Wax esters

Abstract

The invention relates to a method for producing optionally at least partially saponified wax esters, to the corresponding products obtainable by the method according to the invention and to the use thereof in topical applications.

Description

Field of the Invention

[0001] The present invention relates to a process for producing optionally at least partially saponified wax esters, to the corresponding products obtainable by the process of the invention and to their use in topical applications. Prior Art

[0002] Natural waxes are a class of waxes divided into subgroups of vegetable waxes, animal waxes and mineral waxes.

[0003] Examples include cotton wax, carnauba wax, candelilla wax, esparto wax, guaruma wax, Japanese wax, cork wax, lignite wax, microcrystalline waxes, pure ceresin and ozokerite, as well as beeswax, preen gland fat, wool wax, shellac wax and spermaceti wax, and microwaxes, pure ceresin and ozokerite.

[0004] Oxidation of these natural waxes provides wax oxides, also synonymously called acid waxes.

[0005] DE102018116113A1 describes the production of natural wax oxides from rice bran wax and / or sunflower wax having an acid value of >45 mg KOH / g to <70 mg KOH / g and their production process.

[0006] DE102013007638 A1 describes a process for producing acid waxes / wax oxides having an acid value of 100 - 160 mg KOH / g obtained by chromic sulfuric acid oxidation of a mixture of natural wax esters (rice husk wax, carnauba wax, sunflower wax or sugar cane wax) and α-olefins, and the (partial saponification) esters of such acid waxes with monoethylene glycol and butanediol, and their use for producing shoe polish.

[0007] DE10231886A1 describes carnauba wax oxide and its production method. Repeated treatment with chromic sulfuric acid enables the production of an almost white carnauba wax oxide with an increased acid value of ≥60, ≥80, preferably ≥100 mg KOH / g in said method - by at least partial cleavage of wax esters and oxidation of the present alcohols to the corresponding carboxylic acids after purification with dilute sulfuric acid and water. The composition of the thus obtained carnauba wax acid (=carnauba wax oxide) is as follows: wax monocarboxylic acids (about 59%), wax dicarboxylic acids (about 4%) and wax esters (about 33%). The wax monocarboxylic acids in carnauba wax oxide have chains with even and odd carbon atoms from C13 to C34. Monocarboxylic acids mainly having 32 (16.5%) and 24 (11.1%) carbon atoms, and monocarboxylic acids containing 20, 22, 26, 28 and 30 carbon atoms (in each case about 6 - 7%) are also present in similar amounts. In addition, C16 and C18 monocarboxylic acids are present in equal amounts (4.3%), and the other monocarboxylic acids are each in an amount of about 2 - 3%.

[0008] WO2014060081A1 discloses rice bran wax oxide with an acid value of at least 70 mg KOH / g, preferably at least 100 mg KOH / g, more preferably at least 140 mg KOH / g as a raw material for chemical derivatization to produce synthetic ester wax, and its use for the production of (semi)synthetic and partially saponified ester waxes by esterification with one or more monohydric or polyhydric alcohols. Rice bran wax mainly consists of monoesters of long-chain saturated unbranched fatty acids and long-chain unbranched aliphatic alcohols. C22 and C24 are dominant in the acid component, while C26, C28, C30, C32 and C34 are dominant in the alcohol component. Here, when rice bran wax is pre-hydrolyzed under harsh alkaline conditions, chromic acid oxidation results in a high acid value. The said rice bran wax oxide contains free C16 to C36 carboxylic acids, with C24 being the main component, and significant amounts of C22 and C24 are also present. The rice bran wax oxide also contains small amounts (5 - 15%) of aliphatic α,ω-dicarboxylic acids (C10 - C32). Examples of uses include additives in plastic processing (internal and external lubricants, release agents, mold release agents, pigment dispersants), as components of care products (ointments, polishes, emulsions) or cosmetic formulations, as additives for printing inks, for wear protection, as additives for paints for matting or for improving scratch resistance.

[0009] DE2450342 describes mixed oxides of bark wax, the esterification of such mixed oxides with ethylene glycol, and the use of this product for the production of self-polishing emulsions for floors, for the production of shoe cleaners, as a lubricant and release agent for processing polyvinyl chloride, and for the production of hydrophobic emulsions for particle boards.

[0010] DE102013003366A1 describes dimethylaminopropylamides of oxides of natural waxes and their use in cosmetic compositions, in particular hair care products.

[0011] DE102014001709A1 describes combinations of cationic hair treatment agents with dimethylaminopropylamides of oxides of natural waxes and their use in cosmetic formulations, in particular hair care products.

[0012] Commercially available cosmetic film formers for sunscreen and makeup formulations are mainly high molecular weight synthetic / petrochemical-based non-biodegradable polymers such as polyurethanes, polyacrylates, polyolefins, polyvinylpyrrolidone or their corresponding copolymers. Examples thereof are products sold under the trade names Antaron / Ganex (Ashland), Baycusan (Covestro) or SP (Evonik).

[0013] Suitable hydrophilic and thus suitably water-soluble / water-swellable film formers based on natural polymers have also been described and are based on, for example, polysaccharides such as starch, cellulose and their derivatives or polypeptides. However, these do not exhibit good water resistance and also often exhibit insufficient sun protection factor (SPF) enhancing properties in sunscreen or makeup formulations.

[0014] Products based on renewable raw materials are attracting increasing attention from consumers not only from an environmental perspective but also from a toxicological perspective. For example, partial esters of polyols and fatty acids have found diverse application areas in cosmetics and other fields. Corresponding products with "film-forming properties" are already on the market. Examples of these include:

[0015] Syncrowax TM ORM (Croda; INCI: sorbitol / sebacic acid copolymer behenate), Cera Bellina #106 (Koster Keunen; INCI: polyglyceryl-3 beeswax),

[0016] PG1-IS (Surfatech Corp.; INCI: polyglyceryl-3 stearate / isostearate dimer dilinoleate copolymer),

[0017] SurfaCare S (Surfatech Corp.; INCI: polyglyceryl oleate / linoleate / linolenate), LexFilmSun natural (Inolex; INCI: caprylyl glycerin / sebacic acid copolymer), SolAmaze TMNatural polymer (Nouryon; INCI: Diisostearoyl polyglyceryl-3 dimer dilinoleate (and) caprylic / capric triglyceride),

[0018] Pelemol 6GPR (Phoenix Chem; INCI: Polyglyceryl-6 polyricinoleate) and

[0019] Nomcort HK-G (Nisshin Oillio Group; INCI: Behenyl behenate / eicosanedioate), Nomcort HK-P (INCI: Polyglyceryl-10 behenate / eicosanedioate) and Nomcort SG (INCI: Tribehenin / isostearate / eicosanedioate) from Nisshin Oillio Group.

[0020] However, compared to the above synthetic / petrochemical-based polymers, the film-forming properties of all these products are insufficient.

[0021] Due to the diverse possibilities of variation, esters of polyglycerol are a particularly interesting group of products:

[0022] WO2018033259A1 discloses polyglycerol esters obtainable by esterification of 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 fatty acid selected from linear unsaturated and branched saturated fatty acids having 14 to 24 carbon atoms.

[0023] The object of the present invention is to provide excellent film-forming agents, especially for sunscreen formulations.

[0024] Description of the Invention

[0025] Surprisingly, it has been found that the wax esters described below are capable of achieving the object of the present invention.

[0026] The present invention thus provides a method for producing optionally at least partially saponified wax esters.

[0027] The present invention further provides a product obtainable by the method of the present invention and a formulation comprising the same.

[0028] The present invention further provides the use of the wax esters of the present invention.

[0029] One advantage of the present invention is that, unlike the above-mentioned polyacrylates, the wax esters described herein can be prepared entirely from renewable raw materials.

[0030] A further advantage of the present invention is that the wax esters described herein can be prepared based on the principles of green chemistry.

[0031] Another advantage of the present invention is that formulations free of polyethylene glycol ethers can be provided.

[0032] A further advantage of the present invention is that, unlike the above-mentioned polyacrylates, the wax esters described herein are biodegradable.

[0033] A further advantage is that the wax esters described herein have good ecotoxicological characteristics.

[0034] A further advantage of the wax esters according to the present invention is that they are very mild to the skin, non-irritating and non-toxic.

[0035] Another advantage of the wax esters according to the present invention is that they have improved sensory properties in formulations. The viscosity of the sunscreen formulation decreases after application. The formulation is absorbed into the skin more quickly because the absorption increases during application and within 5 minutes thereafter.

[0036] Another advantage of the wax esters according to the present invention is that they impart an enhanced "velvety-silkiness" in formulations.

[0037] A further advantage of the present invention is that the wax esters described herein have good skin moisturizing effects.

[0038] Another advantage of the present invention is that the wax esters described herein confer an increased sun protection factor to sunscreen formulations.

[0039] Another advantage is that the wax esters described herein are very suitable for sunscreen formulations having very high concentrations of ultraviolet protection filters.

[0040] A further advantage of the wax esters according to the present invention is that they confer very high water resistance to formulations. In sunscreen formulations, this ensures extended ultraviolet protection in water or after bathing.

[0041] Another advantage of the wax esters according to the present invention is that when used in cosmetic applications, they impart increased abrasion resistance to color pigments.

[0042] In the case of pigment-containing formulations, a further advantage of the wax esters according to the present invention is that they allow good dispersion of the pigments in the formulations.

[0043] A further advantage of the wax esters according to the present invention is that they have good compatibility with formulations containing ultraviolet protection filters or pigments.

[0044] Generally, the wax esters described herein confer good stability to formulations.

[0045] Another advantage of the wax esters according to the invention is that they are easy to process, since they can be easily mixed with typical cosmetic oils and can be quickly incorporated into the corresponding emulsions.

[0046] A further advantage of the wax esters according to the invention is that they impart a high gloss to solid or waxy formulations such as lipsticks.

[0047] A further advantage of the wax esters according to the invention is that they are particularly resistant to electrolytes, which means that formulations containing a large amount of salt, for example, remain stable.

[0048] A further advantage of the wax esters according to the invention is that they have a structuring and thickening effect in formulations with a high oil content or even in pure oils.

[0049] The present invention provides a method for producing optionally at least partially saponified wax esters, which comprises the following method steps:

[0050] A) providing a natural wax,

[0051] B) oxidizing the natural wax to a natural wax oxide,

[0052] C) esterifying the natural wax oxide with at least one polyol, optionally additionally with at least one selected from monocarboxylic acids and polycarboxylic acids, especially dicarboxylic acids, and optionally

[0053] D) at least partially saponifying the wax ester obtained in method step C),

[0054] provided that if only one polyol is used in method step C), the one polyol has a hydroxyl value of less than 1240 mg KOH / g, preferably less than 1200 mg KOH / g, more preferably less than 1150 mg KOH / g.

[0055] Suitable methods for determining the hydroxyl value are in particular those according to DGF C-V 17a(53), Ph.Eur.2.5.3 Method A and DIN 53240.

[0056] Unless otherwise stated, all specified percentages (%) are by mass.

[0057] The natural waxes provided are preferably obtained from renewable raw material sources, especially those that are non-fossil / petrochemical in origin. Examples of such natural waxes from renewable sources are alfalfa wax, bamboo wax, cotton wax, beeswax, candelilla wax, caranday wax, carnauba wax, dammar wax, Douglas fir wax, esparto wax, flax wax, hemp wax, coffee wax, cork wax, oleander wax, microcoelum wax, raffia wax, rice wax, rice bran wax, retamo wax, bark wax, sisal wax, tea wax, wool wax, and sugarcane wax, with carnauba wax being particularly preferred.

[0058] The natural waxes provided preferably have a high content of wax esters. Based on the total natural wax, the proportion of the corresponding fatty oil component (e.g., rice bran oil in the case of rice wax) should not be greater than 50% by weight, preferably not greater than 30% by weight, more preferably not greater than 5% by weight.

[0059] Preferably, the natural waxes provided contain, in total, 0.05% to 35% by weight, preferably 0.1% to 25% by weight, more preferably 1.0% to 20% by weight of aliphatic ω-hydroxycarboxylic acids and / or aliphatic α,ω-alkanediols and / or esters of aliphatic ω-hydroxycarboxylic acids and / or esters of aliphatic α,ω-alkanediols, where the weight percentages are based on the total natural wax.

[0060] Preferably, the aliphatic monocarboxylic acids present in the wax esters of the natural waxes provided have a chain length of C20 or higher to an extent of 10% to 98% by weight, preferably 20% to 95% by weight, more preferably 30% to 90% by weight, based on all the aliphatic monocarboxylic acids present.

[0061] Preferably, the ω-hydroxycarboxylic acids present in the wax esters of the natural waxes provided have a chain length of C24 or higher to an extent of 0.1% to 50% by weight, preferably 1% to 45% by weight, more preferably 10% to 40% by weight, based on all the ω-hydroxycarboxylic acids present.

[0062] The natural waxes provided may also contain phospholipids, sterol derivatives, sterol esters, oryzanol, tocotrienols, glycolipids, and / or squalene, more particularly in a total amount of less than 12% by weight, preferably less than 5% by weight, more preferably less than 2% by weight, and particularly preferably less than 1% by weight, based on the total weight of the natural waxes provided.

[0063] In method step B) of the method according to the invention, the natural waxes provided are preferably oxidized under at least partial cleavage of the wax esters present in the natural waxes provided.

[0064] During the oxidation process, the primary alcohols present in the reaction mixture are at least partially oxidized to the corresponding carboxylic acids.

[0065] Preferably, process step B) of the method according to the invention is carried out in two or more stages, for example initially by at least partial saponification and / or (preferably alkaline) hydrolysis and subsequent oxidation.

[0066] The oxidation of the natural wax in process step B) of the method according to the invention can be carried out in one or more stages. The oxidation process can be carried out in the presence of an oxidation promoter (preferably not more than 10% by weight, preferably not more than 5% by weight, more preferably not more than 1% by weight, based on the total reaction mixture). The oxidation promoter accelerates the oxidation by phase transfer, ester activation or by catalysis by virtue of its chemical properties. Suitable examples include those described in WO2014060082A1 and the documents cited therein.

[0067] Preferably, the oxidation process in process step B) of the method according to the invention is carried out by mechanical dispersion (e.g., with ultrasound, dissolution disks, etc.). Preferably, the oxidation in process step B) of the method according to the invention is carried out with chromic sulfuric acid.

[0068] Equally very suitable alternative methods to chromic sulfuric acid oxidation are described, for example, in WO2020025813A1 (oxidation by oxoammonium cations and a co-oxidant) and WO2020025814A1 (preliminary saponification and subsequent oxidation by aminooxy radicals and co-oxidants such as chlorites and bromites).

[0069] When metal-catalyzed oxidation has been carried out in process step B) of the method according to the invention, the metal soaps present are preferably removed by washing (e.g., with an aqueous solution of oxalic acid and sulfuric acid) or centrifugation before further reaction.

[0070] In the case of chromium salts, the purity of the wax oxides of the present invention preferably complies with the specifications of the German Pharmacopoeia regarding Ceramontanglycoli.

[0071] In process step B) of the method according to the invention, two or more natural waxes can be provided.

[0072] In process step B) of the method according to the invention, it is also possible to add other esters, diesters, paraffins, monofunctional and polyfunctional carboxylic acids, fatty alcohols, aldehydes and / or other substances that provide the corresponding oxides under the conditions to the natural waxes provided.

[0073] Therefore, the chain distribution of aliphatic monocarboxylic acids and aliphatic α,ω-dicarboxylic acids in the resulting mixed oxides can be significantly different from the chain distribution of pure natural wax oxides.

[0074] The cleavage of wax esters and subsequent oxidation of the hydroxyl groups of wax alcohols or ω-hydroxycarboxylic acids or oxidative cleavage of unsaturated components (such as unsaturated carboxylic acids) results in an increase in the saponification value (SV) of the natural wax oxides obtained thereby.

[0075] According to the invention, preferably, the natural wax oxide obtained in process step B) of the process according to the invention has a saponification value of 60 to 260 mg KOH / g, preferably 80 to 240 mg KOH / g, more preferably 100 to 220 mg KOH / g.

[0076] Suitable 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.

[0077] The proportion of true wax esters, i.e., esters not affected by the cleavage and subsequent oxidation of wax esters, is preferably less than 65% by weight, more preferably less than 50% by weight, particularly preferably less than 40% by weight, and especially preferably less than 30% by weight, where the weight percentages are based on the total natural wax oxide.

[0078] According to the invention, preferably, the natural wax oxide obtained in process step B) of the process according to the invention has an acid value (AV) of 30 to 200 mg KOH / g, preferably 50 to 190 mg KOH / g, more preferably 70 to 180 mg KOH / g.

[0079] Suitable methods for determining the acid value are in particular those according to DGF C-V 2, DIN ENISO 2114, Ph.Eur.2.5.1, ISO 3682 and ASTM D 974.

[0080] According to the invention, preferably, the natural wax oxide obtained in process step B) of the process according to the invention is characterized by a very low content of unsaturated and / or aromatic compounds. Thus, the natural wax oxide obtained in process step B) of the process according to the invention preferably has an iodine value (IV) of ≤40 g I2 / 100 g, preferably ≤20 g I2 / 100 g, more preferably ≤10 g I2 / 100 g, and particularly preferably ≤5 g I2 / 100 g.

[0081] A suitable method for determining the iodine value in the present invention is EN 14111:2003.

[0082] According to the invention, preferably, the natural wax oxide obtained in process step B) of the process according to the invention is characterized in that the dropping point measured according to DINISO 2176 is between 40 °C and 130 °C, preferably between 50 °C and 105 °C, more preferably between 70 °C and 90 °C, and particularly preferably between 75 °C and 87 °C.

[0083] According to the present invention, preferably, the natural wax oxide obtained in method step B) of the method according to the present invention has a content of aliphatic monocarboxylic acids with a chain length of 8 to 34 carbon atoms of 30 to 90% by weight, preferably 40 to 80% by weight, more preferably 50 to 70% by weight, where the weight percentages are based on all aliphatic monocarboxylic acids and aliphatic α,ω-dicarboxylic acids present in the natural wax oxide.

[0084] According to the present invention, preferably, the natural wax oxide obtained in method step B) of the method according to the present invention has a content of aliphatic α,ω-dicarboxylic acids with a chain length of 8 to 34 carbon atoms of 1 to 40% by weight, preferably 2 to 35% by weight, more preferably 20 to 30% by weight, where the weight percentages are based on all aliphatic monocarboxylic acids and α,ω-dicarboxylic acids present in the natural wax oxide. This proportion of aliphatic α,ω-dicarboxylic acids can directly originate from the natural wax (e.g., by cleavage and in-situ oxidation of esters of present aliphatic α,ω-diols, cleavage and in-situ oxidation of esters of present ω-hydroxycarboxylic acids, or oxidative cleavage of unsaturated components such as oleic acid esters or the like) and / or by cleavage and in-situ oxidation of added components (oils, glycerides, etc., see below), and / or they can be added before further reactions (e.g., addition of sebacic acid or the like).

[0085] According to the present invention, preferably, the natural wax oxide obtained in method step B) of the method according to the present invention has a total content of aliphatic α,ω-dicarboxylic acids with a chain length of 8 to 34 carbon atoms and aliphatic monocarboxylic acids with a chain length of 8 to 34 carbon atoms of greater than 60% by weight, preferably greater than 70% by weight, more preferably greater than 80% by weight, where the weight percentages are based on the total natural wax oxide.

[0086] According to the present invention, preferably, the natural wax oxide obtained in method step B) of the method according to the present invention has a content of aliphatic monocarboxylic acids with a chain length of 20 or more carbon atoms of at least 40% by weight, preferably at least 60% by weight, more preferably at least 80% by weight, where the weight percentages are based on all aliphatic monocarboxylic acids present in the natural wax oxide.

[0087] According to the present invention, preferably, the natural wax oxide obtained in method step B) of the method according to the present invention has a content of aliphatic monocarboxylic acids with an odd chain length of 9 to 29 carbon atoms of at least 0.01% by weight, preferably at least 0.5% by weight, more preferably at least 5.0% by weight, particularly preferably at least 10.0% by weight, where the weight percentages are based on all aliphatic monocarboxylic acids present in the natural wax oxide.

[0088] According to the invention, preferably, the natural wax oxide obtained in process step B) of the process according to the invention has a content of aliphatic α,ω-dicarboxylic acids with a chain length of 12 to 29 carbon atoms of more than 50% by weight, preferably more than 60% by weight, even more preferably more than 80% by weight, where the percentages by weight are based on all aliphatic α,ω-dicarboxylic acids present in the natural wax oxide.

[0089] According to the invention, preferably, the natural wax oxide obtained in process step B) of the process according to the invention has a content of aliphatic α,ω-dicarboxylic acids with a chain length of 18 or more carbon atoms of more than 20% by weight, preferably more than 40% by weight, even more preferably more than 60% by weight, where the percentages by weight are based on all aliphatic α,ω-dicarboxylic acids present in the natural wax oxide.

[0090] According to the invention, preferably, the natural wax oxide obtained in process step B) of the process according to the invention has a content of aliphatic α,ω-dicarboxylic acids with an odd chain length of 9 to 29 carbon atoms of at least 0.01% by weight, preferably at least 0.5% by weight, even more preferably at least 5.0% by weight, particularly preferably at least 10.0% by weight, where the percentages by weight are based on all aliphatic α,ω-dicarboxylic acids present in the natural wax oxide.

[0091] The above percentages by weight of aliphatic monocarboxylic acids and α,ω-dicarboxylic acids are always determined as relative GC area percentages according to the following method:

[0092] The distribution of aliphatic monocarboxylic acids and α,ω-dicarboxylic acids in the sample to be analyzed can be determined by GC.

[0093] This method involves the derivatization of the wax oxide and subsequent simultaneous determination by GC / FID. If the distribution of aliphatic monocarboxylic acids and α,ω-dicarboxylic acids in wax esters is to be determined, the wax esters need to be hydrolyzed alkaline first. For this purpose, an initial charge of 150 mg of the wax ester to be analyzed in 2.00 ml of 1 M aqueous KOH is hydrolyzed at 95 °C with stirring for 30 minutes. The reaction solution is then cooled to room temperature and adjusted to pH 2 - 3 with 2 M aqueous HCl. The carboxylic acids thus precipitated are then extracted with diethyl ether (3 × 3.00 ml), and the extract is concentrated to dryness by evaporation.

[0094] Then, 0.05 g of this extract or wax oxide is dissolved in 10 ml of toluene to form a clear solution while heating to 60 °C. 0.25 ml of the still warm clear solution is mixed with 0.5 ml of BSTFA [N,O-bis(trimethylsilyl)trifluoroacetamide] and 0.05 ml of TMCS [trimethylchlorosilane]. The aliphatic monocarboxylic acids and aliphatic α,ω-dicarboxylic acids are quantitatively converted into their trimethylsilyl esters at 80 °C within 30 minutes and then analyzed by GC / FID.

[0095] This was carried out in a gas chromatograph equipped with a column injector, a capillary column, and a flame ionization detector under the following conditions:

[0096] Injector: CoC, Track Oven

[0097] Injection volume: 0.5 μl

[0098] Column: 30 m * 0.32 mm DB5-HT 0.1 μm

[0099] Carrier gas: Hydrogen, constant flow rate, 2 ml / min

[0100] Temperature program: 65 °C at 10 °C / min to 365 °C

[0101] Then held at 365 °C for 15 minutes.

[0102] Detector: FID at 365 °C

[0103] Hydrogen 35 ml / min

[0104] Air 240 ml / min

[0105] Make-up gas 12 ml / min

[0106] The aliphatic monocarboxylic acids and aliphatic α,ω-dicarboxylic acids present in the sample are separated according to chain length. Peaks are assigned by comparison with the retention times of the corresponding commercially available aliphatic monocarboxylic acids and aliphatic α,ω-dicarboxylic acids.

[0107] The relative proportions of the individual acids can be determined by evaluating the respective peak areas.

[0108] In process step C), the natural wax oxide is esterified with at least one polyol, provided that if only one polyol is used in process step C), the one polyol has a hydroxyl value of less than 1240 mg KOH / g, preferably less than 1200 mg KOH / g, more preferably less than 1150 mg KOH / g.

[0109] Suitable reaction conditions for process step C) are a temperature between 120 °C and 260 °C and atmospheric pressure or a reduced pressure in the range between 20 mbar and 800 mbar, especially between 50 and 500 mbar. Process step C) can be carried out in the presence of a catalytic amount of a base or a catalytic amount of an acid, the base being especially selected from metal hydroxides, metal oxides, and metal carbonates such as NaOH, Ca(OH)2, KOH, Zn(OH)2, CaO, ZnO, Na2CO3, CaCO3, or K2CO3, the acid being especially sulfuric acid, phosphoric acid, hypophosphorous acid, methanesulfonic acid, ethanesulfonic acid, or p-toluenesulfonic acid. Corresponding methods can be found in standard chemistry textbooks, such as

[0110] A preferred method according to the invention is characterized in that the at least one polyol has three or more, preferably four or more, in particular more than six carbon atoms. In the case of using a plurality of polyols, it goes without saying that the mixture should have on average three or more, preferably four or more, in particular more than six carbon atoms.

[0111] In the case of using a plurality of polyols, according to the invention it is preferred that such a mixture has a hydroxyl value of less than 1240 mg KOH / g, preferably less than 1200 mg KOH / g, more preferably less than 1150 mg KOH / g.

[0112] A preferred method according to the invention is characterized in that the at least one polyol comprises polyglycerol, wherein, based on all polyols, polyglycerol preferably constitutes at least 20% by weight, preferably at least 40% by weight, more preferably at least 60% by weight, in particular preferably at least 80% by weight.

[0113] For the purposes of the present invention, the term "polyglycerol" is understood to mean polyglycerol which may also contain glycerol. Thus, any glycerol component should also be taken into account when calculating amounts, masses, etc. Its polymerization characteristics mean that polyglycerol is a statistical mixture of various compounds. Polyglycerol may have ether bonds between two primary positions, one primary position and one secondary position or two secondary positions of glycerol monomers. The polyglycerol backbone is thus usually not composed entirely of linearly linked glycerol units, but may also contain branches and rings. For details see, for example, "Original synthesis of linear, branched and cyclicoligoglycerol standards", Cassel et al., J. Org. Chem. 2001, 875-896.

[0114] According to the invention it is preferred that the average degree of polymerization of the polyglycerol used in step C) is from 2 to 20, preferably from 2.5 to 16, most preferably from 3 to 12.

[0115] For the calculation, the average degree of polymerization of polyglycerol <n>From the hydroxyl value (OHV, in mg KOH / g) according to the formula <n>= (112200 – 18*OHV) / (74*OHV – 56100) calculation.

[0116] A preferred method according to the invention is characterized in that the polyglycerol present in the at least one polyol has a content of cyclic oligomers (i.e., oligomers containing one or more rings) of 1.0 wt% to 50 wt%, preferably 2.0 wt% to 40 wt%, more preferably 3.0 wt% to 30 wt%.

[0117] In process step C) of the method according to the invention, the additional polyols preferably used are selected from:

[0118] Decane-1,10-diol, dodecane-1,12-diol, hexane-1,2-diol, octane-1,2-diol, 1,2-pentanediol, 1,4-bis(hydroxymethyl)cyclohexane, pentane-1,5-diol, 2,2,4-trimethylpentane-1,3-diol, 2,2-bis(4-hydroxycyclohexyl)propane, 2,2-dimethylpropane-1,3-diol (neopentyl glycol), 2,4-diethylpentane-1,5-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 2-butyl-2-ethylpropane-1,3-diol, 2-ethylhexane-1,3-diol, 2-methylpropane-1,3-diol, 2-methyl-2-propylpropane-1,3-diol, 2-sec-butyl-2-methylpropane-1,3-diol, 3-hexyne-2,5-diol, ditrimethylolpropane, isosorbide, pinacol, tricyclodecane dimethanol, and tripentaerythritol.

[0119] In process step C) of the method according to the invention, the additional polyols preferably used together with at least one additional polyol are selected from:

[0120] 1,2-Butanediol, 1,2-propanediol, 1,3-butanediol, propane-1,3-diol, butane-1,4-diol, 1,4-sorbitan, 1,5-sorbitan, diglycerol, dipentaerythritol, erythritol, glycerol, isomalt, lactitol, maltitol, mannitol, pentaerythritol, sorbitol, trimethylolethane, trimethylolpropane, xylitol, and xylitol.

[0121] In process step C) of the method according to the invention, the natural wax oxide is optionally additionally esterified with at least one selected from monocarboxylic acids and polycarboxylic acids, especially dicarboxylic acids, more preferably aliphatic α,ω-dicarboxylic acids with a chain length of 8 to 34 carbon atoms and aliphatic monocarboxylic acids with a chain length of 8 to 34 carbon atoms.

[0122] This can be achieved by simply adding the acid (e.g., from other natural waxes, fats, oils, fatty acid partial esters, or the acid itself) from an acyl donor.

[0123] In optional method step D) of the method according to the invention, the wax esters obtained in method step C) are at least partially saponified.

[0124] For this purpose, water and preferably an alkali metal hydroxide such as NaOH, KOH, Ca(OH)2 and Zn(OH)2, a metal oxide such as CaO, a metal carbonate such as Na2CO3 and CaCO3 and / or an aqueous alkali solution are added to the wax esters, and the mixture thus obtained is saponified and optionally then dried under reduced pressure, in particular at a temperature above the melting point of the wax esters concerned, preferably between 70 and 100 °C, preferably with stirring.

[0125] The invention further provides optionally at least partially saponified wax esters obtainable by the method according to the invention.

[0126] These have the surprising property of being able to structure oils particularly well and also enhance the UV filtering effect of light protection filters.

[0127] The preferred optionally at least partially saponified wax esters of the invention correspond in their preferred degree to the corresponding preferred methods of the invention that can be used to obtain them.

[0128] These optionally at least partially saponified wax esters of the invention have an excellent use profile in cosmetic formulations.

[0129] The invention accordingly further provides formulations, in particular cosmetic formulations, especially for topical application, which comprise the optionally at least partially saponified wax esters of the invention.

[0130] Formulations according to the invention preferably comprise the optionally at least partially saponified wax esters of the invention shown above as preferred.

[0131] Preferably, the formulations according to the invention additionally comprise at least one substance selected from UV protection filter substances and pigments, in particular UV protection filter substances.

[0132] The UV protection filter substances present can be, for example, organic substances capable of absorbing ultraviolet radiation and re-emitting the absorbed energy in the form of longer wavelength radiation (such as heat).

[0133] UVB filters can be oil-soluble or water-soluble. Examples of oil-soluble UVB light protection filters include:

[0134] 3-benzylidene camphor derivatives such as 3-(4-methylbenzylidene) camphor (INCI: 4-Methylbenzylidene camphor), 4-aminobenzoic acid derivatives such as 2-ethylhexyl 4-(dimethylamino) benzoate (INCI: Diethylhexyl PABA), 2-hydroxyethyl 4-{bis[2-(2-hydroxyethoxy)ethyl]amino} benzoate (INCI: PEG-25 PABA), cinnamic acid esters such as 2-ethylhexyl 4-methoxycinnamate (INCI: Ethylhexyl methoxycinnamate), isopentyl 4-methoxycinnamate (INCI: Isoamyl p-methoxycinnamate), 2-ethylhexyl 2-cyano-3,3-diphenylacrylate (INCI: Octocrylene), salicylic acid esters such as 2-ethylhexyl salicylate (INCI: Ethylhexyl salicylate), menthyl salicylate (INCI: Menthol salicylate), 3,3,5-trimethylcyclohexyl salicylate (INCI: Homosalate), triethanolamine 2-hydroxybenzoate (1:1) (INCI: TEA-salicylate), benzophenone derivatives such as 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 such as tris(2-ethylhexyl) 4,4',4''-(1,3,5-triazine-2,4,6-triyltris(imino))tribenzoate (INCI: Ethylhexyl triazone, for example available from BASF under the trade name Uvinul T 150), iscotrizinol (INCI: Diethylhexyl butamido triazone) and 2,4,6-tris(4-biphenylyl)-1,3,5-triazine (INCI: Triclosan).

[0135] An additional UVB filter is (3-(4-(2,2-bis(ethoxycarbonyl)vinyl)phenoxy)allyl)methoxysiloxane / dimethylsiloxane copolymer (INCI: Polysilicone-15), which is available, for example, under the trade name Parsol SLX.

[0136] Useful water-soluble UVB sunscreen filters include, for example:

[0137] Salts of 2 - phenylbenzimidazole - 5 - sulfonic acid, such as its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium, and glucammonium salts, as well as the sulfonic acid itself with the INCI name phenylbenzimidazole sulfonic acid, sulfonic acid derivatives of benzophenone, such as 5 - benzoyl - 4 - hydroxy - 2 - methoxybenzenesulfonic acid (INCI: benzophenone - 4) and its salts, benzenesulfonic acid derivatives of 3 - benzylidenecamphor, such as 4 - [(E)-(4,7,7 - trimethyl - 3 - oxobicyclo[2.2.1]hept - 2 - ylidene)methyl]benzenesulfonic acid (INCI: benzylidenecamphorsulfonic acid) and its salts.

[0138] Examples of typical oil - soluble UVA / broad - band photoprotective filters that can be used include derivatives of benzoylmethane, such as 1 - (4 - methoxyphenyl)-3 - [4-(2 - methyl - 2 - propyl)phenyl]-1,3 - propanedione (INCI: butyl methoxydibenzoylmethane) or 1 - (4 - isopropylphenyl)-3 - phenyl - 1,3 - propanedione (INCI: isopropyl dibenzoylmethane), triazine derivatives, such as 2,2'-[6-(4 - methoxyphenyl)-1,3,5 - triazine - 2,4 - diyl]bis{5 - [(2 - ethylhexyl)oxy]phenol} (INCI: bis - ethylhexyloxyphenol methoxyphenyl triazine, which can be obtained from BASF under the trade name Tinosorb S), 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, which can be obtained from 3V Sigma under the trade name Uvasorb K2A), and derivatives of benzophenone, such as 2 - (4 - diethylamino - 2 - hydroxybenzoyl)benzoic acid hexyl ester (INCI: diethylamino hydroxybenzoyl hexyl benzoate).

[0139] Water - soluble UVA / broad - band photoprotective filters that can be used include, for example: 3,3'-(1,4 - phenylenedimethylene)-bis(7,7 - dimethyl - 2 - oxobicyclo[2.2.1]hept - 1 - ylmethanesulfonic acid) and its salts, especially the corresponding sodium, potassium, or triethanolammonium salts, which are also described as benzene - 1,4 - bis(2 - oxo - 3 - norbornylidene methyl - 10 - sulfonic acid) and have the INCI name terephthalylidene dicamphor sulfonic acid (which can be obtained under the trade name Mexoryl SX), 2,2'-(1,4 - phenylene)-bis(6 - sulfo - 1H - benzimidazole - 4 - sulfonic acid) and its salts, the corresponding sodium, potassium, or triethanolammonium salts, such as disodium 2,2'-(1,4 - phenylene)-bis(6 - sulfo - 1H - benzimidazole - 4 - sulfonic acid), which has the INCI name phenyl dibenzimidazole tetrasulfonic acid disodium and the trade name, for example, NeoHeliopan AP.

[0140] Examples of other UVA / broadband filters are, for example, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(2,4,4-trimethyl-2-pentyl)phenol] (INCI: methylene bis-benzotriazolyl tetramethylbutylphenol, which can be obtained, 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: cresol triazone, 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).

[0141] The UV protection filter substances can of course also be present in the composition according to the invention in a mixed form.

[0142] In addition to the soluble UV protection filter substances mentioned, insoluble pigments can also be used for this purpose, namely finely divided metal oxides or salts, such as titanium dioxide, zinc oxide, iron oxide, aluminium oxide, cerium oxide, zirconium oxide, silicates (talc), barium sulphate and zinc stearate. The particles should here have an average diameter of less than 100 nm, for example between 5 and 50 nm, especially between 15 and 30 nm. They can be spherical, but particles with an oval shape or a shape deviating from the spherical in another way can also be used. However, micronised organic pigments are also possible, such as 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(2,4,4-trimethyl-2-pentyl)phenol] (INCI: methylene bis-benzotriazolyl tetramethylbutylphenol, which can be obtained, for example, under the trade name Tinosorb M from BASF) with a particle size < 200 nm, which is available, for example, as a 50% aqueous dispersion.

[0143] In addition, further suitable UV protection filter substances can be found in the review by P. Finkel in Journal, 122, 543 (1996), and in the chapter "The Chemistry of Ultraviolet Filters" by N. A. Shaath in "Principles and Practice of Photoprotection", S. Q. Wang and H. W. Lim (editors), Springer International Publishing, Switzerland, 2016.

[0144] According to a preference of the present invention, the formulation according to the present invention comprises at least two, preferably at least three, more preferably at least four ultraviolet protection filter substances.

[0145] According to a preference of the present invention, the at least one ultraviolet protection filter substance in the formulation according to the present invention is selected from organic ultraviolet protection filter substances, in particular from triazine derivatives.

[0146] According to a particularly preferred embodiment of the present invention, the at least one ultraviolet protection filter substance in the formulation according to the present invention is selected from the group of ultraviolet protection filter substances comprising, preferably consisting of, the following:

[0147] Butyl methoxydibenzoylmethane,

[0148] Ethylhexyl triazone,

[0149] Bis-ethylhexyloxyphenol methoxyphenyl triazine,

[0150] Diethylhexyl butamido triazone,

[0151] Diethylamino hydroxybenzoyl hexyl benzoate,

[0152] Benzophenone-3,

[0153] Benzophenone-4,

[0154] 4-Methylbenzylidene camphor,

[0155] Octocrylene,

[0156] Ethylhexyl methoxycinnamate,

[0157] Ethylhexyl salicylate,

[0158] Homomenthyl salicylate,

[0159] Phenylbenzimidazole sulfonic acid,

[0160] Methylene bis-benzotriazolyl tetramethylbutylphenol,

[0161] Disodium phenyl dibenzimidazole tetrasulfonate,

[0162] Isoamyl p-methoxycinnamate,

[0163] Dimethyl PABA ethylhexyl ester.

[0164] According to a further preference of the present invention, the at least one UV protection filter substance in the formulation according to the present invention is selected from pigments, including 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 oxide, zirconium oxide, aluminum oxide, calcium carbonate, barium sulfate, calcium sulfate, alkali metal magnesium silicate or mixtures thereof.

[0165] Examples of organic pigments can be: carotenoids, chlorophyll, lutein, caramel and salts of the listed examples, as well as colorants obtained from plant fruits or other plant parts, such as those obtained from oranges, cocoa, turmeric, shea butter, sandalwood, onions, carob fruits, red peppers, corn, tomatoes, beetroot, peanuts, grapes, red cabbage, red rice, radishes, elderberries, bilberries, blueberries, raspberries, blackberries, boysenberries, currants, cranberries, saffron, strawberries, cherries, tea, hibiscus, plums, blueberries or mulberries. Also suitable as coloring pigments are substances, for example, that are approved and suitable for cosmetic purposes, such as those listed in the publication "Kosmetische " [Cosmetic colorants], Verlag Chemie, Weinheim, 1984, pages 81 to 106.

[0166] According to a further preference of the present invention, when the formulation according to the present invention contains at least one selected from UV protection filter substances, the formulation further contains a pigment selected from titanium dioxide and zinc oxide. In this regard, the preferably present UV protection filter substances correspond to the preferably mentioned UV protection filter substances above.

[0167] The preferred formulation according to the present invention is characterized in that the optionally at least partially saponified wax esters according to the present invention are present in the formulation according to the present invention in an amount of 0.1% to 20% by weight, preferably 0.25% to 12% by weight, more preferably 0.5% to 6% by weight, where the weight percentages are based on the total formulation.

[0168] The preferred formulation according to the present invention is characterized in that at least one UV protection filter substance in the formulation according to the present invention is present in an amount of 0.1% to 60% by weight, preferably 1% to 50% by weight, more preferably 10% to 40% by weight, where the weight percentages are based on the total formulation.

[0169] The formulation according to the present invention can contain, for example, at least one further additional component selected from

[0170] Emollient

[0171] Co - emulsifier

[0172] Thickener / Viscosity regulator / Stabilizer

[0173] Antioxidant

[0174] Hydrotrope (or polyol)

[0175] Solids and fillers

[0176] Pearlescent additive and opacifier

[0177] Insect repellent

[0178] Self - tanning agent

[0179] Preservative

[0180] Conditioner

[0181] Fragrance

[0182] Colorant

[0183] Cosmetic active substance

[0184] Care additive

[0185] Superfatting agents

[0186] Solvent

[0187] Substances that can be used as exemplary representatives of each category are known to those skilled in the art and can be taken, for example, from German application DE 102008001788.4. This patent application is incorporated herein by reference and is thus considered to form part of this disclosure.

[0188] Regarding further optional components and the amounts of these components, express reference is made to relevant handbooks known to those skilled in the art, such as K. Schrader, "Grundlagen und Rezepturen der Kosmetika” [Fundamentals and formulations of cosmetics], 2nd edition, pages 329 to 341, Hüthig Buch Verlag, Heidelberg.

[0189] The amount of each additive depends on the intended use.

[0190] Typical starting formulations for related applications are known in the prior art and are included, for example, in the manufacturer's manuals of related bases and active substances. These existing formulations can generally be used as they are. However, any desired modifications required for adjustment and optimization can be made in a straightforward manner by simple experiments.

[0191] The formulations according to the invention can be used, for example, in the form of emulsions, suspensions, solutions, creams, ointments, pastes, gels, oils, powders, aerosols, sticks, sprays, cleaning products, cosmetic products or sunscreen products.

[0192] The invention further provides the use of the optionally at least partially saponified wax esters of the invention for the production of formulations, in particular formulations for topical application, in particular cosmetic formulations, in particular sunscreen formulations.

[0193] The invention further provides the use of the optionally at least partially saponified wax esters of the invention as film-forming agents.

[0194] The invention further provides the use of the optionally at least partially saponified wax esters of the invention for enhancing the sun protection factor of ultraviolet protection filter substances.

[0195] The invention further provides the use of the optionally at least partially saponified wax esters of the invention for reducing the rinsability and / or abrasion of formulations from surfaces.

[0196] In the uses according to the invention, it is preferred to use the components mentioned above in the context of the formulations according to the invention as the components preferably present.

[0197] The following examples illustrate the invention by way of example and are not intended to limit the invention to the embodiments specified in the examples, the scope of application of the invention being apparent from the entire specification and the claims. Examples

[0198] Example 001 (of the invention):

[0199] A mixture of commercially available polyglycerol-3 from Spiga Nord (OHV = 1100 mg KOH / g, 50.0 g) and commercially available natural wax oxide -cos K-4419 (AV = 138 mg KOH / g, SV = 172 mg KOH / g, 295.9 g) was heated to 240 °C with stirring and N2 passing through, and the water formed was continuously distilled off until an acid value of 2.5 mg KOH / g was reached. The melting point of the product was 83 °C and the saponification value was 159 mg KOH / g.

[0200] Example 002 (of the invention):

[0201] A mixture of commercially available polyglycerol-3 from Spiga Nord (OHV = 1100 mg KOH / g, 30.3 g) and commercially available natural wax oxide from Voelpker -cos K-4419 (AV = 138 mg KOH / g, SV = 172 mg KOH / g, 89.7 g) was heated to 240 °C with stirring and N₂ passing through, and the water formed was continuously distilled off until an acid value of 2.1 mg KOH / g was reached. The melting point of the product was 80 °C and the saponification value was 139 mg KOH / g.

[0202] Example 003 (of the present invention):

[0203] A mixture of commercially available polyglycerol-3 from Spiga Nord (OHV = 1100 mg KOH / g, 50.0 g) and commercially available natural wax oxide from Voelpker -cos K-4419 (AV = 138 mg KOH / g, SV = 172 mg KOH / g, 74.0 g) was heated to 240 °C with stirring and N₂ passing through, and the water formed was continuously distilled off until an acid value of 1.2 mg KOH / g was reached. The melting point of the product was 80 °C and the saponification value was 109 mg KOH / g.

[0204] Example 004 (of the present invention):

[0205] A mixture of commercially available polyglycerol-3 from Spiga Nord (OHV = 1100 mg KOH / g, 21.4 g) and commercially available natural wax oxide from Voelpker -cos K-4419 (AV = 138 mg KOH / g, SV = 172 mg KOH / g, 98.6 g) was heated to 240 °C with stirring and N₂ passing through, and the water formed was continuously distilled off until an acid value of 2.5 mg KOH / g was reached. The melting point of the product was 80 °C and the saponification value was 151 mg KOH / g.

[0206] Example 005 (of the present invention):

[0207] A mixture of commercially available polyglycerol-6 from Spiga Nord (OHV = 989 mg KOH / g, 80.6 g) and commercially available natural wax oxide from Voelpker A mixture of -cos K-4419 (AV = 138 mg KOH / g, SV = 172 mg KOH / g, 119.4 g) was heated to 240 °C with stirring and N₂ passing through, and the water formed was continuously distilled off until an acid value of 2.3 mg KOH / g was reached. The melting point of the product was 80 °C and the saponification value was 109 mg KOH / g.

[0208] Example 006 (of the present invention):

[0209] A mixture of commercially available polyglycerol-6 from Spiga Nord (OHV = 989 mg KOH / g, 50.5 g) and commercially available natural wax oxide from Voelpker -cos K-4419 (AV = 138 mg KOH / g, SV = 172 mg KOH / g, 149.5 g) was heated to 240 °C with stirring and N₂ passing through, and the water formed was continuously distilled off until an acid value of 2.3 mg KOH / g was reached. The melting point of the product was 80 °C and the saponification value was 138 mg KOH / g.

[0210] Example 007 (of the present invention):

[0211] A mixture of commercially available polyglycerol-3 from Spiga Nord (OHV = 1116 mg KOH / g, 34.0 g), commercially available natural wax oxide from Voelpker -cos K-4419 (AV = 138 mg KOH / g, SV = 172 mg KOH / g, 100.8 g) and behenic acid (92%, AV = 165 mg KOH / g, 65.2 g) was heated to 240 °C with stirring and N₂ passing through, and the water formed was continuously distilled off until an acid value of 2.0 mg KOH / g was reached. The melting point of the product was 72 °C and the saponification value was 159 mg KOH / g.

[0212] Example 008 (of the present invention):

[0213] A mixture of commercially available polyglycerol-3 from Spiga Nord (OHV = 1116 mg KOH / g, 49.1 g), commercially available natural wax oxide from Voelpker -cos K-4419 (AV = 138 mg KOH / g, SV = 172 mg KOH / g, 145.5 g) and sebacic acid (99%, 5.4 g) was heated to 240 °C with stirring and N₂ passing through, and the water formed was continuously distilled off until an acid value of 0.7 mg KOH / g was reached. The melting point of the product was 83 °C and the saponification value was 150 mg KOH / g.

[0214] Example 16a-i (not of the present invention):

[0215] a. SP 13 SunUp MB (Evonik, INCI: C10 - 30 alkyl acrylate)

[0216] b. Antaron V - 220 (Ashland, INCI: VP / eicosene copolymer)

[0217] c. PDI (Evonik, INCI: diisostearoyl polyglyceryl - 3 dimer dilinoleate)

[0218] d. GPS (Evonik, INCI: polyglyceryl - 4 diisostearate / polyhydroxystearate / sebacate)

[0219] e. Cera Bellina #106 (Koster Keunen; INCI: polyglyceryl - 3 beeswax),

[0220] f. CosmoSurf PG1 - IS (Surfatech Corp.; INCI: polyglyceryl - 3 stearate / isostearate dimer dilinoleate copolymer),

[0221] g. LexFilm TM Sun Natural MB (Inolex, INCI: caprylyl glycerin / sebacic acid copolymer)

[0222] h. Polyglycerol ester according to Example 1 of WO2018033259

[0223] i. Polyglycerol ester according to Example 14 of WO2018033259

[0224] Application Example 101: In vitro SPF enhancement test of cosmetic formulations

[0225] Compared with the esters not of the present invention or the commercial products not of the present invention sold as film - forming agents, the wax esters according to the present invention are characterized by a strong film - forming tendency. The film - forming property in sunscreen formulations can be quantitatively demonstrated by an in vitro SPF test.

[0226] This was carried out by preparing an O / W sunscreen emulsion on a laboratory scale of 200 g, in which various film - forming agents were incorporated in the same way each time according to the following formulation (Table 1). The emulsion was prepared according to the methods commonly known to those skilled in the art for producing lotions.

[0227] Table 1: Composition of O / W sunscreen emulsion for in vitro determination of SPF

[0228]

[0229] 24.5 mg of reference formulation A or test formulation B were each uniformly applied (1 mg / cm 2 ) and spread on polymethyl methacrylate plates (PMMA; 7.0 cm x 3.5 cm, 2 μm roughness, GmbH&Co.KG). For each measurement, six replicate determinations were made, i.e., each formulation was applied to 6 individual PMMA plates. These were placed in an oven at 30 °C for 30 minutes, after which the SPF of the plates was determined using a Labsphere UV2000S ultraviolet transmittance analyzer according to the Colipa Guideline (2011), with 4 measurement points per PMMA plate in each case. The individual SPF values for each PMMA plate / formulation were recorded and the mean value was determined. The mean SPF value of each formulation containing the film-forming agent was divided by the mean SPF value of formulation A without the film-forming agent. The results are listed in Table 2 below.

[0230] Table 2: Relative in vitro SPF values of the example products in formulation B

[0231]

[0232] *Examples of the present invention

[0233] The results in Table 2 show that for the examples of the present invention, in all cases, the SPF enhancement values exceed 1.40 (relative to reference formulation A without the film-forming agent). In fact, the best wax esters according to the present invention achieve better values than those using polyacrylate SP 13 Sun Up and those using VP / eicosene copolymers. Values significantly better than those of the plant-based reference substances of the prior art are obtained.

[0234] Application Example 102: Oil structuring

[0235] 5 g of the corresponding wax esters according to the present invention or two non-invention examples and a mixture of 95 g of various (cosmetic) oils were stirred at 70 °C for 30 minutes, then stored at 25 °C for 24 hours, and the properties of the resulting mixture were examined. The results are listed in Table 3 below.

[0236] Table 3: Oil structuring ability

[0237]

[0238] The results show that Examples 001 to 008 of the present invention are comparable to polyacrylate based on petrochemical raw materials in terms of oil thickening As effective as SP 13 Sun Up (Example 16a), while the plant-based reference substance Cera Bellina #106 (Example 16e) did not show any oil structuring.

[0239] Formulation Examples

[0240] The following formulation examples demonstrate the usability of the wax esters of the present invention in cosmetic emulsions and do not limit the subject matter of the present invention.

[0241] Unless otherwise stated, all percentage values are by weight. The production and homogenization steps are carried out according to common methods.

[0242] If necessary, the pH is adjusted with acid or base, which is correspondingly noted in the formulation. Since the amount of the required acid or base may depend on the batches of other ingredients, it is usually entered as q.s. (= an appropriate amount) in the examples herein. Different pH values also need to be adjusted according to the preservatives used. The conventional pH values used and adjusted to in the example formulations are between pH 3.5 and 8.0.

[0243] The example formulations listed below are produced in each case with each wax ester of the present invention from Examples 001 to 008 (hereinafter referred to as "Example X"); for each example formulation, eight different formulations are thus prepared.

[0244] Fun in the Sun SPF 30 Spray

[0245]

[0246]

[0247] Oil Release Sun Care Lotion SPF 50

[0248]

[0249]

[0250] Alcoholic Sun Care Spray SPF 30

[0251]

[0252] Alcoholic Sun Care Spray SPF 30

[0253]

[0254]

[0255] Transparent Sun Care Spray SPF 25

[0256]

[0257] Water Resistant Aerosol Spray SPF 30

[0258]

[0259]

[0260] Water Resistant Aerosol Spray SPF 30

[0261]

[0262] Light O / W Sun Care Lotion

[0263]

[0264]

[0265] Dry Touch Hand Moisturizing Cream

[0266]

[0267]

[0268] Age Defense BB Cream SPF 15

[0269]

[0270]

[0271] Moisture Caring BB Cream SPF 15

[0272]

[0273]

[0274] Anhydrous stick

[0275]

[0276] O / W Sun Protect&Bronz

[0277]

[0278] Sun Care Foam SPF 50

[0279]

[0280]

[0281] W / O Sun Protection Shake-Shake

[0282]

[0283]

[0284] Light Sun Care W / O Shake-Shake SPF30PA+++

[0285]

[0286]

[0287] W / O Organic shake-shake SPF50+PA++++

[0288]

[0289]

[0290] Sun Care Cream SPF 30

[0291]

[0292] On the go UV protection stick SPF 50

[0293]

[0294]

[0295] Transparent UV protection water spray SPF 30

[0296]

[0297]

[0298] Sun Care Cream SPF 25

[0299]

[0300]

[0301] Inorganic water-resistant O / W sunscreen SPF 20

[0302]

[0303] Feel the sun spray SPF 50

[0304]

[0305]

[0306] Natural Sun Protection Stick

[0307]

[0308]

[0309] W / O Quick-Breaking Cream SPF 15

[0310]

[0311] W / O Sun Care Lotion SPF 8, water-resistant

[0312]

[0313] W / O Sun Care Lotion, water-resistant

[0314]

[0315]

[0316] Cationic Sun Screen SPF 19, Waterproof

[0317]

[0318] Waterproof Cationic Sun Screen SPF 15

[0319]

[0320]

[0321] Everyday Sunshine Cream SPF 15

[0322]

[0323]

[0324] High Sun Protection Lotion O / W SPF 50

[0325]

[0326]

[0327] Icy O / W Sun Care Lotion SPF 25

[0328]

[0329] Low viscosity W / O sun care lotion SPF30PA+++

[0330]

[0331]

[0332] Sun Care Aqua Gel SPF50+,PA++++

[0333]

[0334]

[0335] High Protection O / W Sun Care Cream with SPF 50+ PA+++

[0336]

[0337]

[0338] Sun Care Cream with SPF 15

[0339]

[0340]

[0341] W / O Foundation

[0342]

[0343]

[0344] W / O Foundation

[0345]

[0346] SPF 30 Sunscreen Lotion Containing Water-Soluble Emulsifier and Natural Water-Based Thickeners

[0347]

[0348]

[0349] SPF 30 Sunscreen Lotion Containing Oil-Soluble Emulsifier and Natural Water-Based Thickeners

[0350]

[0351]

[0352] SPF 30 Sunscreen Lotion, Mineral UF Filter, and Natural Water-Based Thickeners

[0353]

[0354] < / n> < / n>

Claims

1. A process for producing optionally at least partially saponified wax esters, which comprises the following process steps: A) providing a natural wax, B) oxidizing the natural wax to a natural wax oxide, C) esterifying the natural wax oxide with at least one polyol, optionally additionally with at least one selected from monocarboxylic acids and polycarboxylic acids, especially dicarboxylic acids, and optionally D) at least partially saponifying the wax esters obtained in process step C), provided that if only one polyol is used in process step C), the one polyol has a hydroxyl value of less than 1240 mg KOH / g, preferably less than 1200 mg KOH / g, more preferably less than 1150 mg KOH / g.

2. The method according to claim 1, wherein The natural wax provided is obtainable from renewable sources, and the natural wax is preferably selected from alfalfa wax, bamboo wax, cotton wax, beeswax, candelilla wax, palm wax, carnauba wax, dammar resin, Douglas fir wax, esparto wax, flax wax, hemp wax, coffee wax, cork wax, oleander wax, microcoelum wax, raffia wax, rice wax, rice bran wax, vine wax, bark wax, sisal wax, tea wax, wool wax and sugarcane wax, with carnauba wax being particularly preferred.

3. The method according to claim 1 or 2, characterized in that The natural wax provided contains in total 0.05% to 35% by weight, preferably 0.1% to 25% by weight, more preferably 1.0% to 20% by weight of aliphatic ω-hydroxycarboxylic acids and / or aliphatic α,ω-alkanediols and / or esters of aliphatic ω-hydroxycarboxylic acids and / or esters of aliphatic α,ω-alkanediols, where the weight percentages are relative to the total natural wax.

4. The method according to at least one of the preceding claims, characterized in that The oxidation in process step B) is carried out with chromic sulfuric acid.

5. The method according to any one of the preceding claims, characterized in that The natural wax oxide obtained in process step B) has an acid value (AV) of 30 to 200 mg KOH / g, preferably 50 to 190 mg KOH / g, more preferably 70 to 180 mg KOH / g, and / or an iodine value (IV) of ≤ 40 g I2 / 100 g, preferably ≤ 20 g I2 / 100 g, more preferably ≤ 10 g I2 / 100 g, particularly preferably ≤ 5 g I2 / 100 g, and / or a dropping point between 40 °C and 130 °C, preferably between 50 °C and 105 °C, more preferably between 70 °C and 90 °C, particularly preferably between 75 °C and 87 °C.

6. The method according to any one of the preceding claims, characterized in that The natural wax oxide obtained in process step B) has a content of aliphatic monocarboxylic acids with an odd chain length of 9 to 29 carbon atoms of at least 0.01% by weight, preferably at least 0.5% by weight, more preferably at least 5.0% by weight, particularly preferably at least 10.0% by weight, where the weight percentages are relative to all aliphatic monocarboxylic acids present in the natural wax oxide.

7. The method according to any one of the preceding claims, characterized in that The at least one polyol has three or more, preferably four or more, especially more than six carbon atoms.

8. The method according to any one of the preceding claims, characterized in that The at least one polyol contains polyglycerol.

9. The method according to claim 8, wherein Based on all polyols, polyglycerol constitutes at least 20% by weight, preferably at least 40% by weight, more preferably at least 60% by weight, particularly preferably at least 80% by weight.

10. The method according to claim 8 or 9, characterized in that Polyglycerol has a content of cyclic oligomers of 1.0% to 50% by weight, preferably 2.0% to 40% by weight, more preferably 3.0% to 30% by weight.

11. Optionally at least partially saponified wax esters obtainable by the method according to at least one of claims 1 to 10.

12. A formulation, in particular a cosmetic formulation, comprising the wax esters according to claim 11 and at least one substance optionally selected from the group consisting of UV protection filter substances and pigments, in particular a UV protection filter substance.

13. The formulation according to claim 12, characterized in that The wax esters are present in an amount of from 0.1% to 20% by weight, preferably from 0.25% to 12% by weight, more preferably from 0.5% to 6% by weight, where the weight percentages are based on the total formulation.

14. Use of the wax esters according to claim 11 for the production of a formulation, in particular a cosmetic formulation, in particular a sunscreen formulation.

15. Use of the wax esters according to claim 11 as a film-forming agent, for enhancing the sun protection factor of UV protection filter substances or for reducing the rinsability and / or abrasion of the formulation from a surface.

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