characterized in that the polyglycerol used has a content of cyclic isomers of 1% by weight to 50% by weight, preferably of 2% by weight to 40% by weight, more preferably of 3% by weight to 30% by weight.

5. Polyglycerol partial ester according to at least one of the preceding claims, characterized in that the short-chain dicarboxylic acid is selected from aliphatic, linear dicarboxylic acids, especially oxalic acid, malonic acid, tartronic acid, succinic acid, maleic acid, tartaric acid, malic acid, fumaric acid, sorbic acid, α-ketoglutaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid and brassylic acid, with particular preference given to adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.

6. Polyglycerol partial ester according to at least one of the preceding claims, characterized in that the long-chain dicarboxylic acid is selected from the group comprising dimer fatty acids.

7. Polyglycerol partial ester according to at least one of the preceding claims, characterized in that the long-chain, saturated and linear monocarboxylic acids are selected from hydroxysubstituted and unsubstituted, especially unsubstituted, fatty acids.

8. Polyglycerol partial ester according to at least one of the preceding claims, characterized in that the total content of aromatic mono- and dicarboxylic acids based on all mono- and dicarboxylic acids used is from 0.1% by weight to 35% by weight, preferably from 0% by weight to 25% by weight, more preferably from 0% by weight to 10% by weight.

9. Polyglycerol partial ester according to at least one of the preceding claims, characterized in that it has a degree of esterification of 35% to 100%, preferably of 50% to 98%, more preferably of 68% to 95%.

10. Polyglycerol partial ester according to at least one of the preceding claims, characterized in that it has a HLB value of from 2.0 to 8.0, preferably from 2.5 to 7.5 and more preferably from 3 to 5.2, wherein the HLB is calculated Z r as defined in the specification.

11. Polyglycerol partial ester according to at least one of the preceding claims, characterized in that it has an iodine value of less than 20, preferably less than 12, particularly preferably less than 5, wherein the iodine value in determined by the method EN 14111:2003.

12. Polyglycerol partial ester according to at least one of the preceding claims, characterized in that it has a melting point of greater than 35°C, preferably greater than 40°C, in particular greater than 50°C, more preferably within a range from 51°C to 100°C, wherein the melting point is determined using the capillary method based on DIN 53181, DIN EN ISO 3146, DGF C-IV 3a and Ph. Eur. 2.2.14.

13. Method for preparing a polyglycerol partial ester, comprising the method steps of A) providing a polyglycerol having an average degree of condensation N of 2.4 to 15.0, preferably 2.6 to 100, especially 2.8 to 6.0, B) providing a carboxylic acid mixture comprising: at least one short-chain dicarboxylic acid having 4 to 18, preferably 4 to 14, more preferably 6 to 10, carbon atoms, at least one long-chain dicarboxylic acid having 24 to 44, preferably 30 to 40, more preferably 34 to 38, carbon atoms, and at least one long-chain, saturated and linear monocarboxylic acid having 18 to 32, preferably 18 to 26, more preferably 20 to 22, carbon atoms, wherein the sum total of all short-chain and long-chain dicarboxylic acids present in the carboxylic acid mixture comes to at least 75% by weight, preferably at least 85% by weight, more preferably at least 95% by weight, based on all the dicarboxylic acids present in the carboxylic acid mixture, wherein the sum total of all long-chain, saturated and linear monocarboxylic acids present in the carboxylic acid mixture comes to at least 75% by weight, preferably at least 85% by weight, more preferably at least 95% by weight, based on all the monocarboxylic acids present in the carboxylic acid mixture, C) esterifying the polyglycerol with the carboxylic acid mixture, wherein the molar ratio of all carboxyl groups present in the carboxylic acid mixture to all hydroxyl groups present in the polyglycerol used is at least 35 to 100, preferably at least 50 to 98, more preferably at least 68 to 95, characterized in that the molar ratio of polyglycerol a) to the sum total of the dicarboxylic acid components b1) and b2) to carboxylic acid component c) is from 1.0:1.0:1.0 to 4.0:1.0:10.0, preferably from 1.0:1.0:1.5 to 3.0:1.0:8.0.

14. Formulation, especially a cosmetic formulation, comprising 1) polyglycerol partial esters according to at least one of Claims 1 to 12 or obtainable according to the method of Claim 13, and optionally 2) at least one substance selected from the group comprising UV light protection filter substances and pigments, especially UV light protection filter substances.

15. Formulation according to Claim 14, characterized in that component 2) is selected from the group of UV light protection filter substances comprising butyl methoxydibenzoylmethane, ethylhexyl triazone, bis-ethylhexyloxyphenol methoxyphenyl triazine, diethylhexyl butamido triazone, diethylamino hydroxybenzoyl hexyl benzoate, benzophenone-3, benzophenone-4, 4-methylbenzylidene camphor, octocrylene, ethylhexyl methoxycinnamate, ethylhexyl salicylate, homomenthyl salicylate, phenylbenzimidazole sulfonic acid, methylene bis-benzotriazolyl tetramethylbutylphenol, disodium phenyl dibenzimidazole tetrasulfonate, isoamyl p-methoxycinnamate and ethylhexyl dimethyl PABA and / or is selected from the group of inorganic pigments, comprising in particular activated carbon, talc, iron oxide pigments, titanium dioxide, zinc oxide, silica, cerium oxides, zirconium oxides, aluminium oxides, calcium carbonate, barium sulfate, chromium oxides, manganese oxides, bismuth oxychloride, ultramarine, calcium sulfate and alkali magnesium silicates.

16. Formulation according to Claim 14 or 15, characterized in that component 1) is present in an amount of 0.1% by weight to 20% by weight, preferably of 0.25% by weight to 12% by weight, more preferably of 0.5% by weight to 6% by weight, and component 2) is present in an amount of 0.1% by weight to 60% by weight, preferably of 1% by weight to 50% by weight, more preferably of 3% by weight to 40% by weight.

17. Use of a polyglycerol partial ester according to at least one of Claims 1 to 12 or obtainable according to the method of Claim 13 as a film former, to boost the sun protection factor of UV light protection filter substances or to reduce the rinseability and / or the wear of a formulation from a surface.