202300092 Foreign Filing 1 Polyglycerol partial ester comprising oleic Field of the invention The invention relates to a polyglycerol partial ester obtainable by esterification of a) a polyglycerol mixture, b) poly(hydroxycarboxylic) acid, c) at least one dicarboxylic acid having 6 to 12, preferably 9 to 10, carbon atoms, more preferably selected from azelaic acid and sebacic acid, and d) oleic acid. Prior art EP1500427 discloses polyglycerol partial ester of poly(hydroxystearic) acid and polyfunctional carboxylic acids, obtainable by esterification of a a) polyglycerol mixture with b) poly(hydroxystearic) acid and c) di- and/or tricarboxylic acids and optionally/or with d) dimer fatty acids, and e) fatty acids having 6 to 22 C atoms. These polyglycerol partial esters allow formulation of highly liquid emulsions which have a pleasant sensation on the skin and at the same time an improved resistance to freezing-thawing. These polyglycerol partial ester, however, are not capable of stabilizing high amount of oil in water- in-oil-emulsions. EP3500550 discloses polyglycerol partial esters obtainable by esterification of a polyglycerol with a carboxylic acid mixture comprising: a) at least one polyhydroxycarboxylic acid of a hydroxycarboxylic acid having 8 to 32 carbon atoms, b) at least one short-chain dicarboxylic acid having 2 to 16 carbon atoms, c) at least one long-chain dicarboxylic acid having 24 to 44 carbon atoms, and d) at least one fatty acid selected from linear, unsaturated and branched, saturated fatty acids having 14 to 24 carbon atoms. EP3325582 discloses lubricating oil compositions comprising (a) 0.2 to 5% by weight of polyglycerol partial esters, based on the total weight of the lubricating oil composition, characterized in that the polyglycerol partial esters are obtainable by esterification of a polyglycerol mixture with
202300092 Foreign Filing 2 (i) polyfunctional carboxylic acids and (ii) saturated or unsaturated, linear or branched fatty acids and/or (ii) poly(hydroxystearic acid), wherein the degree of esterification of the polyglycerol mixture is between 30 and 75% of the OH groups; (b) 85 to 99.8% by weight of an apolar base stock selected from the group consisting of API Group II, III and IV and/or mixtures thereof, based on the total weight of the lubricating oil composition; and (c) 0 to 10% by weight of a polar ester oil of Group V according to the definition of the American Petroleum Institute (API), based on the total weight of the lubricating oil composition. It is an objective of the invention to improve the skin sensation of formulations even further and to reduce the whitening of formulations when applied to the skin. Description of the invention that, surprisingly, polyglycerol partial esters as described in claim 1 solve the problem underlying the instant invention. The present invention therefore provides a polyglycerol partial ester obtainable by esterification of a) a polyglycerol mixture, b) poly(hydroxycarboxylic) acid, preferably selected from poly(hydroxystearic) acid and poly(ricinoleic) acid, wherein poly(hydroxystearic) acid is particularly preferred, c) at least one dicarboxylic acid having 6 to 12, preferably 9 to 10, carbon atoms, more preferably selected from azelaic acid and sebacic acid, and d) oleic acid. The invention further provides a method for preparing a polyglycerol partial ester comprising the method steps of A) providing a polyglycerol, preferably having an average degree of condensation N of 2.4 to 15.0, preferably 2.6 to 10.0, especially 2.8 to 8.0, B) providing a carboxylic acid mixture comprising: poly(hydroxycarboxylic) acid, preferably selected from poly(hydroxystearic) acid and poly(ricinoleic) acid, wherein poly(hydroxystearic) acid is particularly preferred, at least one dicarboxylic acid having 4 to 18, preferably 4 to 14, more preferably 8 to 12, carbon atoms, and oleic acid, C) esterifying the polyglycerol with the carboxylic acid mixture.
202300092 Foreign Filing 3 An advantage of the present invention is that the polyglycerol partial esters described herein may be prepared from exclusively renewable raw materials. A further advantage is that the polyglycerol partial esters described herein can be prepared on the basis of principles of green chemistry. Another advantage of the present invention is that formulations can be provided that are polyglycol ether-free. A further advantage is that the polyglycerol partial esters described herein are biodegradable. A further advantage is that the polyglycerol partial esters described herein have a good ecotoxicological profile. A further advantage of the polyglycerol partial esters described herein is that they are very mild on the skin, not irritating and non-toxic. 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 more rapid absorption into the skin since absorption is increased during application and for 5 min thereafter on the skin. Another advantage of the polyglycerol partial esters described herein is that they give rise to enhancement of “velvety-silkiness” in formulations. A further advantage is that the polyglycerol partial esters described herein have a good skin- moisturizing effect. 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. 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. Another advantage of the polyglycerol partial esters according to the instant invention is that they impart increased wear resistance to the colour pigments when used in make-up applications. In the context of pigment-containing formulations, a further advantage of the polyglycerol partial esters according to the instant invention is that they permit good dispersion of pigments in the formulations. A further advantage of the polyglycerol partial esters described herein is that they have good compatibility with formulations containing UV protection filters or pigments. In general, the polyglycerol partial esters described herein impart good stability to the formulations. Another advantage of the polyglycerol partial esters according to the instant invention is that they are easily processable since they mix readily with typical cosmetic oils and can be rapidly incorporated into corresponding emulsions. A further advantage of the polyglycerol partial esters described herein is that they impart high gloss to solid or waxy formulations such as lipsticks.
202300092 Foreign Filing 4 Yet another advantage of the polyglycerol partial esters according to the instant invention is that they are particularly tolerant to electrolytes, which means that, for example, formulations containing large amounts of salt remain stable. A further advantage of the polyglycerol partial esters according to the instant invention is that they have a structuring and viscosity-increasing effect in formulations having high oil contents or even pure oils. One advantage of the present invention is that formulations based on polyglycerol partial esters described herein can be prepared by a cold process without heating. Another advantage of the present invention is that the polyglycerol partial esters according to the instant invention are very tolerant towards different oil phase contents in the emulsions. A further advantage is that the polyglycerol partial esters according to the instant invention are very tolerant towards different oil phase compositions in the emulsions. Another advantage is that the polyglycerol partial esters according to the instant invention have a pleasant, less “technical” odor. Another advantage of the present invention is that even high proportions of natural oils such as almond oil are well stabilized in emulsions. Another advantage of the present invention is that emulsions can be stabilized over a wide viscosity range from sprays to lotions to creams. A further advantage of the present invention is that emulsions based on emulsifiers according to the instant invention have very good compatibility with propellants, such as mixtures of propane, n- butane and iso-butane, and thus simplify the production of aerosol systems. A further advantage of the present invention is that the skin feel of the emulsions stabilized with the described polyglycerol partial esters is at least as good as with the emulsifiers of the prior art. Another advantage is that the present invention can be used as emulsifier and lubricity additive for metal working fluids (neat oils or water based fluids) where it provides excellent emulsion stabilizing properties, reduces oil droplet coalescence, increases lubricity properties e.g. of base oils especially at high frictions, is soluble even in GTL oils, gives best additional lubricity under stress, and reduces applied torque during tapping. Further, the present invention provides excellent stability of rolling oil emulsions with reduced coalescence, good lubricity and good surface quality. Another advantage is that the present invention can be used as friction modifiers for lubricants. Another advantage is that the present invention can reduce the friction coefficient. Another advantage is that the present invention can lead to more efficient friction reduction due to a lower treat rate and/or a better combination of oil compatibility and friction reducing performance. The polyglycerol partial esters according to the instant 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. 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.
202300092 Foreign Filing 5 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. The same applies to the term “polyglycerol partial ester” in the context of the present invention. The polyglycerol partial ester obtainable by esterification of carboxylic acids according to the instant 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 acid, it will be apparent to those skilled in the art that the molar ratio of polyglycerol a) to dicarboxylic acid component b) 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. 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. For the present invention, it is preferred that the polyglycerol esterified into the polyglycerol partial ester has an average degree of condensation N of 2.4 to 15.0, preferably 2.6 to 10.0, especially 2.8 to 8.0. 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: (112200 ^18 ^ OHV ) N ^ ^ ) for determining the hydroxyl value are in particular those according to
a , Method A and DIN 53240. Unless otherwise stated, all stated percentages (%) are percentages by weight. Polyglycerol partial esters preferred in accordance with the invention are characterized in that the polyglycerol esterified into the polyglycerol partial ester has a glycerin content of 0.05% by weight
202300092 Foreign Filing 6 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 esterified into the polyglycerol partial ester. The stated percentages by weight are determined by the GC method described hereinbelow. Polyglycerol partial esters preferred in accordance with the invention are characterized in that the polyglycerol esterified into the polyglycerol partial ester 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 esterified into the polyglycerol partial ester. The stated percentages by weight are determined by the GC method described hereinbelow. It is advantageous when the polyglycerol esterified into the polyglycerol partial ester has a polydispersity index of more than 0.6, preferably of more than 1.0, more preferably of more than 1.2. For the purposes of the present invention, the polydispersity index is calculated as ^|^
^ − ^| ⋅ ^
^ ^ where ni is the degree of condensation oligomer i, N the average degree of
condensation of the polyglycerol and how to determine] and xi the proportion of the oligomer i in the polyglycerol mixture, as determined in the GC method described hereinbelow. 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. 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. 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 ml
202300092 Foreign Filing 7 Injected volume: 1 µl Column: 30 m * 0.32 mm HP10.25 µm Carrier gas: Helium, inlet pressure 70 kPa Temp. program: 80°C to 300°C at 8°C/min; Detector: FID at 320°C Hydrogen 35 ml/min Air 240 ml/min Make-up gas (purge gas) 35 ml/min When using these conditions, the methyl carboxylate esters are separated according to their chain length. The relative content of the individual carboxylic acids (chain-length distribution) is evaluated as a percentage of the peak area. 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. 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 µl Carrier 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/min Detector (FID): 375°C 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. The peak areas of the individual oligomers are separated by a perpendicular line applied at the lowest point of the trough between peaks. 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.
202300092 Foreign Filing 8 The relative ratio of the individual polyglycerol oligomers and isomers is calculated from the GC peak area obtained as described above. 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. Polyglycerol partial esters preferred in accordance with the invention are characterized in that polyglycerol esterified into the polyglycerol partial ester 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, where the percentages by weight are based on the total amount of polyglycerol esterified into the polyglycerol partial ester. The stated percentages by weight are determined by the GC method described above. The poly(hydroxycarboxylic) acids esterified into the polyglycerol partial ester according to the present invention can be prepared, for example, by polycondensation of hydroxycarboxylic acids, preferably 12-hydroxystearic acid, which is obtainable by hardening of ricinoleic acid or technical- grade castor oil fatty acids. Polyglycerol partial esters preferred in accordance with the invention are characterized in that the poly(hydroxycarboxylic) acid esterified into the polyglycerol partial ester has an average degree of condensation P of 1.5 to 9.0, preferably of 2.0 to 7.0, more preferably 3.0 to 5.0. The average degree of condensation of poly(hydroxycarboxylic) acids P can be determined as follows: 56106 with P = average degree of condensation of poly(hydroxycarboxylic) ^
^ − 18.02 ^ =
^^^^^^^^ − 18.02 acid AV = Acid value [mg KOH/g] MMonomer = Molecular weight of the monomer [g/mol], e.g.300.48 g/mol for hydroxystearic acid Polyglycerol partial esters preferred in accordance with the invention are characterized in that the poly(hydroxycarboxylic) acid esterified into the polyglycerol partial ester has an acid value of between 188 mg KOH/g and 20 mg KOH/g, preferably between 97 mg KOH/g and 33 mg KOH/g, more preferably between 65 mg KOH/g and 40 mg KOH/g.
202300092 Foreign Filing 9 Polyglycerol partial esters preferred in accordance with the invention are characterized in that the dicarboxylic acid is selected from azelaic acid and sebacic acid, especially sebacic acid. Polyglycerol partial esters preferred in accordance with the invention are characterized in that the oleic acid is provided in form of a technical grade oleic acid, e.g. with an overall content of oleic acid referring to all fatty acids contained in the technical grade oleic acid mixture of at least 60 wt.- %, preferably of at least 65 wt.-%, even more preferably of at least 68 wt.-%, Preferably the above technical grade oleic acid mixture has an overall content of linoleic (C18:2) acid of from 10.0 wt.-% to 15.0 wt.-% referring to all fatty acids contained in the technical grade oleic acid mixture. Polyglycerol partial esters preferred in accordance with the invention are characterized in that the molar ratio of the poly(hydroxycarboxylic) acid esterified into the polyglycerol partial ester, the at least one dicarboxylic acid esterified into the polyglycerol partial ester and the oleic acid esterified into the polyglycerol partial ester is in the range of 0.50 : 1.00 : 2.90 to 4.00 : 1.00 : 6.50, preferably 0.60 : 1.00 : 2.80 to 3.50 : 1.00 : 5.80, more preferably 0.70 : 1.00 : 2.75 to 2.50 : 1.00 : 5.20, and most preferably 0.75 : 1.00 : 2.70 to 1.50 : 1.00 : 4.50. The molecular weight of poly(hydroxycarboxylic) acids can be determined as follows: ^
= 56106 with M = Molecular weight of the poly(hydroxycarboxylic) acid [g/mol], ^
^ AV = Acid value [mg KOH/g] Polyglycerol partial esters preferred in accordance with the invention are characterized in that they have a degree of esterification of 50% to 98%, preferably of 55% to 95%, more preferably of 60% to 90%, more preferably of 65% to 85%. The determination of the degree of esterification of the polyglycerol partial esters of the invention is described as follows: 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: ^
^^^^^ ! ^"#^^$!$%&#$ ^ = 100 ∙ ()^ − ^^) (
)^ − ^^ + ,-^)
where SV = saponification value, AV = acid value and OHV = value. 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.
202300092 Foreign Filing 10 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. In this context, it is particularly preferable that the polyglycerol partial ester of the invention has an acid value within a range from 0.1 mg KOH/g to 25.0 mg KOH/g, preferably within a range from 0.5 mg KOH/g to 15.0 mg KOH/g, preferably within a range from 2.0 mg KOH/g to 11.0 mg KOH/g. Polyglycerol partial esters preferred in accordance with the invention are characterized in that the sum of the components b) to d) makes up at least 80 wt.-%, preferably at least 85 wt.-%, more preferably at least 90 wt.-%, more preferably at least 95 wt.-%, of all carboxylic acids esterified into the polyglycerol partial esters according to the instant invention. 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 1.0 to 9.0, preferably from 1.5 to 7.5 and more preferably from 2.5 to 6.0. 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 acid). 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. Polyglycerol partial esters preferred in accordance with the invention are characterized in that they have an iodine value of 28.0 g I/100 g to 52.0 g I/100 g, preferably 31.0 g I/100 g to 49.0 g I/100 g, more preferably of 34.0 to 46.0 g I/100 g. A suitable method for determining the iodine value in the context of the present invention is EN 14111:2003. It is preferable in accordance with the invention that the polyglycerol partial ester of the invention has a viscosity at 25 °C of 100 mPas to 10000 mPas, preferably 500 mPas to 8000 mPas, more preferably 1000 mPas to 6000 mPas.
202300092 Foreign Filing 11 A suitable method for determining the viscosity is using a Brookfield RV viscometer (with spindle SC4-21, running at 20 RPM and displaying a % torque of 53.0; torque constant = 1, spindle multiplier constant = 5, spindle shear rate constant = 0.93) and a Brookfield Thermosel. Polyglycerol partial esters according to the instant 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, preferably having an average degree of condensation N of 2.4 to 15.0, preferably 2.6 to 10.0, especially 2.8 to 8.0, B) providing a carboxylic acid mixture comprising: poly(hydroxycarboxylic) acid, preferably selected from poly(hydroxystearic) acid and poly(ricinoleic) acid, wherein poly(hydroxystearic) acid is particularly preferred, at least one dicarboxylic having 6 to 12, preferably 9 to 10, carbon atoms, more preferably selected from azelaic acid and sebacic acid, and oleic acid, C) esterifying the polyglycerol with the carboxylic acid mixture. In the method according to the invention, preference is given to using those polyglycerols, poly(hydroxycarboxylic) acids, dicarboxylic acids and oleic acid 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. 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. If method step C) is carried out as a one-pot reaction, the carboxylic acid mixture is esterified with the polyglycerol. If method step C) is carried out as a stepwise process, the monocarboxylic acids (e.g. the poly(hydroxycarboxylic) acid and oleic acid) and the dicarboxylic acid are added sequentially and esterified with the polyglycerol; strictly speaking, the monocarboxylic acids and the dicarboxylic acid 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 acid in a second step. However, the reverse stepwise synthetic sequence comprising an initial reaction of the polyglycerol with the dicarboxylic acid and then a subsequent reaction with the monocarboxylic acids is possible, too. Splitting the individual reactants into several portions and multistage reactions is another possible application. Since the polyglycerol partial esters according to the instant invention have an excellent use profile in cosmetic formulations, the present invention further provides a formulation, especially a cosmetic
202300092 Foreign Filing 12 formulation, comprising 1) the polyglycerol partial ester according to the instant invention or a polyglycerol partial ester obtainable by the method according to the invention. Preferably, the formulation according to the instant invention is characterized in that it comprises a further component 2) at least one antioxidant. Preferred antioxidants, which according to the instant invention are preferably present in the formulation according to the invention, are chosen from the group containing, preferably consisting of, 3,5-di-tert-butyl-4-hydroxytoluene (BHT), 2-tert-butyl-4- hydroxyanisole and 3-tert-butyl-4-hydroxyanisole, tert-butylhydroquinone (TBHQ), digalloyl trioleate, propyl gallate, octyl gallate, dodecyl gallate, mercaptoacetic acid, sodium thioglycolate, rosmarinic acid, carnosic acid, chlorogenic acid, isoascorbic acid, dexpanthenol, siderophores including catechols, hydroxamates, such as, for example, deferoxamines B, D1, D2, E and H, citrates, cysteine and its derivatives, such as, for example, cysteine hydrochloride and acetylcysteine, ascorbic acid and its derivatives (e.g. ascorbyl glucoside, ascorbyl palmitate, ascorbyl dipalmitate, ascorbyl tetraisopalmitate, magnesium ascorbate, magnesium ascorbyl phosphate), vitamin E (α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and α-tocotrienol, β- tocotrienol, γ-tocotrienol and δ-tocotrienol) and its derivatives (e.g. vitamin E acetate, vitamin E linoleate, vitamin E nicotinate, vitamin E succinate), hesperetin, naringenin, flavonoids, taxifolin, catechin, epicatechin, resveratrol and its derivatives (in particular its oligomers), carotenoids (e.g. lycopene, β-carotene, lutein), isosakuranetin, quercetin, eriodictyol, aromadendrin, acacetin, luteolin, kaempferol, apigenin, diosmetin, chrysoeriol, chrysin, galangin, limocitrin, phytic acid and its derivatives, in particular its salts. Preferably mixtures of the abovementioned antioxidants can also be used. Particularly preferred are phytic acid and its derivatives, in particular its salts, and also vitamin E (for example in the form of α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol, α-tocotrienol, β-tocotrienol, γ-tocotrienol and/or δ-tocotrienol) and its derivatives, in particular as vitamin E acetate, vitamin E linoleate, vitamin E nicotinate or vitamin E succinate, and also their mixtures. Preferably, the formulation according to the instant invention comprises a further component 2) at least a mixture of at least two different tocopherols, preferably a mixture consisting of D-alpha- Tocopherol, preferably 0 to 30% by weight, D-beta-Tocopherol, preferably 0 to 20% by weight, D- gamma-Tocopherol, preferably 40 to 80% by weight, D-delta-Tocopherol, preferably 0 to 40% by weight. In preferred formulations according to the invention, the antioxidants are present in an amount of from 0.001% by weight to 5.0% by weight, preferably from 0.01% by 35 weight to 1.0% by weight, particularly from 0.02% by weight to 0.35% by weight, the percentages by weight referring to the total formulation. A preferred formulation according to the instant invention is characterized in that
202300092 Foreign Filing 13 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, if applicable, preferably component 2) is present in an amount of 0.001% by weight to 5.0% by weight, preferably from 0.01% by weight to 1.0% by weight, particularly from 0.02% by weight to 0.35% by weight, the percentages by weight referring to the total formulation. Preferably, the formulation according to the instant invention is characterized in that it comprises component 2A) at least one preservative. Preferred preservatives, which according to the instant invention are preferably present in the formulation according to the invention, are chosen from the group comprising, preferably consisting of, anisic acid, levulinic acid, benzoic acid, sorbic acid, salicylic acid, pentylene glycol, glyceryl caprylate, glyceryl caprate, phenyl propanol, phenethyl alcohol and triethylcitrate. Preferably mixtures of the abovementioned preservatives are used. Preferred formulations according to the instant invention are characterized in that, the component 2A) is present in an amount of from 0.01% by weight to 15.0% by weight, preferably from 0.05% by weight to 10.0% by weight, particularly from 0.1% by weight to 8.0% by weight, the percentages by weight referring to the total formulation. A preferred formulation according to the instant 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 2A) is present in an amount of from 0.01% by weight to 15.0% by weight, preferably from 0.05% by weight to 10.0% by weight, particularly from 0.1% by weight to 8.0% by weight, the percentages by weight referring to the total formulation. Preferably, the formulation according to the instant invention is characterized in that it comprises component 2B) at least one selected from ester emollients and triglycerides. Preferred ester emollients, which according to the instant invention are preferably present in the formulation according to the invention, are chosen from the group comprising, preferably consisting of, butyl stearate, butylene glycol dicaprylate/dicaprate, C12-15 alkyl benzoate, caprylic/capric triglyceride, cetearyl ethylhexanoate, cetearyl isononanoate, cetyl ethylhexanoate, cetyl palmitate, cetyl ricinoleate, cetyl ricinoleate, coco-caprylate, coco-caprylate/caprate, decyl oleate, dibutyl adipate, diisobutyl adipate, diisopropyl adipate, diisostearyl malate, ethylhexyl cocoate, ethylhexyl ethylhexanoate, ethylhexyl isononanoate, ethylhexyl palmitate, ethylhexyl stearate, hexyl laurate, hexyldecyl laurate, isoamyl cocoate, isoamyl laurate, isocetyl palmitate, isononyl isononanoate,
202300092 Foreign Filing 14 isopropyl isostearate, isopropyl laurate, isopropyl myristate, isopropyl palmitate, isopropyl stearate, isostearyl isostearate, isostearyl neopentanoate, isostearyl palmitate, isotridecyl isononanoate, lauryl oleate, myristyl myristate, octyl palmitate, octyl stearate, octyldodecyl myristate, octyldodecyl neopentanoate, oleyl erucate, oleyl oleate, pentaerythrityl tetraisostearate, phenoxyethyl caprylate, propylene glycol dicaprylate, propylene glycol dicaprylate/dicaprate, stearyl caprylate, stearyl heptanoate, stearyl palmitate, tricaprylin, triethylhexanoin, triheptanoin, triisononanoin and triisostearin, more preferably butylene glycol dicaprylate/dicaprate, C12-15 alkyl benzoate, caprylic/capric triglyceride, cetearyl ethylhexanoate, cetearyl isononanoate, cetyl ethylhexanoate, cetyl ricinoleate, ethylhexyl cocoate, ethylhexyl palmitate, ethylhexyl stearate, hexyl laurate, isoamyl cocoate, isoamyl laurate, isopropyl myristate, isopropyl palmitate, isostearyl isostearate, lauryl oleate, myristyl myristate, octyl palmitate, octyl stearate, oleyl erucate, stearyl heptanoate and tricaprylin. Said triglyceride preferably is a natural oil, more preferably with an iodine value (IV) of 0.5 g I/100 g – 150.0 g I/100 g, preferably 10.5 g I/100 g – 120.0 g I/100 g, more preferably 25.0 g I/100 g – 110.0 g I/100 g, most preferably 40.0 g I/100 g – 100.0 g I/100 g. Preferred formulations according to the instant invention are characterized in that, the component 2B) is present in an amount of from 0.1% by weight to 35.0% by weight, preferably from 0.5% by weight to 30.0% by weight, particularly from 1.0% by weight to 25.0% by weight, the percentages by weight referring to the total formulation. A preferred formulation according to the instant 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 2B) is present in an amount of from 0.1% by weight to 35.0% by weight, preferably from 0.5% by weight to 30.0% by weight, particularly from 1.0% by weight to 25.0% by weight, the percentages by weight referring to the total formulation. A preferred formulation according to the instant 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, component 2A) is present in an amount of from 0.01% by weight to 15.0% by weight, preferably from 0.05% by weight to 10.0% by weight, particularly from 0.1% by weight to 8.0% by weight, and component 2B) is present in an amount of from 0.1% by weight to 35.0% by weight, preferably from 0.5% by weight to 30.0% by weight, particularly from 1.0% by weight to 25.0% by weight, the percentages by weight referring to the total formulation.
202300092 Foreign Filing 15 The formulations according to the instant invention can comprise for example at least one further additional component selected from the group comprising emollients, emulsifiers, co-emulsifiers, thickeners/viscosity regulators/stabilizers, hydrotropes (or polyols), solids and fillers, pearlescent additives and opacifiers, insect repellents, self-tanning agents, conditioning agents, perfumes, colorants, cosmetic active substances, care additives, refatting agents, electrolytes organic and inorganic UV filters pigments sensory particles solvents. 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. This patent application is hereby incorporated as reference and is thus considered to form part of the disclosure. 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. The amounts of the respective additives depend on the intended use. 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. Formulations according to the instant 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.
202300092 Foreign Filing 16 Formulations according to the instant invention preferably are emulsions, most preferably water-in- oil-emulsions, also known as w/o-emulsions. Consequently, they preferably comprise an oil phase. 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 ingredient, especially as emulsifier and/or lubricity additive, in metalworking fluids. 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. The examples adduced hereinafter describe the present invention by way of example, without any intention that the invention, the scope of application of which is apparent from the entirety of the description and the claims, be restricted to the embodiments specified in the examples. Examples: Example 1: (non-inventive) polyglycerol partial esters according to example 13 of EP1500427 with isostearic acid A mixture of polyglycerol (OHV = 1190 mg KOH/g, 63.0 g), isostearic acid (Palmera IS-30 from KLK Emmerich GmbH, AV = 196 mg KOH/g, iodine value = 1.2 g I/100 g, 91.1 g, 0.313 mol) and sebacic acid (20.2 g, 0.100 mol) was heated to 240 °C with stirring and nitrogen passing through. The resulting water was continuously distilled until an acid value of 4.3 mg KOH/g was reached. Then, poly(hydroxystearic) acid (AV = 45 mg KOH/g, 141.7 g, 0.114 mol) was added, the mixture was heated to 240 °C with stirring and nitrogen passing through and the resulting water was continuously distilled until an acid value of 3.1 mg KOH/g was reached. Molar ratio of the poly(hydroxycarboxylic) acid to dicarboxylic acid to isostearic acid = 1.14 : 1.00 : 3.13 Example 2: (inventive) polyglycerol partial esters with oleic acid, sebacic acid and poly(hydroxystearic) acid A mixture of polyglycerol (OHV = 1190 mg KOH/g, 63.0 g), oleic acid (Palmera A1818 from KLK Emmerich GmbH, AV = 200 mg KOH/g, iodine value = 92 g I/100 g, 87.8 g, 0.313 mol) and sebacic acid (20.2 g, 0.100 mol) was heated to 240 °C with stirring and nitrogen passing through. The resulting water was continuously distilled until an acid value of 4.8 mg KOH/g was reached. Then,
202300092 Foreign Filing 17 poly(hydroxystearic) acid (AV = 45 mg KOH/g, 141.7 g, 0.114 mol) was added, the mixture was heated to 240 °C with stirring and nitrogen passing through and the resulting water was continuously distilled until an acid value of 3.7 mg KOH/g was reached. Molar ratio of the poly(hydroxycarboxylic) acid to dicarboxylic acid to oleic acid = 1.14 : 1.00 : 3.13 Example 3: (inventive) polyglycerol partial esters with oleic acid, azelaic acid and poly(hydroxystearic) acid A mixture of polyglycerol (OHV = 1100 mg KOH/g, 175.41 g), oleic acid (Palmera A1818 from KLK Emmerich GmbH, AV = 200 mg KOH/g, iodine value = 92 g I/100 g, 363.3 g, 1.29 mol), azelaic acid (67.7 g, 0.360 mol) and poly(hydroxystearic) acid (AV = 47.5 mg KOH/g, 435.6 g, 0.369 mol) was heated to 240 °C with stirring and nitrogen passing through. The resulting water was continuously distilled until an acid value of 4.1 mg KOH/g was reached. Molar ratio of the poly(hydroxycarboxylic) acid to dicarboxylic acid to oleic acid = 1.03 : 1.00 : 3.60 Example 4: Sensory comparison of examples 2 and 3 and 1 To differentiate the sensorial properties of the inventive emulsifier against the state of the art, formula 1a to 1c was prepared. The effect of the emulsifier on the skin feel was tested by a panel of trained panelists. Each panelist applied 25 μL of each formulation on a test field with defined size on his inner forearm. The formulation was homogenously distributed with a finger in circular movements. The sensory was evaluated directly after application and 5 min later. Formula 1a 1b 1c Polyglycerol ester according to example 2 3.5 Polyglycerol ester according to example 3 3.5 Polyglycerol ester according to example 1 (non-inventive) 3.5 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 3.0 3.0 3.0 Diethylamino Hydroxybenzoyl Hexyl Benzoate 3.0 3.0 3.0 Ethylhexyl Salicylate 4.0 4.0 4.0 Ethylhexyl Triazone 3.0 3.0 3.0 Homosalate 5.0 5.0 5.0 Isoamyl Laurate 4.5 4.5 4.5 Decyl Cocoate 4.0 4.0 4.0 Triethyl Citrate; Caprylyl Glycol; Benzoic Acid (Verstatil® 1.0 1.0 1.0 TBO; Evonik Industries AG)
202300092 Foreign Filing 18 Zink Stearate 0.5 0.5 0.5 Water Ad 100 Ad 100 Ad 100 Surprisingly formula 1a and 1b differentiated from formula 1c by a less pronounced whitening and an overall lighter, smoother skin feel directly after application and 5 min later. The following table shows the sensorial differences between the inventive emulsifiers and the benchmark: Table 1: Formula 1a Formula 1b Formula 1c Sensorial properties inventive inventive non-inventive Whitening - - - - 0 Oiliness + + + + Absorption 0 0 - Slipperiness 0 0 - Waxiness after 5 min 0 0 + Absorption after 5 min 0 0 - Slipperiness after 5 min 0 0 - Stickiness - - - - - after 5 min + + very strong, + strong, 0 medium, - low, - - very low Example 5: (inventive) polyglycerol partial esters with oleic acid, sebacic acid and poly(hydroxystearic) acid A mixture of polyglycerol (OHV = 1124 mg KOH/g, 48.2 g), oleic acid (Palmera A1818 from KLK Emmerich GmbH, AV = 200 mg KOH/g, iodine value = 92 g I/100 g, 80.1 g, 0.286 mol) and sebacic acid (14.9 g, 0.074 mol) was heated to 240 °C with stirring and nitrogen passing through. The resulting water was continuously distilled until an acid value of 1.5 mg KOH/g was reached. Then, poly(hydroxystearic) acid (AV = 49 mg KOH/g, 156.7 g, 0.137 mol) was added and the mixture was heated at 240 °C with stirring and nitrogen passing through and the resulting water was continuously distilled until an acid value of 2.5 mg KOH/g was reached. Molar ratio of the poly(hydroxycarboxylic) acid to dicarboxylic acid to oleic acid = 1.85 : 1.00 : 3.86 Example 6: (inventive) polyglycerol partial esters with oleic acid, sebacic acid and poly(hydroxystearic) acid
202300092 Foreign Filing 19 A mixture of polyglycerol (OHV = 1100 mg KOH/g, 67.5 g), oleic acid (Palmera A1818 from KLK Emmerich GmbH, AV = 200 mg KOH/g, iodine value = 92 g I/100 g, 130.4 g, 0.463 mol) and sebacic acid (24.3 g, 0.120 mol) was heated to 240 °C with stirring and nitrogen passing through. The resulting water was continuously distilled until an acid value of 4.9 mg KOH/g was reached. Then, poly(hydroxystearic) acid (AV = 47.5 mg KOH/g, 127.8 g, 0.108 mol) was added, the mixture was heated to 240 °C with stirring and nitrogen passing through and the resulting water was continuously distilled until an acid value of 6.1 mg KOH/g was reached. Molar ratio of the poly(hydroxycarboxylic) acid to dicarboxylic acid to oleic acid = 0.90 : 1.00 : 3.86 Example 7: (inventive) polyglycerol partial esters with oleic acid, sebacic acid and poly(hydroxystearic) acid A mixture of polyglycerol (OHV = 1100 mg KOH/g, 58.0 g), oleic acid (Palmera A1818 from KLK Emmerich GmbH, AV = 200 mg KOH/g, iodine value = 92 g I/100 g, 112.2 g, 0.398 mol) and sebacic acid (20.9 g, 0.103 mol) was heated to 240 °C with stirring and nitrogen passing through. The resulting water was continuously distilled until an acid value of 4.7 mg KOH/g was reached. Then, poly(hydroxystearic) acid (AV = 47.5 mg KOH/g, 158.8 g, 0.134 mol) was added, the mixture was heated to 240 °C with stirring and nitrogen passing through and the resulting water was continuously distilled until an acid value of 6.0 mg KOH/g was reached. Molar ratio of the poly(hydroxycarboxylic) acid to dicarboxylic acid to oleic acid = 1.30 : 1.00 : 3.86 Example 8: Emulsification performance comparison examples 2, 3, 6, 7 and 5 The emulsification performance was evaluated in formula 18. The emulsion was prepared in a hot/cold process using polyglycerol esters according to examples 2,3,6, 7 and 5. The formulas containing the inventive polyglycerol esters 2, 3, 6 and 7 showed a higher heat stability than the emulsion containing the inventive polyglycerol ester 5: After 3 days storage at 45°C and 50°C, the emulsions stabilized with the emulsifiers 2, 3, 6 and 7 showed no instabilities and an inferior emulsification performance (strong oil separation) was observed for example 5. Formula 18a 18b 18c 18d 18e Polyglycerol ester according to example 2 3.0 Polyglycerol ester according to example 3 3.0 Polyglycerol ester according to example 6 3.0 Polyglycerol ester according to example 7 3.0 Polyglycerol ester according to example 5 3.0 Coco-Caprylate/Caprate 11.0 11.0 11.0 11.0 11.0
202300092 Foreign Filing 20 Undecane / Tridecane 10.0 10.0 10.0 10.0 10.0 Carpylic/Carpric Triglyceride 9.0 9.0 9.0 9.0 9.0 Hydrogenated Castor Oil 0.075 0.075 0.075 0.075 0.075 Parrafin and Cera Micorcristallina 0.075 0.075 0.075 0.075 0.075 Ethylhexyl Palmitate 0.85 0.85 0.85 0.85 0.85 Magnesiumsulfate heptahydrate 1.5 1.5 1.5 1.5 1.5 Glycerin 3.0 3.0 3.0 3.0 3.0 Water Ad 100 Ad 100 Ad 100 Ad 100 Ad 100 Phenoxyethanol, Caprylyl Glycol 0.8 0.8 0.8 0.8 0.8 Polyglycerol Stability after Stability after ester 3 days 3 days according to storage at 45°C storage at 50°C example Formula 18a 2 stable stable Formula 18b 3 stable stable Formula 18c 6 stable stable Formula 18d 7 stable stable Formula 18e 5 Oil separation Oil separation Example 9: Freeze stability comparison examples 2, 3, 6, 7 and 5 The freeze stability was evaluated in formula 19. The emulsions containing polyglycerol esters according to examples 2, 3, 6, 7 and 5 were frozen to –15°C and then allowed to warm to room temperature (25 °C) again. Three of these freeze/thaw cycles were consecutively performed and the stability of the emulsions was evaluated. Surprisingly the formulas containing the inventive polyglycerol esters 2, 3, 6 and 7 showed a higher freeze stability than the emulsion containing the polyglycerol ester 5 as formula 19e showed a full separation of water and oil. Formula 19a 19b 19c 19d 19e Polyglycerol ester according to example 2 2.0 Polyglycerol ester according to example 3 2.0 Polyglycerol ester according to example 6 2.0 Polyglycerol ester according to example 7 2.0 Polyglycerol ester according to example 5 2.0 Cera alba (bees wax) 0.5 0.5 0.5 0.5 0.5 Hydrogenated castor oil 0.5 0.5 0.5 0.5 0.5
202300092 Foreign Filing 21 Persoa gratissima (avocado) oil 12.0 12.0 12.0 12.0 12.0 Simmondsia Chinensis (Jojoba) seed oil 12.0 12.0 12.0 12.0 12.0 Tocopherylacetate 0.5 0.5 0.5 0.5 0.5 ad ad ad ad ad Water 100 100 100 100 100 Glycerin 3.0 3.0 3.0 3.0 3.0 Magnesiumsulfate heptahydrate 1.5 1.5 1.5 1.5 1.5 Aqua (and) Sodium Levulinate (and) Potassium 1,5 1,5 1,5 1,5 1,5 Sorbate Polyglycerol ester 3 x (freeze to –15°C ^ thaw to according to example 25°C) Formula 19a 2 stable Formula 19b 3 stable Formula 19c 6 stable Formula 19d 7 stable Formula 19e 5 phase separation Formulation examples The following examples show that the inventive emulsifier can be used for the stabilization of versatile cosmetic formulations as well as for the dispersion of pigments and other solids. Furthermore, the examples show the compatibility with typical co-emulsifiers, cosmetic oils, emollients, waxes, and stabilizers as well as the tolerance against emulsion-destabilizing components such as UV-filters, antimicrobials, electrolytes and active ingredients. The present invention is described by the examples listed below, without any intention to limit the invention, the scope of application of which arises from the entire description and the claims, to the embodiments specified in the examples. The example formulations listed below were prepared with each of the polyglyceryl esters of examples 2, 3, 5, 6 and 7 according to the invention; thus in consequence each example formulation explicitly discloses five distinct formulations. Cooling Body Lotion
202300092 Foreign Filing 22 Formula 2a 2b Polyglycerol ester according to example 2, 3, 5, 6 or 2.0 1.5 7: Polyglyceryl-4 Diisostearate/ - 0.5 Polyhydroxystearate/Sebacate (ISOLAN
® GPS; Evonik Industries AG) Castor wax 0.5 0.5 Beeswax 0.5 0.5 Ethylhexyl Stearate 10.0 10.0 Diethylhexyl Carbonate 8.5 8.5 Dimethicone (Belsil DM 5; Wacker Chemical Corp.) 6.0 6.0 Tocopherylacetate 0.5 0.5 Glycerin 3.0 3.0 Water Ad 100 Ad 100 Sodium chloride 1.0 1.0 Ethanol 20.0 20.0 Natural W/O cream Formula 3a 3b Polyglycerol ester according to example 2, 3, 5, 3.0 2.5 6 or 7: Diisostearyl Polyglyceryl-3 Dimer Dilinoleate - 0,5 (ISOLAN
® PDI; Evonik Industries AG) Diethylhexyl Carbonate 7.0 7.0 Oleyl Erucate 3.0 3.0 Almond oil 7.0 7.0 Shea butter 2.0 2.0 Cetyl Ricinoleate 1.0 1.0 Beeswax 0.6 0.6 Castor wax 0.4 0.4 Glycerin 5.0 5.0 Water Ad 100 Ad 100 Magnesium sulfate heptahydrate 1.5 1.5 Sodium Benzoate, Potassium Sorbate 0.5 0.5 (Euxyl K 712; Schülke & Mayr GmbH)
202300092 Foreign Filing 23 Cold processable lotion Formula 4a 4b 4c 4d Polyglycerol ester according to example 3.0 3.0 2.5 2.5 2, 3, 5, 6 or 7: Polyglyceryl-3 Oleate - - 0.5 0.5 (ISOLAN
® GO 33; Evonik Industries AG) Isoamyl Cocoate 5.0 5.00 5.0 5.0 Diethylhexyl Carbonate 12.0 12.0 12.0 12.0 Phenoxyethyl Caprylate 4.0 4.0 4.0 4.0 Zink stearate 0.5 0.5 0.5 0.5 Water Ad 100 Ad 100 Ad 100 Ad 100 Glycerin 3.0 3.0 3.0 3.0 Sodium chloride 1.5 7.0 1.5 7.0 Phenoxyethanol; Ethylhexylglycerin 0.7 0.7 0.7 0.7 (Verstatil
® PE; Evonik Industries AG) Moisturizing lotion with urea Formula 5a 5b Polyglycerol ester according to example 2, 3, 2.0 1.5 5, 6 or 7: Cetyl PEG/PPG-10/1 Dimethicone - 0.5 (ABIL
® EM 180; Evonik Industries AG) Microcrystalline wax 0.5 0.5 Castor wax 0.5 0.5 C12-15 Alkyl Benzoate 7.5 7.5 Lauryl Oleate (TEGOSOFT
® LO; Evonik 5.0 5.0 Industries AG) Ethylhexyl Palmitate 5.0 5.0 Caprylic/Capric Triglyceride 5.0 5.0 Glycerin 3.0 3.0 Urea 20.0 20.0 Magnesiumsulfate Heptahydrate 1.0 1.0 Water Ad 100 Ad 100 Phenoxyethanol; Ethylhexylglycerin 0.70 0.70 (Verstatil
® PE; Evonik Industries AG) Parfume 0.10 0.10
202300092 Foreign Filing 24 W/O lotion with silky-velvety skin feel Formula 6a 6b 6c Polyglycerol ester according to example 2, 3, 5, 6 2.5 2.0 2.0 or 7: Cetyl PEG/PPG-10/1 Dimethicone - 0.5 - (ABIL
® EM 90; Evonik Industries AG) Bis-PEG/PPG-14/14 Dimethicone; Dimethicone - - 1.0 (ABIL
® EM 97 S; Evonik Industries AG) Microcrystalline wax 0.1 0.1 0.1 Castor wax 0.1 0.1 0.1 Diethylhexyl Carbonate 11.8 11.8 11.8 Myristyl Myristate 1.0 1.0 1.0 Dimethicone (Belsil DM 5; Wacker Chemical 8.0 8.0 8.0 Corp.) Dimethicone (ABIL
® 350; Evonik Industries AG) 0.5 0.5 0.5 Glycerin 3.0 3.0 3.0 Magnesium sulfate heptahydrate 1.5 1.5 1.5 Water Ad 100 Ad 100 Ad 100 Benzyl Alcohol; Ethylhexylglycerin; Tocopherol 0.7 0.7 0.7 (Euxyl K 900; Schülke & Mayr GmbH) Baby care Formula 7a 7b 7c 7e 7f 7g 7f Polyglycerol ester according to 3.0 2.0 2.0 2.0 2.0 2.0 example 2, 3, 5, 6 or 7: Sorbitan Oleate (TEGO
® SMO V; 1.0 Evonik Industries AG) PEG-30 Dipolyhydroxystearate 1.0 (Arlacel P135; Croda) Polyglyceryl-3 Diisostearate 1.0 (Lameform TGI; BASF SE)
202300092 Foreign Filing 25 Glyceryl Oleate, Polyglyceryl-3 1.0 Polyricinoleate, Olea Europaea (Olive) Oil Unsaponifiables (Plantasens Natural Emulsifier CP5; Clariant) Paraffinum Liquidum; Petrolatum; - 1.0 Ozokerite; Glyceryl Oleate; Lanolin Alcohol (PROTEGIN
® XN; Evonik Industries AG) Lauryl PEG-9 1.0 Polydimethylsiloxyethyl Dimethicone (KF-6038; Shin-Etsu Chemical Co.) Castor wax 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Microcrystalline wax 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Oleyl Erucate 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Isoamyl Cocoate 3.8 3.8 3.8 3.8 3.8 3.8 3.8 Ethylhexyl Palmitate 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Almond oil 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Zink oxide 20.0 20.0 20.0 20.0 20.0 20.0 20.0 Glycerin 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Magnesium sulfate Heptahydrate 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Sodium Lactate; Sodium PCA; 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Glycine; Fructose; Urea; Niacinamide; Inositol; Sodium Benzoate; Lactic Acid (LACTIL
®; Evonik Industries AG) Betaine (TEGO
® Natural Betaine; 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Evonik Industries AG) Water Ad Ad Ad Ad Ad Ad Ad 100 100 100 100 100 100 100
202300092 Foreign Filing 26 Benzyl Alcohol; Ethylhexylglycerin; 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Tocopherol (Euxyl K 900; Schülke & Mayr GmbH) Foot care Formula 8a 8b 8c 8d 8e 8f Polyglycerol ester according to example 2, 3.0 2.5 3.0 3.0 3.0 3.0 3, 5, 6 or 7: Petrolatum; Ozokerite; Hydrogenated - 0.5 - - - - Castor Oil; Glyceryl Isostearate; Polyglyceryl-3 Oleate (PROTEGIN
® W; Evonik Industries AG) Castor wax 0.1 0.1 0.1 0.1 0.1 0.1 Microcrystalline wax 0.1 0.1 0.1 0.1 0.1 0.1 Diethylhexyl Carbonate 9.0 9.0 9.0 9.0 9.0 9.0 Ethylhexyl Palmitate 9.0 9.0 9.0 9.0 9.0 9.0 Stearyl Heptanoate 8.8 8.8 8.8 8.8 8.8 8.8 Glycerin 3.0 3.0 3.0 3.0 3.0 3.0 Magnesium sulfate Heptahydrate 1.0 1.0 1.0 1.0 1.0 1.0 Ceramide NP; Ceramide AP; Ceramide 5.0 5.0 5.0 5.0 5.0 5.0 EOP; Phytosphingosine; Cholesterol; Sodium Lauroyl Lactylate; Carbomer; Xanthan Gum (SK-INFLUX
® V; Evonik Industries AG) Betaine 3.0 3.0 3.0 3.0 3.0 3.0 (TEGO
® Natural Betaine; Evonik Industries AG) Water Ad Ad Ad Ad Ad Ad 100 100 100 100 100 100 Benzyl Alcohol; Ethylhexylglycerin; 0.7 0.7 Tocopherol (Euxyl K 900; Schülke & Mayr GmbH)
202300092 Foreign Filing 27 Zinc Sulfate 1.5 1.5 Glyceryl Caprate (Dermosoft
® GMC MB; 0.5 Evonik Dr. Streatmans GmbH) Glyceryl Caprylate (Dermosoft® GMCY 0.5 MB; Evonik Dr. Streatmans GmbH) Pentylene Glycol (Dermosoft® Pentiol 3.0 eco; Evonik Dr. Streatmans GmbH) Triethyl Citrate (and) Glyceryl Caprylate 1.0 (and) Benzoic Acid (Verstabil® TBG; Evonik Dr. Streatmans GmbH) Sun protection SPF 30 UVA with insect repellent Formula 9a 9b Polyglycerol ester according to example 2, 3, 5, 6 3.0 2.0 or 7: Polyglyceryl-2 Dipolyhydroxystearate - 1.0 (Dehymuls PGPH; BASF SE) Oleyl Erucate 1.5 1.5 Diethylhexyl Carbonate 1.5 1.5 Diethylamino Hydroxybenzoyl Hexyl Benzoate 5.4 5.4 Ethylhexyl Methoxycinnamate 10.0 10.0 Octocrylene 2.0 2.0 Polyacrylamide; C13-14 Isoparaffin; Laureth-7 2.1 2.1 (Sepigel 305; Seppic) Ethyl Butylacetylaminopropionate 4.0 4.0 Tocopheryl Acetat 0.5 0.5 Glycerin 3.0 3.0 Ethanol 0.5 0.5 Magnesium sulfate heptahydrate 1.0 1.0 Water Ad 100 Ad 100 Benzyl Alcohol; Ethylhexylglycerin; Tocopherol 0.7 0.7 (Euxyl K 900; Schülke & Mayr GmbH) Parfume 0.1 0.1
202300092 Foreign Filing 28 Sun protection SPF 30 UVA according to eco-criteria Formula 10a 10b Polyglycerol ester according to example 2, 3, 5, 6 or 7: 3.0 2.0 Polyglyceryl-3 Polyricinoleate (Cithrol PG3PR; Croda Int. Plc) - 1.0 Isoamyl Cocoate 2.0 2.0 Decyl Cocoate 10.0 10.0 Isopropyl Palmitate 10.0 10.0 Zinc Oxide (Zinc Oxide PI; Symrise) 16.0 16.0 Titanium Dioxide [nano]; Alumina; Stearic Acid (Eusolex T-S; 9.0 9.0 Merck KGaA) Water Ad 100 Ad 100 Glycerin 3.0 3.0 Magnesium sulfate heptahydrate 1.0 1.0 Sodium Benzoate, Potassium Sorbate (Euxyl K 712; Schülke & 0.5 0.5 Mayr GmbH) Sun protection spray SPF 30 UVA Formula 11a 11b Polyglycerol ester according to example 2, 3, 5, 6 or 7: 2.0 1.5 Lauryl PEG-10 Tris(Trimethylsiloxy)silylethyl Dimethicone (ES-5300 - 0.5 Formulation Aid; Dow Corning Corp.) Ethylhexyl Methoxycinnamate; Diethylamino Hydroxybenzoyl Hexyl 7.5 7.5 Benzoate (Uvinul A+B; BASF SE) Ethylhexyl Salicylate 5.0 5.0 Homosalate 15.0 15.0 Butyl Methoxydibenzoylmethane 3.0 3.0 Benzophenone-3 6.0 6.0 Octocrylene 10.0 10.0 Triisostearin 2.0 2.0 Microcrystalline wax 1.2 1.2 Castor wax 0.8 0.8 Cetyl Dimethicone 2.0 2.0 Diethylhexyl Carbonate 2.0 2.0 Water Ad 100 Ad 100 Sodium chloride 1.0 1.0 Ethylenediaminetetraacetic acid 0.1 0.1
202300092 Foreign Filing 29 Propylene glycol 3.0 3.0 Phenoxyethanol; Ethylhexylglycerin (Verstatil
® PE; Evonik Industries AG) 0.7 0.7 Sun protection spray SPF 50 UVA Formula 12a 12b 12a 12b Polyglycerol ester according to example 2, 3, 5, 6 or 2.5 2.5 3.0 3.0 7: Cetyl PEG/PPG-10/1 Dimethicone (ABIL
® EM 90; 1.0 1.0 - - Evonik Industries AG) Microcrystalline wax 0.3 0.3 0.3 0.3 Castor wax 0.3 0.3 0.3 0.3 Diethylhexyl Carbonate 2.4 2.4 - - Phenoxyethyl Caprylate - - 3.9 3.9 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 6.0 6.0 - - Diethylamino Hydroxybenzoyl Hexyl Benzoate 7.0 7.0 5.0 5.0 Butyl Methoxydibenzoylmethane - - 4.5 4.5 Ethylhexyl Salicylate 3.0 3.0 5.0 5.0 Ethylhexyl Methoxycinnamate 7.0 7.0 - - Octocrylene - - 9.0 9.0 Homosalate 3.0 3.0 5.0 5.0 Ethylhexyl Triazone 1.0 1.0 2.0 2.0 Titanium Dioxide; Silica; Dimethicone (Parsol TX; 2.0 2.0 2.0 2.0 DSM Nutritional Products Llc.) Water Ad Ad Ad Ad 100 100 100 100 Glycerin 3.0 3.0 3.0 3.0 Magnesium sulfate heptahydrate 1.5 1.5 1.5 1.5 Benzyl Alcohol; Ethylhexylglycerin; Tocopherol 0.7 0.7 0.7 0.7 (Euxyl K 900; Schülke & Mayr GmbH) Sun protection lotion with SPF 50 according to FDA-criteria Formula 13a 13b Polyglycerol ester according to example 2, 3, 5, 6 or 7: 2.0 1.5
202300092 Foreign Filing 30 Lauryl PEG-10 Tris(Trimethylsiloxy)silylethyl Dimethicone (ES-5300 - 0.5 Formulation Aid; Dow Corning Corp.) Ethylhexyl Methoxycinnamate; Diethylamino Hydroxybenzoyl Hexyl 7.5 7.5 Benzoate (Uvinul A+B; BASF SE) Ethylhexyl Salicylate 5.0 5.0 Homosalate 15.0 15.0 Butyl Methoxydibenzoylmethane 3.0 3.0 Benzophenone-3 6.0 6.0 Octocrylene 10.0 10.0 Triisostearin 2.0 2.0 Microcrystalline wax 1.2 1.2 Castor wax 0.8 0.8 Cetyl Dimethicone 2.0 2.0 Diethylhexyl Carbonate 2.0 2.0 Water Ad 100 Ad 100 Sodium chloride 1.0 1.0 Ethylenediaminetetraacetic acid 0.1 0.1 Propylene glycol 3.0 3.0 Phenoxyethanol; Ethylhexylglycerin (Verstatil
® PE; Evonik Industries AG) 0.7 0.7 Foundation Formula 14a 14b 14c 14d 14e 14f 14g Polyglycerol ester according to example 4.5 2.5 3.0 2.5 2.0 2.0 3.0 2, 3, 5, 6 or 7: Bis-(Glyceryl/Lauryl) Glyceryl Lauryl - 2.0 - - - - Dimethicone; Caprylic/Capric Triglyceride (ABIL
® EM 120; Evonik Industries AG) Polyglyceryl-4 Isostearate (ISOLAN
® GI - - 1.0 - - - 34; Evonik Industries AG) Cetyl Diglyceryl - - - 1.0 - - Tris(Trimethylsiloxy)silylethyl Dimethicone (DC-5600; Dow Corning Corp.) Lauryl Polyglyceryl-3 - - - - 1.0 - Polydimethylsiloxyethyl Dimethicone (KF-6105; Shin-Etsu Chemical Co.)
202300092 Foreign Filing 31 Polyglyceryl-4 Isostearate; Cetyl - - - - - 2.0 PEG/PPG-10/1 Dimethicone; Hexyl Laurate (ABIL
® WE 09; Evonik Industries AG) Polyglyceryl-6 Polyhydroxystearate 1.0 (and) Polyglyceryl-6 Polyricinoleate (EMULIUM
® ILLUSTRO; Gattefossé) Isoamyl Cocoate 10.8 10.8 10.8 10.8 10.8 10.8 10.8 Oleyl Erucate 8.0 8.0 8.0 8.0 8.0 8.0 8.0 Titanium Dioxide, Alumina, 4.0 4.0 4.0 4.0 4.0 4.0 4.0 (Triethoxycaprylylsilane Hombitan AC360; Sachtleben) Iron Oxides (Sicovit Braun 70 E 172; 2.1 2.1 2.1 2.1 2.1 2.1 2.1 Rockwood) Nylon-12 (TEGOLON
® 12-20; Evonik 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Industries AG) Cylcopentasiloxane 3.5 3.5 3.5 3.5 3.5 3.5 3.5 Disteardimonium Hectorite (Bentone 38 1.0 1.0 1.0 1.0 1.0 1.0 1.0 V CG; Elementis) Propylencarbonat 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Water Ad Ad Ad Ad Ad Ad Ad 100 100 100 100 100 100 100 Magnesium sulfate heptahydrate 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Glycerin 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Creatine 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Ceteareth-25; Glycerin; Cetyl Alcohol; 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Behenic Acid; Cholesterol; Ceramide EOP; Ceramide EOS; Ceramide NP; Ceramide NS; Ceramide AP; Caprooyl Phytospingosine; Caprooyl Sphingosine (SKINMIMICS
®; Evonik Industries AG) Benzyl Alcohol; Ethylhexylglycerin; 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Tocopherol (Euxyl K 900; Schülke & Mayr GmbH) CC (Color Control) Fluid Formula 15a 15b 15c 15d 15e 15f 15g
202300092 Foreign Filing 32 Polyglycerol ester according to 3.0 2.0 2.5 3.0 2.5 2.0 1.0 example 2, 3, 5, 6 or 7: Polyglyceryl-4 - 1.0 - - - - - Diisostearate/Polyhydroxysteara te/Sebacate (ISOLAN
® GPS; Evonik Industries AG) Sorbitan Oleate (TEGO
® SMO - - 0.5 - - - - V; Evonik Industries AG) PEG-30 Dipolyhydroxystearate - - - 1.0 - - - (Arlacel P135; Croda) Polyglyceryl-3 Diisostearate - - - - 1.5 - - (Lameform TGI; BASF SE) Glyceryl Oleate, Polyglyceryl-3 - - - - - 1.0 - Polyricinoleate, Olea Europaea (Olive) Oil Unsaponifiables (Plantasens Natural Emulsifier CP5; Clariant) Lauryl PEG-9 - - - - - - 1.0 Polydimethylsiloxyethyl Dimethicone (KF-6038; Shin- Etsu Chemical Co.) Ethylhexyl Methoxycinnamate; 10.0 10.0 10.0 10.0 10.0 10.0 10.0 Diethylamino Hydroxybenzoyl Hexyl Benzoate (Uvinul A+B; BASF SE) Cylcopentasiloxane 3.5 3.5 3.5 3.5 3.5 3.5 3.5 Disteardimonium Hectorite 1.0 1.0 1.0 1.0 1.0 1.0 1.0 (Bentone 38 V CG; Elementis) Propylencarbonat 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Titanium Dioxide, Alumina, 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Triethoxycaprylylsilane Talc 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Iron Oxides; 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Triethoxycaprylylsilane Iron Oxides; 0.12 0.12 0.12 0.12 0.12 0.12 0.12 Triethoxycaprylylsilane Iron Oxides; 0.08 0.08 0.08 0.08 0.08 0.08 0.08 Triethoxycaprylylsilane Diethylhexyl Carbonate 4.0 4.0 4.0 4.0 4.0 4.0 4.0
202300092 Foreign Filing 33 C12-15 Alkyl Benzoate 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Isopropyl Palmitate 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Nylon-12 (TEGOLON
® 12-20; 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Evonik Industries AG) Water Ad Ad Ad Ad Ad Ad Ad 100 100 100 100 100 100 100 Glycerin 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Sodium chloride 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Tetrapeptide-30; Glycerin 0.3 0.3 0.3 0.3 0.3 0.3 0.3 (TEGO Pep 4-Even; Evonik Industries AG) Phenoxyethanol; 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Methylparaben; Ethylparaben; Propylparaben (Phenonip XB; Clariant) AP/Deo spray or aerosol spray Formula 16a 16b 16c 16d Polyglycerol ester according to 3.0 2.0 3.0 2.0 example 2, 3, 5, 6 or 7: Polyglyceryl-4 Diisostearate/Polyhydroxy- ® - 1.0 - 1.0 stearate/Sebacate (ISOLAN GPS; Evonik Industries AG) Isopropyl Palmitate 20.0 20.0 20.0 20.0 Diethylhexyl Carbonate 7.0 7.0 7.0 7.0 Water Ad 100 Ad 100 Ad 100 Ad 100 Glycerin 2.0 2.0 2.0 2.0 Aluminum Chlorohydrate (50% aq.) 30.0 30.0 30.0 30.0 Parfume 1.0 1.0 1.0 1.0 Mix emulsions 16c-d with Propellant - - propellant in a mass ratio of 5:2 Sun protection aerosol SPF 50 UVA
202300092 Foreign Filing 34 Formula 17a 17b 17c 17d Polyglycerol ester according to example 4.0 4.0 4.0 4.0 2, 3, 5, 6 or 7: Cetyl PEG/PPG-10/1 Dimethicone - - 1.0 1.0 (ABIL
® EM 90; Evonik Industries AG) C12-15 Alkyl Benzoate 10.0 10.0 10.0 10.0 Diethylhexyl Carbonate 13.0 13.0 13.0 13.0 Bis-Ethylhexyloxyphenol Methoxyphenyl 4.0 4.0 4.0 4.0 Triazine Diethylamino Hydroxybenzoyl Hexyl 5.0 5.0 5.0 5.0 Benzoate Ethylhexyl Salicylate 5.0 5.0 5.0 5.0 Ethylhexyl Methoxycinnamate 4.0 4.0 4.0 4.0 Water Ad 100 Ad 100 Ad 100 Ad 100 Glycerin 3.0 3.0 3.0 3.0 UV-filter solution 20.0 20.0 20.0 20.0 Magnesium sulfate heptahydrate 1.0 1.0 1.0 1.0 Benzyl Alcohol; Ethylhexylglycerin; 0.7 0.7 0.7 0.7 Tocopherol (Euxyl K 900; Schülke & Mayr GmbH) Mix emulsion 17a-d with propellant in a mass ratio of 2:1