Electrostatically sprayable cosmetic formulations

Abstract

The present invention relates to electrostatically sprayable cosmetic formulations that have sufficient sun protection factor and water resistance and that provide sufficient, i.e., near complete, coverage of the skin surface when applied to the surface of the skin by electrostatic spraying.

Description

[Technical field]

[0001] The present invention relates to electrostatically sprayable cosmetic formulations which can be easily applied to a subject, provide improved protection, particularly against harmful UV-A and UV-B radiation, and also provide good water resistance. [Background technology]

[0002] Solar ultraviolet radiation with wavelengths of about 280 to about 400 nm, namely short-wave ultraviolet (UV-B) (280 nm to 320 nm) and long-wave ultraviolet (UV-A) (320 nm to 400 nm), is responsible for skin damage such as sunburn or cell mutation, but it is also well known to cause loss of skin elasticity, suppress immune function, promote premature signs of aging and other undesirable health effects. On the other hand, for most people, tanning the skin for cosmetic purposes is preferred. Skin tanning is caused by longer wavelength ultraviolet radiation up to about 420 nm. To prevent or reduce the adverse effects of solar radiation, various sunscreen products are commercially available. In addition to this main function of sunscreens, it is also desirable for the sunscreen to exhibit good resistance to sweat, fresh water or salt water when the subject is exposed to water.

[0003] Currently available sunscreens have high protection against UV-A and UV-B solar radiation and exhibit good water resistance.

[0004] However, although from a theoretical point of view the sunscreen formulations known in the prior art show sufficient protection against solar radiation, in practice the protection against harmful solar radiation leaves much to be desired. One of the reasons for this is that the sunscreen formulations are not applied to the surface of the skin in the correct way.

[0005] Most sunscreen preparations are lotions that can be applied to the surface of the skin by a limited number of methods. A simple method is to apply lotion by hand. This method has many disadvantages. In particular, this method does not ensure that a sufficient amount of sunscreen lotion is applied to the surface of the skin, and in particular, this application method does not provide sufficient coverage of the skin. Moreover, in some cases, an unnecessarily large amount of sunscreen preparation is applied to the surface of the skin, which causes an unpleasant sensation.

[0006] Another application method, which ensures that a sufficient amount of sunscreen formulation is applied to the surface of the skin, but is also suitable, is to use a pump spray or a pre-pressurized aerosol container, which allows the formulation to be atomized and sprayed by a propellant gas.However, traditional aerosol sprays often use volatile compounds as propellants, which can be harmful to the environment and to health, and are actually regulated in many countries.In addition, it is almost impossible to generate a constant and homogeneous flow of sunscreen formulation.Therefore, this application method also does not allow sufficient coverage of the skin surface, i.e., nearly 100% coverage.

[0007] In the last few years in the field of cosmetics, further application methods have been of interest, in which the cosmetic is applied to the subject by electrostatic spraying. Such methods are described, for example, in WO 94 / 11119 or WO 2001 / 012139.

[0008] This application method can be performed without the use of environmentally harmful propellants and provides a constant and homogenous flow of the product, so that a sufficient amount of a cosmetic formulation, e.g., a sunscreen formulation, can be applied to the surface of the skin, such that nearly complete coverage of the skin may be possible.

[0009] In the prior art, different electrostatic spraying devices are known, for example as described in WO 94 / 11119, US 2010 / 0116897 or DE 102017108610.2. In electrostatic spraying devices, a voltage generator generates a high voltage which electrically charges the cosmetic compounds. As a result, the cosmetic is sprayed.

[0010] However, the biggest problem with this application method is that known cosmetic formulations, such as sunscreen formulations, are not electrostatically sprayable because they do not have suitable electrical properties, such as resistivity, dielectric constant, etc., and / or other properties, such as high surface tension, viscosity, etc., that do not allow for electrostatic spraying. For example, like many other cosmetic lotions and creams, sunscreen formulations contain emollients in addition to UV-A and UV-B filters.

[0011] Emollients, also called cosmetic oils, are compounds that soften and smooth the skin's scales, helping to reduce rough and flaky skin. They are often occlusives, i.e. substances that provide a protective layer that helps prevent moisture (water) loss from the skin. Examples of emollients are silicones such as dimethicone or cyclomethicone, vegetable oils, butters such as coca butter or shea butter, alcohols such as stearyl alcohol or cetyl alcohol, and petrolatum derivatives such as petrolatum jelly or mineral oil. In sunscreen formulations, emollients are further used as solubilizers for crystalline UV filters. Due to their electrical properties, i.e. resistivity and dielectric constant, most emollients exhibit worse electrostatic sprayability. The same is true for UV filters that are commonly used in sunscreen formulations.

[0012] Furthermore, even if some cosmetic formulations have suitable electrical properties, it is still not possible to electrostatically spray these formulations so that all parts of the skin are covered by the cosmetic formulation, which results in a so-called streak effect on the skin, i.e. the applied cosmetic formulation creates a "striped pattern" on the skin. [Brief description of the drawings]

[0013] [Figure 1] 1 shows diagrammatically the undesirable "streaks" on the skin that result when a cosmetic formulation cannot be sprayed evenly and therefore homogeneous distribution of the formulation on the skin is not possible.

[0014] [Diagram 2] 1 shows the skin surface before treatment on the forearm of two subjects (reference measurement).

[0015] [Diagram 3] 1 shows the skin surface of a subject's forearm treated with the formulation of Comparative Example 1 according to Spray Test 1 below.

[0016] [Figure 4] 1 shows the skin surface of a subject's forearm treated with the formulation of Comparative Example 2 according to Spray Test 1 below.

[0017] [Diagram 5] 1 shows the skin surface of a subject's forearm treated with the formulation of Comparative Example 3 according to Spray Test 1 below.

[0018] It was therefore an object of the present application to provide an electrostatically sprayable cosmetic formulation which has a sun protection efficiency comparable to that of sunscreen formulations known in the prior art, and which further provides almost 100% coverage of the skin surface, i.e. the distribution of the formulation on the skin is homogenous and therefore no streak effect occurs.

[0019] Surprisingly, it has been found that when a cosmetic formulation comprises ethanol and a polar emollient (cosmetic oil) that is liquid at 20° C. in combination with a film-forming agent mixture comprising at least one polyalkyleneoxy-terminated polyamide and at least one acrylate, the cosmetic formulation exhibits improved electrostatic sprayability, i.e. in particular no streak effect occurs and therefore almost complete coverage of the skin can be achieved.

[0020] [Figure 6] 6 shows a schematic representation of complete coverage of the skin by using the cosmetic preparation of the present invention, i.e. no streak effect occurs. Enlarged cross section "Detail A" of Fig. 6 shows a portion of the skin covered with the cosmetic preparation according to the present invention.

[0021] [Figure 7] 1 shows the skin surface of the forearm of a subject treated with the formulation of Comparative Example 4 (left side) and with the formulation of the invention SPF 30 (right side) according to spray test 2 as described below.

[0022] According to the present invention, to ensure that the cosmetic formulation is electrostatically sprayable, ethanol must be used in combination with a liquid polar emollient in sufficient quantity so that the polarity of the emollients is greater than their log K ow is given by the value.

[0023] Additionally, it has been found that the use of a film former mixture comprising a polyalkyleneoxy-terminated polyamide in combination with an acrylate in a cosmetic formulation improves the electrostatic sprayability of the cosmetic formulation while using an intermediate range of ethanol in the formulation, and also provides an increase in the Sun Protection Factor (SPF) of the cosmetic formulation.

[0024] Furthermore, it has been found that by using the film-forming agent mixture according to the invention, it is not necessary to use thickeners in the cosmetic formulation.

[0025] Therefore, the present invention provides a pharmaceutical composition comprising, based on the total weight of the formulation: a) 20 to 60% by weight of ethanol; b) Liquid at 20°C and log K ow 10 to 55 wt. % of a skin softener having a molecular weight of 2.0 to 10; c) 10 to 55% by weight of a UV-A and / or UV-B filter; d) 0.5 to 15 wt. % of a polymeric film former mixture comprising at least one polyalkyleneoxy-terminated polyamide and at least one acrylate; e) 0 to 4% by weight of cosmetic additives; An electrostatically sprayable cosmetic formulation is provided, in which the amount of water present in the formulation is less than 5% by weight, based on the total weight of the formulation, and the sum of the weights of the ingredients is 100%.

[0026] The cosmetic formulations defined above exhibit the desired electrostatic spraying behavior, ie no strike effect, improved Sun Protection Factor (SPF) and good water resistance.

[0027] As used herein, the abbreviation "wt.-%" or "w / w" means "percent by weight" and, unless otherwise expressly stated or apparent in the context, refers to the weight of compound relative to the (total) weight of a formulation of compound or substrate.

[0028] The term "comprising" also includes "consisting essentially of" and "consisting of."

[0029] As used herein, the use of "a" in the singular also includes the plural ("some") and vice versa, unless the context clearly dictates otherwise.

[0030] A cosmetic preparation in the sense of the present invention is a preparation selected from the group consisting of sunscreen, skin care, hairspray, cosmetic foundation, lipstick, hair dye, and self-tanning preparation.The cosmetic preparation can be used alone or in a mixture with other cosmetic preparations.Preferably, the cosmetic preparation is a sunscreen preparation.

[0031] Electrostatically sprayable cosmetic formulations having a particular combination of components according to the invention preferably have a viscosity of 15 to 100 GOhm mm 2 / m, preferably 20 to 85GOhm mm 2 / m, the specific electrical resistivity is 80GOhm mm 2 / m or less, 60GOhm·mm 2 / m or less, 50GOhm·mm 2 / m or less, and most preferably 35 to 48 GOhm mm 2 / m. This ensures that the formulation is well electrostatically sprayable and therefore does not cause undesirable streak effects on the skin.

[0032] Furthermore, in order to provide a cosmetic formulation that exhibits good electrostatic spray behavior, the formulation preferably has a surface tension, measured by the stamp method described below (see measurement method), of 15 to 50 m / Nm, more preferably 20 to 45 m / Nm, 22 to 40 m / Nm, more preferably 25 to 35 m / Nm.

[0033] Furthermore, the dielectric constant of the cosmetic preparation according to the present invention may be at least 2.0, preferably at least 2.3, more preferably at least 2.5, and most preferably at least 2.6. In particular, the dielectric constant of the cosmetic preparation is preferably 2.4 to 25.0, more preferably 2.4 to 20.0, or 2.4 to 10.0, and most preferably 2.4 to 5.0. Hereinafter, a method for measuring the dielectric constant according to the present invention will be described (see Measurement Method).

[0034] Furthermore, the cosmetic formulation of the present invention may have a viscosity of 0.65 mPa·s to 5000 mPa·s, preferably 1.0 to 1000 mPa·s, 5.0 to 500 mPa·s, more preferably 10.0 to 100 mPa·s, measured as described below (see measurement methods). In particular, good spray behavior of the cosmetic formulation can be observed when the cosmetic formulation has a viscosity of less than 4.0 mPa·s. Cosmetic formulations with a viscosity of at least 8.0 mPa·s show sufficient spray behavior.

[0035] Any electrostatic device known in the art can be used to spray the cosmetic preparation on the subject.However, it is preferred to use a device as described in DE 102017108610.2 (which is further specified in DE 102017108612.9, DE 102017108613.7, DE 102107108614.5 and DE 102107108615.3).

[0036] As mentioned above, the cosmetic formulation contains a sufficient amount of ethanol in combination with a liquid polar emollient so that the formulation has the necessary electrostatic properties and therefore exhibits good electrostatic spray behavior.

[0037] Furthermore, it was found that the sprayability of the emollients, and therefore of the entire cosmetic formulation, as well as that of other ingredients present in the cosmetic formulation, can be positively influenced by the presence of ethanol in the formulation. For example, the highly viscous UV-B filter octocrylene shows worse electrostatic sprayability, especially at low voltages. However, when octocrylene is mixed with ethanol, the spray quality can be improved (see results in Table 1 below). The spray tests were performed with a distance of 13 cm from the spray nozzle to the outside left side of the metal tube. The preset voltages for the three subsequent tests were 20 kV, 30 kV and 40 kV, respectively. A voltage of 3.7 V was used for the fluid pump. After each test liquid change, the tube system was rinsed with isopropanol and / or ethanol. The spray behavior of the formulations was evaluated optically and the spray pattern was rated on the following scale: good, moderate, poor, almost unsprayable.

[0038] [Table 1]

[0039] A general trend can be seen in which spray quality increases with ethanol content. However, high ethanol contents in cosmetic formulations, particularly sunscreen formulations, are undesirable because ethanol has a tendency to be drying and irritating to the skin.

[0040] According to the present invention, when ethanol is used in combination with an emollient and a film-forming agent mixture as defined herein, the amount of ethanol present in the cosmetic formulation can be reduced. In that case, an ethanol content of 20-60% by weight, based on the total weight of the formulation, is sufficient. In particular, the ethanol content is at least 25% by weight, at least 35% by weight, at least 40% by weight, more preferably at least 45% by weight or less, but preferably 58% by weight or less, 55% by weight or less, more preferably 52% by weight or less, based on the total weight of the formulation. In a preferred embodiment of the present invention, the ethanol content is 50-55% by weight, based on the total weight of the formulation. In another preferred embodiment, the ethanol content is 42-46% by weight or 38-42% by weight, based on the total weight of the composition.

[0041] The emollients (cosmetic oils) of the present invention are those emollients commonly used in cosmetics such as sunscreen formulations, i.e., materials that provide a protective layer that helps prevent moisture (water) loss from the skin as described above. Additionally, the emollient must be liquid at 20° C. and polar.

[0042] In the cosmetic field, one possibility to define the polarity of a compound is the n-octanol / water partition coefficient (K ow The objective of this study is to determine the partition coefficient (P) of a compound in a mixture of these two immiscible phases at equilibrium. The partition coefficient thus measures how hydrophilic ("water loving") or hydrophobic ("water phobic") a test compound is. n-Octanol / water partition coefficients are most often expressed as a decade logarithm K ow or log P. The determination of the n-octanol / water partition coefficient is described, for example, in J. Sangster's "Octanol-Water Partition Coefficients: Fundamentals and Physical Chemistry" (Wiley Series In solution chemistry Vol. 2), John Wiley & Sons, Chichester, 1997.

[0043] According to the present invention, the logarithm K of the emollient suitable for the cosmetic formulation of the present invention ow is 2.0 to 10.0, preferably 2.5 to 9.5, 3.0 to 8.5, and more preferably 3.5 to 7.5.

[0044] Any emollient known in the prior art that meets the above requirements is suitable for the cosmetic preparation of the present invention.Examples of suitable emollients are phenoxyethyl caprylate, PPG-3 myristyl ether, dibutyl adipate, dicaprylyl carbonate, isoamyl cocoate, diethylhexyl carbonate, isopropyl myristate, isopropyl palmitate, PPG-14 butyl ether, decyl cocoate, PPG-15 stearyl ether, C12-C15 alkyl benzoate and combinations thereof.

[0045] The cosmetic formulation of the present invention preferably contains at least two, at least three, at least four, but not more than 10, preferably not more than eight, more preferably not more than five different emollients. In particular, the cosmetic formulation preferably contains phenoxyethyl caprylate, PPG-3 myristyl ether, dibutyl adipate, dicaprylyl carbonate, and combinations thereof as emollients. In particular, the cosmetic formulation of the present invention preferably contains a mixture of these four emollients.

[0046] The different emollients are used in different or equal amounts in the formulation, such that the total amount of emollients is 10-55% by weight, based on the total weight of the formulation. Preferably, the total amount of emollients present in the formulation is 15-50%, 20-45%, 22-40%, 23-30% by weight, based on the total weight of the formulation.

[0047] The cosmetic preparation of the present invention exhibits sufficient sun protection. This property is indicated by the so-called sun protection factor (SPF). SPF is a measure of the proportion of sunburn-causing UV radiation that reaches the skin. For example, "SPF 15" means that 1 / 15 of the sunburn-causing UV radiation reaches the skin, assuming that the sunscreen is applied evenly at a thickness dose of 2 milligrams per square centimeter. The determination of the SPF of a sunscreen preparation is described in detail in ISO 24444:2010(E).

[0048] The cosmetic formulation of the present invention has an SPF of at least 15, preferably at least 20, at least 25, at least 30, more preferably at least 50 or more, as measured according to ISO 24444:2010(E). A sunscreen formulation having an SPF of 60 or more is designated as an SPF50+ sunscreen formulation. Most preferably, the cosmetic formulation of the present invention has an SPF of at least 30.

[0049] The ability to protect a subject from the harmful UV rays of the sun depends, inter alia, on the amount of UV-A and UV-B filters present in the cosmetic formulation. Generally, a mixture of UV-A and UV-B filters is used. In the present invention, the cosmetic formulation comprises UV-A and / or UV-B filters in an amount of 10-55% by weight, preferably 12-50% by weight, 15-40% by weight, 20-35% by weight, more preferably 16-32% by weight or 18-31% by weight, based on the total weight of the formulation.

[0050] Furthermore, for good electrostatic sprayability of the formulation, the UV-A and / or UV-B filters have a log K of 2.0 to 7.0, preferably 2.5 to 6.5, more preferably 3.0 to 6.0. ow It is preferred that the compound has the formula:

[0051] As mentioned above, generally, a mixture of UV-A and UV-B filters is used in sunscreen formulations.This also applies to the cosmetic formulation of the present invention, where the amount of UV-A and UV-B filters can be equal or different.Preferably, the concentration of UV-A and UV-B filters used in the cosmetic formulation of the present invention complies with the requirements of Annex VI of Regulation (EC) No. 1223 / 2009 on cosmetics.

[0052] In particular, it is preferred that the cosmetic formulation comprises at least 4, at least 5 but not more than 10, preferably not more than 8, different UV filters which may be UV-A and / or UV-B filters.

[0053] Any UV filter known in the prior art and that does not adversely affect the electrostatic sprayability of the formulation can be used in the present invention. Suitable UV filters are disclosed in Annex VI of the Cosmetics Regulation (EC) No. 1223 / 2009. Some examples of these are phenylene-1,4-bis-(2-benzimidazyl)-3,3'-5-5'-tetrasulfonate; phenylbenzimidazole sulfonic acid; 2-phenylbenzimidazole-5-sulfonate; 1,4-di(2-oxo-10-sulfo-3-bornylidenemethyl)benzene and its salts; 4-(2-oxo-3-bornylidenemethyl)-benzenesulfonic acid; 2-methyl-5-(2-oxo-3-bornylidenemethyl)sulfonate; 2,2'-methyl-5-(2-oxo-3-bornylidenemethyl)sulfonate; ETHYLHEXYL SALICYLATE;TEREPHTHALIDENEDICAMPHORSULFONATE;4-(DIMETHYLAMINO)BENZOIC ACID;2-(2H-BENZOTRIAZOL-2-YL)-4-METHYL-6-[2-METHYL-3-[1,3,3,3-TETRAMETHYL-1-[(TRIMETHYLSILYL)OXY]-DISILOXANYL]PROPYL]PHENOL;3-(4-METHYLBENZYLIDENE)-CAMPHOR;Ethylhexyl salicylate;Terephthalidenicamphorsulfonic acid;4-(DIMETHYLAMINO)BENZOIC ACID 2-Hydroxy-4-methoxybenzophenone;2-Hydroxy-4-methoxy-4'-methylbenzophenone;2,2-Dihydroxy-4-methoxybenzophenone;Hexyl-2-(4'-diethylamino-2'-hydroxybenzyl) ester;4-(Dimethylamino)benzoic acid amyl ester;4-Methoxybenzalmalon-di(2-ethylhexyl) ester;4-Methoxycinnamate(2-ethylhexyl) ester;4-Methoxycinnamate;2-Hydroxy-4-methoxybenzophenone;2-Hydroxy-4-methoxy-4'-methylbenzophenone;2,2-Dihydroxy-4-methoxybenzophenone;Hexyl-2-(4'-diethylamino-2'-hydroxybenzyl) ester 4-(tert-butyl)-4'-methoxydibenzoylmethane;Homomethyl salicylate (INCI: Homosalate);2-Ethylhexyl-2-hydroxybenzoate;2-Ethylhexyl-2-cyano-3,3-diphenylacrylate (INCI: Octocrylene);Dimethicodiethyl benzalmalonate;3-(4-(2,2-ethoxycarbonyl-vinyl)-phenoxy)-propenyl)-methoxy-siloxane / dimethylsiloxane copolymer;2,4-Bis-{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine (INCI: Bis-ethylhexyloxyphenol methoxyphenyl triazine); Dioctylbutyramido triazone (INCI: Diethylhexyl-butamido triazone); 2,4-Bis-[5-1-(dimethylpropyl)benzoxazol-2-yl-(4-phenyl)-imino]-6-(2-ethylhexyl)-imino-1,3,5-triazine (CAS number 288254-16-0); Ethylhexyl triazine; 4,4',4' '-(1,3,5-triazine-2,4,6-triyltriimino)-tris-benzoic acid-tris-2-ethylhexyl ester (or: 2,4,6-tris[anilino-(p-carbo-2'-ethyl-1'-hexyloxy)]-1,3,5-triazine (INCI: ethylhexyl triazone); 2,4,6-tribiphenyl-4-yl-1,3,5-triazine; butyl-methoxydibenzoylmethane; isoamyl-p-methoxycinnamate and diethylaminohydroxybenzoylhexylbenzoate.

[0054] Preferably, the UV filter is selected from the group consisting of homosalate, butyl methoxydibenzoylmethane, octocrylene, diethylhexylbutamidotriazone, ethylhexyl salicylate, bis-ethylhexyloxyphenol methoxyphenyl triazine, diethylamino hydroxybenzoyl hexyl benzoate, and combinations thereof.

[0055] In particular, the cosmetic formulation preferably comprises a mixture of UV-A and UV-B filters consisting of butyl methoxydibenzoylmethane, octocrylene, diethylhexylbutamidotriazone, ethylhexyl salicylate, optionally bis-ethylhexyloxyphenol methoxyphenyl triazine, optionally diethylamino hydroxybenzoyl hexyl benzoate, and optionally homosalate.

[0056] In addition to the specific combination of ethanol, emollients and UV-A / UV-B filters as described above, according to the present invention, in order to improve the sprayability of the cosmetic formulation, the cosmetic formulation must contain a film-former mixture comprising at least one polyalkyleneoxy-terminated polyamide and at least one acrylate. Furthermore, the use of the film-former mixture according to the present invention allows the SPF to be increased without the need to increase the amount of UV filters present in the formulation, thus maintaining good sprayability of the formulation.

[0057] Any polyalkyleneoxy-terminated polyamide known in the art may be used in the present invention, for example, as described in U.S. Patent Application Publication No. 2014 / 0212363. However, polyalkyleneoxy-terminated polyamides may be used in combination with polyethylene glycol. Poly Preferably, it is a condensation product of dilinoleic acid, ethylene diamine and polypropylene glycol diamine end-capped with propylene glycol (PEG-PPG)-32 / 10 aminopropyl methyl ether. More preferably, the polyalkyleneoxy-terminated polyamide is selected from the group consisting of polyamide-3, polyamide-4 and mixtures thereof, such as, for example, OleoCraft MP-30, OleoCraft MP-32, OleoCraft HP-31, OleoCraft HP-33, SYLVASOL 80, SYLVACLEAR AF1900V, SYLVACLEAR PE1800V, SYLVACLEAR PA1200V and SYLVACLEAR WF1500V available from Arizona Chemical or Croda. Preferably, the polyalkyleneoxy-terminated polyamide is polyamide-3.

[0058] Further, according to the present invention, the acrylate can be any known in the art, such as, for example, acrylates / dimethicone copolymer, styrene acrylate copolymer, or vinyl acetate (VA) / butyl maleate / isobornyl acrylate copolymer, but preferably the acrylate is an acrylate / amide copolymer. More preferably, the acrylate / amide copolymer is an acrylate / amide copolymer having an alkyl group having 6 to 16 carbon atoms. Most preferably, the acrylate / amide copolymer is an acrylate / octyl acrylamide copolymer. This polymer contains carboxyl groups attached to the polymer backbone and octyl side chains, and is commercially available, for example, under the trademarks DERMACRYL 2.0 or DERMACRYL 79 from AkzoNobel, Germany.

[0059] According to the invention, the film-forming mixture may contain, in addition to polyalkyleneoxy-terminated polyamides and acrylates, as film-forming agents, monomers, copolymers, cross- and terpolymers of organosilicone hybrids, biopolymers, abietic acid derivatives, polyolefins, silicone resins as known in the prior art, in particular vinyl acetates, maleates, alkyl esters, long- and short-chain carboxylic acids, polyamides, ethanol (and) crotonic acid / vinyl C 8-12 These may include esters / VA / bis-vinyl dimethicone crosspolymer, isododens (and) acrylates / dimethicone copolymer, acrylates / dimethicone copolymer (and) cyclopentasiloxane, methyl dihydroabietic acid, hydrogenated polycyclopentadiene isoalkyl (and) isododecane, vinylpyrrolidone (VP) / hexadecane copolymer, hydrogenated dimer dilinoleic acid / dimethyl carbonate copolymer, trimethylpentanediol / adipic acid / glycerin crosspolymer, or combinations thereof.

[0060] As mentioned above, the cosmetic formulation of the present invention comprises the polymeric film-forming agent mixture in an amount of 0.5-15% by weight, based on the total weight of the formulation, preferably in an amount of 0.7-13% by weight, 1-10% by weight, 2-8% by weight, 3-7% by weight, more preferably 4-6% by weight, based on the total weight of the formulation.

[0061] Furthermore, according to the present invention, it is preferred that the amount of polyalkyleneoxy-terminated polyamide present in the film-former mixture is greater than the amount of acrylate, preferably the amount of polyalkyleneoxy-terminated polyamide is 2, 3 or 4 times higher than the amount of acrylate used in the film-former mixture.

[0062] In particular, the cosmetic formulation comprises the polyalkyleneoxy-terminated polyamide in an amount of 0.5-10% by weight, preferably 1-8% by weight, 2-6% by weight, more preferably 3-5% by weight, based on the total weight of the formulation.

[0063] The acrylates are preferably used in the cosmetic formulation in an amount of 0.2 to 3% by weight, preferably 0.5 to 2% by weight, more preferably 1 to 1.5% by weight, based on the total weight of the formulation.

[0064] Most preferably, the amount of polyalkyleneoxy-terminated polyamide present in the cosmetic formulation of the present invention is from 2 to 4% by weight and the amount of acrylate is from 0.5 to 2% by weight, based on the total weight of the formulation.

[0065] In a preferred embodiment of the invention, the film-former mixture comprises (consists of) 1-5 wt. % polyalkyleneoxy-terminated polyamide and 0.5-2.5 wt. % acrylate, based on the total weight of the formulation, hi another embodiment, the film-former mixture consists of 3 wt. % polyalkyleneoxy-terminated polyamide and 1 wt. % acrylate.

[0066] The water resistance of the cosmetic preparations according to the invention, as usually determined and described below (see measurement methods), is preferably greater than 60%, more preferably greater than 70%, even more preferably greater than 80% and most preferably greater than 90%.

[0067] In general, in addition to the active compounds described above, cosmetic formulations also contain cosmetic additives such as cosmetically acceptable carriers, oils, sterols, amino acids, moisturizers, powders, colorants, pigments, dyes, pH adjusters, fragrances, essential oils, vitamin E, provitamins, essential fatty acids, sphingolipids, self-tanning compounds, and the like, and combinations thereof. These additives and combinations thereof may also be present in the cosmetic formulations of the present invention.

[0068] According to the present invention, the additives are preferably selected from the group consisting of fragrances, humectants such as glycerin, vitamins and / or provitamins such as tocopherols and / or tocopheryl acetate, and combinations thereof.

[0069] The cosmetic preparation of the present invention contains 0 to 4% by weight, preferably 0.1 to 3% by weight, more preferably 0.2 to 2% by weight of cosmetic additives, based on the total weight of the preparation.

[0070] Furthermore, the amount of water present in the cosmetic formulation of the present invention is less than 5% by weight, preferably less than 3% by weight, less than 1% by weight, more preferably less than 0.1% by weight, based on the total weight of the formulation. The water content of the formulation of the present invention is preferably 2.5% by weight or less, more preferably 0.5% by weight or less. In particular, it is preferred that the cosmetic formulation of the present invention is water-free, i.e., the water content of the cosmetic formulation of the present invention is zero. According to the present invention, the term "water-free" includes that each compound used in the cosmetic formulation is free of water residues, for example, water-free denatured ethanol or water-free glycerin (Glycerin Ph.Eur.99%) is preferably used in the cosmetic formulation of the present invention.

[0071] Furthermore, since the compounds used in the cosmetic preparations of the present invention, in particular the active compounds such as UV filters, are completely soluble in the preparations of the present invention, the preparations of the present invention have improved stability, in particular with respect to storage, and therefore it is not necessary to use thickeners in the cosmetic preparations of the present invention, such as those described, for example, in WO 01 / 12139. Thickeners are, for example, silicones, waxes, clays, silicas, salts, natural and synthetic esters, fatty alcohols, and mixtures thereof.

[0072] In a further embodiment of the present invention, the electrostatically sprayable cosmetic formulation comprises: a) 35 to 55% by weight of ethanol; b) 18 to 27% by weight of an emollient that is liquid at 20°C and has a log K OW A skin softener having a viscosity of 2.0 to 10; c) 16 to 40% by weight of a UV-A / UV-B filter mixture; d) 2-5 wt. % of a polymeric film-former mixture comprising at least one polyalkyleneoxypolyamide and at least one acrylate, the amount of polyalkyleneoxypolyamide being at least two times greater than the amount of acrylate present in the film-former mixture; e) 1 to 4% by weight of a cosmetic additive mixture; The amount of water present in the formulation is less than 1% by weight, based on the total weight of the formulation, the sum of the weights of the ingredients being 100%.

[0073] In a further preferred embodiment of the present invention, the electrostatically sprayable cosmetic formulation comprises, based on the total weight of the formulation: a) 35 to 55% by weight of ethanol; b) 18-27% by weight of an emollient mixture consisting of phenoxyethyl caprylate, PPG-3 myristyl ether, dibutyl adipate, and dicapryl carbonate; c) 16-40% by weight of a UV-A / UV-B filter mixture consisting of butyl methoxydibenzoylmethane, octocrylene, diethylhexylbutamidotriazon, ethylhexyl salicylate, optionally bis-ethylhexyloxyphenol methoxyphenyl triazine, optionally diethylamino hydroxybenzoyl hexyl benzoate and optionally homosalate; d) 2-5 wt. % of a polymeric film former mixture consisting of polyamide 3 and acrylates / octylacrylamide copolymer; e) 1 to 3.5% by weight of a cosmetic additive mixture consisting of fragrance, tocopherol tocopheryl acetate, and optionally glycerin; The amount of water present in the formulation is less than 1% by weight, based on the total weight of the formulation, the sum of the weights of the ingredients being 100%.

[0074] In an even more preferred embodiment of the present invention, the cosmetic formulation consists of a mixture of compounds as defined above, and the cosmetic formulation does not contain water.

[0075] In particular, the electrostatically sprayable cosmetic formulation comprises, based on the total weight of the formulation: a) 40 to 55% by weight of ethanol; b) 18-27% by weight of an emollient mixture consisting of 10-12% by weight of phenoxyethyl caprylate, 0.5-2.5% by weight of PPG-3 myristyl ether, 4.0-6.5% by weight of dibutyl adipate, and 3.5-6% by weight of dicapryl carbonate; c) 16-36% by weight of a UV-A / UV-B filter mixture consisting of 3-5.5% by weight of butyl methoxydibenzoylmethane, 7.5-11% by weight of octocrylene, 1.0-4.5% by weight of diethylhexylbutamidotriazon, 4.5-6.0% by weight of ethylhexyl salicylate, 0-3.0% by weight of bisethylhexyloxyphenol methoxyphenyl triazine, 0-1.5-2.5% by weight of diethylamino hydroxybenzoyl hexyl benzoate, and optionally 0-3.5% by weight of homosalate; d) 2-5 wt. % of a polymeric film former mixture consisting of 1.5-3.5 wt. % of polyamide 3 and 0.5-1.5 wt. % of an acrylates / octylacrylamide copolymer; e) 0.5 to 4.0% by weight of a cosmetic additive mixture consisting of 0 to 2.5% by weight of glycerin, 0.25 to 0.60% by weight of fragrance, 0.1 to 0.3% by weight of tocopherol, and 0.25 to 0.60% by weight of tocopheryl acetate, The sum of the weights of the ingredients is 100% and the cosmetic formulation does not include water.

[0076] The following examples are presented to illustrate the invention in more detail.

[0077] Working Example 1.Measurement method 1.1 Specific electrical resistivity The specific electrical resistivity was measured by an electrospray coating test instrument from DCA Electronics. The measured current was 85μA to over 100μA. The measurement range was 10kΩ to 5MΩ. The measured electrical resistivity was approximately converted to specific electrical resistivity according to ASTM D5682-08.

[0078] 1.2 Surface tension The surface tension of the formulations described herein was measured by two different measurement methods, the stamp method and the bubble pressure method. Due to the low viscosity of the cosmetic formulations according to the present invention, the stamp method was used to measure the surface tension of these cosmetic formulations.

[0079] 1.2.1 Stamp method Metal stamps can be used to measure the surface tension of liquids and highly viscous media (e.g. polymer melts or adhesives). The liquid is applied to the stamp, forming a full surface and a droplet on the stamp. The stamp material does not affect the measurement result.

[0080] The surface tension of the liquid can be calculated from the droplet contour and the liquid concentration using SCA20 software (www.dataphysics-instruments.com, DATAPhysics OCA20) and the Young-Laplace equation.

[0081] JPEG0007671295000002.jpg56170

[0082] In addition to the surface tension, the contact angle and the volume of the droplet are also measured. The measured surface tension is independent of the contact angle. The same surface tension value is measured both when the droplet is expanded and when it is contracted by suction.

[0083] 1.3 Bubble pressure method The bubble pressure method can be used to measure the dynamic surface tension of formulations in liquids. This method is carried out using a tensiometer SITA pro line t15 (www.sita-messtechnik.de), where an air stream is guided through a robust capillary into the sample liquid and the pressure development required for bubble generation is measured at room temperature (automatic mode: bubble life 0.02-20 s). It is preferable to show the surface tension s [mNm] at a bubble life of 20 s.

[0084] 1.2.2 Dielectric constant The dielectric constant was measured by a high frequency liquid dielectric constant meter (time domain reflectometer) "ALPHA TDR-5000" from Zadow Electronics (www.zadow-electronics.de) with two parallel wire sensors of 5 cm length. The measurement method was such that the TDR-500 sent a voltage pulse periodically over time (250 picoseconds) to the sensor cable to determine the dielectric constant (K) of the formulation.

[0085]

number

[0086] 1.4 Conductivity The conductivity was measured by a Sartorious PT-20, handheld conductivity meter, measuring cell PY-CL1 (www.sartorius.de). Measurements were taken at room temperature.

[0087] 1.5 Viscosity Viscosity was measured from 1 to 3000 s by the universal dynamic spectrometer "Physica UDS 200". -1 The measurements were performed at a shear rate of 0.05 and 22°C.

[0088] 1.6 Spray test 1 This spray test examined the sprayability of cosmetic formulations to provide a uniform distribution on the skin surface.

[0089] The conditions for all test configurations were the same. The tested cosmetic formulations were sprayed using the IONIQ spray system, which is described in detail in DE 102017108610.2, DE 102017108612.9, DE 102017108613.7, DE 102107108614.5, DE 102107108 615.3. The tested cosmetic formulations were sprayed on the forearms of three and four subjects, respectively. The spraying time was 0.75 s (scale 1.5) and the voltage of the spraying pump was 2.6 V. After spraying, the IONIQ system was washed with denatured alcohol. The formulations were left to soak and absorb for 30 minutes without further processing or massage. The homogeneous distribution of the formulation on the skin was then measured in vivo by laser scanning microscopy (LSM). The cosmetic formulations tested contained fluorescein, so that the fluorescence of fluorescein could be visualized by irradiation at 488 nm. A mosaic of 4 x 4 mm on the skin surface was recorded at each measurement point.

[0090] 1.7 Spray test 2 The spray test also used an IONIQ spray system, and all test configurations were the same. The cosmetic formulations tested were sprayed onto the subjects' forearms and allowed to soak in and absorb without further treatment. After 1.5 and 30 minutes, the distribution of the formulations on the skin was photographed with a UV camera. The uniformity of the darkening was then evaluated.

[0091] 1.8 Sun Protection Factor (SPF) The SPF was measured in accordance with the international standard ISO24444:2010(E), taking into account all measurement conditions indicated in this international standard.

[0092] 1.9 Water resistance (screening) For the determination of the water resistance of the formulations, the SPF test according to ISO 24444:2010(E) was performed twice on each subject. On one side of the subject's back, the SPF measurement (screening) according to ISO 24444:2010(E) was performed as described above, while on the other side the SPF test was combined with a standardized watering procedure. Watering of the test area was performed according to the COLIPA Guidelines of Evaluating Sun Product Water Resistance 2005.

[0093] 2. Cosmetic preparations All raw materials used are of cosmetic quality and commercially available. The ethanol used was of denatured quality (denaturants: isopropyl and tert-butanol; ethanol 96%) and the glycerin used was Glycerin Ph.Eur. 99.8%. Both compounds are widely used in cosmetics and should be free of water.

[0094] The components of each formulation were mixed together to obtain a homogenous mixture of the formulation.

[0095] Three cosmetic formulations according to the invention were prepared, designated as formulations SPF 50, SPF 30 and SPF 15. The compositions of the formulations are shown in Table 2 below.

[0096] Additionally, six cosmetic formulations were prepared that are not in accordance with the present invention and are designated as Comparative Examples 1 to 6. The compositions of these formulations are shown in Tables 3 and 4 below.

[0097] [Table 2]

[0098] [Table 3]

[0099] [Table 4]

[0100] 3.Results 3.1 Spray test 1 Spray test 1 was carried out using the cosmetic preparations of Comparative Examples 1-3. All three formulations only contain one type of film-former instead of a mixture of film-formers as required by the present invention.

[0101] The formulation of Comparative Example 1 contains Polyamide 3, a polyalkyleneoxy-terminated polyamide film former. The formulation of Comparative Example 2 contains Dermacryl 79, an acrylate film former, and the formulation of Comparative Example 2 contains Polyester 10 / propylene glycol dibenzoate as a film former. The test results are shown in Figures 3-5.

[0102] All three formulations were electrostatically sprayable and showed a homogenous distribution on the surface of the skin according to first impressions. Closer examination of the results showed that the formulation of Comparative Example 1, which contains polyamide 3 as a film former, was the most homogenous application (see Figure 3). However, the formulations of Comparative Examples 2 and 3 showed inhomogeneous areas (see Figures 4 and 5).

[0103] Thus, the best spraying results were obtained using polyalkyleneoxypolyamides as film formers.

[0104] 3.2 Spray test 2 Figure 7 shows the spray results of a formulation according to the invention SPF 30 (right side) and a formulation of Comparative Example 4 (which has an almost similar composition of compounds as the formulation SPF 30, but contains only polyamide 3 as a film-former instead of the film-former mixture). The same application amount was used in all tests.

[0105] The UVA images clearly show that the formulation SPF 30 provided a more homogenous distribution on the skin than the formulation of Comparative Example 4.

[0106] The inventive formulations SPF15 and SPF50 showed the same good sprayability as the SPF30 formulation.

[0107] 3.3 Sun protection factor The SPF of the formulations of Comparative Examples 4 to 6 and the formulation of the present invention was measured. The formulations of the Comparative Examples and the formulation SPF30 contained the same UV filter mixture.

[0108] Like the formulation of Comparative Example 1, the formulation of Comparative Example 4 contains polyamide 3 as a film-forming agent. Although the amount of polyamide 3 in this formulation was very high (6 wt. % based on the total weight of the composition), an SPF of only 24 was obtained.

[0109] In contrast to the formulation of Comparative Example 4, the formulations of Comparative Examples 5 and 6 contained a film-forming agent mixture. Comparative Example 5 used a mixture of polyamide 3 and polyurethane-64, and Comparative Example 6 used a mixture of polyamide 3 and trimethylpentanediol / adipic acid / glycerin crosspolymer. However, although these formulations contained a film-forming agent mixture, the SPF of the formulations was not significantly increased compared to the SPF of the formulation of Comparative Example 4 (the SPF of Comparative Example 5 was 27.9 and the SPF of Comparative Example 6 was 26.3).

[0110] Only by using the film-forming agent mixture according to the invention, i.e. the mixture comprising polyalkyleneoxypolyamide (Polyamide 3) and acrylate (Dermacyl 79), was the SPF of the cosmetic formulation significantly increased (see formulation SPF30 with an SPF of 39.5). The same is true for formulations SPF15 and 50.

[0111] 3.4 Water resistance The formulations SPF 15, 30 and 50 according to the invention show sufficient water resistance. In particular, the formulation SPF 15 has a water resistance of 75% and the formulation SPF 30 has a water resistance of 66.9%.

[0112] [Table 5]

[0113] 3.6 Conclusion The use of a film-forming agent mixture comprising a polyalkyleneoxypolyamide and an acrylate in such cosmetic formulations provides cosmetic formulations that exhibit improved electrostatic sprayability and further provide an increased sun protection factor without increasing the content of UV filters present in the formulation.

Claims

1. A cosmetic formulation for electrostatic spraying, comprising: Based on the total weight of the formulation, a) 20 to 60% by weight of ethanol; b) It is liquid at 20°C and has a logarithm K ow 10 to 55 wt. % of an emollient, c) 10 to 55% by weight of UV-A and / or UV-B filters; d) 2-8 wt. % of a polymeric film former blend comprising at least one polyalkyleneoxy-terminated polyamide, the polyalkyleneoxy-terminated polyamide being a condensation product of dilinoleic acid, ethylene diamine and polypropylene glycol diamine end-capped with polyethylene glycol polypropylene glycol (PEG-PPG)-3 2 / 10 aminopropyl methyl ether (polyamide-3) and at least one acrylates / octylacrylamide copolymer; e) 0-4 wt. % of cosmetic additives; A cosmetic formulation, wherein the amount of water present in the formulation is less than 5% by weight, based on the total weight of the formulation, and the sum of the weights of the ingredients is 100%.

2. 10. The cosmetic formulation for electrostatic spraying of claim 1, wherein the composition does not contain a thickener.

3. 3. The cosmetic formulation for electrostatic spraying according to claim 1 or 2, wherein the amount of said polyalkyleneoxy-terminated polyamide is at least twice as much as the amount of acrylate present in said film-forming agent mixture.

4. A cosmetic formulation for electrostatic spraying according to any one of claims 1 to 3, wherein the amount of polyamide-3 is at least 0.5% by weight and not more than 6% by weight, based on the total weight of the formulation.

5. 5. A cosmetic formulation for electrostatic spraying according to claim 4, wherein the amount of the acrylates / octylacrylamide copolymer is at least 0.2% by weight and no more than 3% by weight, based on the total weight of the formulation.

6. A cosmetic formulation for electrostatic spraying according to any one of claims 1 to 5, wherein the cosmetic formulation comprises at least two different emollients.

7. The emollient may be phenoxyethyl caprylate, PPG-3 myristyl ether, dibutyl adipate, dicapryl carbonate, isoamyl cocoate, diethylhexyl carbonate, isopropyl myristate, isopropyl palmitate, PPG-14 butyl ether, decyl cocoate, PPG-15 stearyl ether, C 12 -C 15 A cosmetic formulation for electrostatic spraying according to any one of claims 1 to 6, wherein the cosmetic formulation is selected from the group consisting of alkyl benzoates and combinations thereof.

8. The UV-A and / or UV-B filters have a logarithm K of 2.0 to 7.0 ow The cosmetic formulation for electrostatic spraying according to any one of claims 1 to 7, comprising:

9. 9. The cosmetic formulation for electrostatic spraying according to any one of claims 1 to 8, wherein the UV-A and / or UV-B filter is selected from the group consisting of butyl methoxydibenzoylmethane, octocrylene, diethylhexylbutamidotriazone, ethylhexyl salicylate, bis-ethylhexyloxyphenol methoxyphenyl triazine, diethylamino hydroxybenzoyl hexyl benzoate, homosalate, and combinations thereof.

10. 10. The cosmetic formulation for electrostatic spraying according to any one of claims 1 to 9, wherein the cosmetic additive is selected from the group consisting of humectants, fragrances, vitamins, provitamins, and combinations thereof.

11. The cosmetic formulation for electrostatic spraying according to any one of claims 1 to 10, wherein the cosmetic formulation is a sunscreen formulation.

12. Based on the total weight of the formulation, a) 35 to 55% by weight of ethanol; b) 18-27% by weight of an emollient blend consisting of phenoxyethyl caprylate, PPG-3 myristyl ether, dibutyl adipate, and dicapryl carbonate; c) 16-40% by weight of a UV-A / UV-B filter mixture consisting of butyl methoxydibenzoylmethane, octocrylene, diethylhexylbutamidotriazone, ethylhexyl salicylate, optionally bis-ethylhexyloxyphenol methoxyphenyl triazine, optionally diethylamino hydroxybenzoyl hexyl benzoate, and optionally homosalate; d) 2-5% by weight of a polymeric film former mixture consisting of polyamide 3 and acrylates / octylacrylamide copolymer; e) 1-3.5% by weight of a cosmetic additive mixture consisting of fragrance, tocopherol, tocopheryl acetate, and optionally glycerin; A cosmetic formulation for electrostatic spraying according to any one of claims 1 to 11, wherein the amount of water present in the formulation is less than 1% by weight, based on the total weight of the formulation, and the sum of the weights of the ingredients is 100%.

13. Based on the total weight of the formulation, a) 20 to 60% by weight of ethanol; b) It is liquid at 20°C and has a logarithm K ow 10 to 55 wt. % of an emollient, c) 10 to 55% by weight of UV-A and / or UV-B filters; e) 0-4 wt. % of cosmetic additives; 1. Use of a film-forming agent mixture comprising at least one polyamide-3 and at least one acrylates / octylacrylamide copolymer for electrostatic spraying of a cosmetic formulation, wherein the amount of water present in said formulation is less than 5% by weight, based on the total weight of the formulation, and the sum of the weights of the ingredients is 100%.

Images