WO2022128908A1 - Formulation cosmétique pulvérisable électrostatiquement - Google Patents

Formulation cosmétique pulvérisable électrostatiquement Download PDF

Info

Publication number
WO2022128908A1
WO2022128908A1 PCT/EP2021/085472 EP2021085472W WO2022128908A1 WO 2022128908 A1 WO2022128908 A1 WO 2022128908A1 EP 2021085472 W EP2021085472 W EP 2021085472W WO 2022128908 A1 WO2022128908 A1 WO 2022128908A1
Authority
WO
WIPO (PCT)
Prior art keywords
formulation
cosmetic
cosmetic formulation
previous
additives
Prior art date
Application number
PCT/EP2021/085472
Other languages
English (en)
Inventor
Charlotte Verdicchi
Eva Harnisch
Annabella Lueck
Alfred Goehring
Thomas Jeltsch
Niklas Wemheuer
Philipp Fanous
Valentin LANGEN
Philipp Gross
Original Assignee
Ioniq Skincare Gmbh & Co. Kg
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from EP20214423.4A external-priority patent/EP4015045A1/fr
Application filed by Ioniq Skincare Gmbh & Co. Kg filed Critical Ioniq Skincare Gmbh & Co. Kg
Publication of WO2022128908A1 publication Critical patent/WO2022128908A1/fr

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34—Alcohols
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34—Alcohols
    • A61K8/345—Alcohols containing more than one hydroxy group
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/35—Ketones, e.g. benzophenone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37—Esters of carboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/88—Polyamides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/90—Block copolymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
    • A61K8/922—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of vegetable origin

Definitions

  • the present invention relates to an electrostatically sprayable cosmetic formulation, which can be easily applied on a subject, provides in particular an improved protection against harmful IIV-A and IIV-B radiation, a good water resistance and additionally a good caring effect.
  • UV radiation of the sun having a wave length of about 280 to about 400 nm i.e. IIV-B (280 nm to 320 nm) and IIV-A radiation (320 nm to 400 nm)
  • IIV-B 280 nm to 320 nm
  • IIV-A radiation 320 nm to 400 nm
  • the tanning of the skin is caused by ultraviolet radiation of longer wave lengths of up to about 420 nm.
  • various sun screen products are on the market.
  • the sun screen shows a good resistance against sweat, fresh or salt water in case the subject is exposed to water.
  • sun screens are commercial available having a high protection against IIV-A and IIV-B sun radiation and which show a good water resistance.
  • Most of the sun screen formulations are lotions which can be applied on the surface of the skin by a limiting number of methods.
  • the simple method is to apply the lotion by hand.
  • This method includes many disadvantages.
  • the method does not ensure that a sufficient amount of the sunscreen lotion is applied on the surface of the skin and in particular this application method does not provide a sufficient coverage of the skin.
  • unnecessary high amounts of the sun screen formulation are applied on skin surface which results into uncomfortable feeling.
  • Another application method, which should ensure that a sufficient amount of the sun screen formulation is applied on the surface of the skin, but in an adequate manner, is the use of pump sprays or pre-pressurized aerosol containers so as to have the formulation atomized and sprayed with the aid of propellant gas.
  • This application method can be carried out without the aid of environmentally unfriendly propellants and provides a constant and uniform flow of the product.
  • the cosmetic formulation e.g. sun screen formulation
  • sun screen formulations are not electrostatically sprayable, since they do not have appropriate electrical characteristics, e.g. resistivity, permittivity etc., and/or have other properties such like a high surface tension, viscosity etc. which do not permit electrostatic spraying.
  • sun screen formulations include in addition to UV-A and UV-B filters emollients and other skin caring additives.
  • Emollients also referred to as cosmetic oils, are compounds that soften and smooth the scales of the skin, which help to reduce rough and flaky skin.
  • 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 a petroleum jelly or mineral oil.
  • emollients are additionally used as solubilizer for crystalline UV filters. Due to their electrical characteristic, i.e. resistivity and permittivity, most of the emollients show a worse electrostatic sprayability. The same applies to other skin caring additives and to the UV filters, which are usually used in sun screen formulations.
  • Skin caring additives that differ from emollients are for example moisture agents such as humectants, occlusive agents, and agents that affect the natural moisturization mechanism of the skin.
  • moisture agents such as fructose, glucose, maltitol, maltose, mannitol, glycerin, glycerol polymers, inositol, lactitol, linolenic acid, but also honey, beeswax, hyaluronic acid, hydrogenated starch hydrolysate, natural moisturizing factor, acetylated lanolin and alcohol thereof, alanine, aspartic acid, barrier sphingolipids, ceramides, ceresin, collagen, collagen, amino acids, serum protein, or extracts and oils of plants, like canola oil, algae extract, aloe barbadensis, aloe-barbadensis extract, aloe barbadensis gel, avocado (persea gratissim
  • Figure 1 schematically shows the undesired “zebra crossing” pattern on the skin, which occurs if the cosmetic formulation is not uniformly sprayable and thus, no homogenous distribution of the formulation on the skin is possible.
  • Figure 2 schematically shows the full coverage of the skin by using a cosmetic formulation of the invention, i.e. no streaking effect occurs.
  • the enlarged section “Detail A” of Figure 6 shows a part of the skin, which is covered with the cosmetic formulation according to the invention.
  • object of the application was to provide an electrostatically sprayable cosmetic formulation that has an improved caring effect, in particular a skin caring effect, by maintaining its good electrostatic sprayability, i.e. the coverage of the surface of the skin in nearly 100 %, and a good sun protection efficiency, i.e. a sun protection efficiency that is comparable to sun screen formulations known in the prior art.
  • the caring effect of the cosmetic formulation can be improved by maintaining a good electrostatic sprayability and a good sun protection efficiency, if the cosmetic formulation comprises in combination with ethanol, at 20 °C liquid polar emollients, polyalkyleneoxy terminated polyamide and acrylate as film forming agents, and UV filters, additives in relative high amounts and wherein at least one compound of the additives is a moisture agent.
  • the additives comprise at least one compound that is a moisture agent.
  • the moisture agent is different from the at 20 °C liquid polar emollient present in the cosmetic formulation of the invention.
  • the polar emollient(s) and the moisture agent(s) of the cosmetic formulation are different compounds. Additionally, the amount of additives used in the cosmetic formulation is relative high in comparison to the amount of additives usually used in cosmetic formulations, in particular used in electrostatically sprayable cosmetic formulations.
  • the cosmetic formulation has to comprise a film forming agent mixture, which contains a polyalkyleneoxy terminated polyamide in combination with an acrylate, ethanol in a sufficient amount and liquid polar emollients, whereby the polarity of the emollients is given by their log K ow value.
  • the present invention provides an electrostatically sprayable cosmetic formulation, which comprises a) 20 to 60 wt.-% ethanol; b) 5 to 50 wt.-% emollients, which are liquid at 20 °C and have a log K ow of 2.0 to 10; c) 10 to 55 wt.-% of UV-A and/or IIV-B filters; d) 0.5 to 15 wt.-% of a polymeric film forming agent mixture comprising at least one polyalkyleneoxy terminated polyamide and at least one acrylate; and e) more than 4 wt.-% of cosmetic additives, based on the total weight of the formulation; wherein at least one compound of the cosmetic additives is a moisture agent, the water content present in the formulation is less than 5 wt.-%, based on the total weight of the formulation, and the sum of the weight of the components is 100 %.
  • the cosmetic formulation as defined above shows due to the relative high content of additives, wherein at least one compound of the cosmetic additives is a moisture agent that is different from the emollients, the desired improved caring effect by maintaining its good electrostatic spraying behavior, high sun protection factor (SPF) and good water resistance.
  • at least one compound of the cosmetic additives is a moisture agent that is different from the emollients
  • Figure 3 shows the untreated skin surface of forearms of a subject (reference measurement).
  • Figure 4 shows the skin surface of forearms of subjects treated with the inventive Formulation SPF 50 according to the spray test 2 as described below.
  • Figure 5 shows the skin surface of forearms of subjects treated with a formulation indicated as SPF 30 according to the spray test 2 as described below, whereby the formulation does not include a sufficient amount of additives according to the invention.
  • wt.-% or “w/w”, as used herein, means “weight percentage” and refers to the weight amount of a compound in relation to the (total) weight of a formulation of compounds or of a substrate if nothing else is explicitly stated or obvious under the circumstances.
  • the cosmetic formulation in the meaning of the invention is a formulation that is selected from the group consisting of sun screen, skin care, hairspray, cosmetic foundation, lipstick, hair dye, and self-tanning formulations.
  • the cosmetic formulation can be used alone or in a mixture comprising other cosmetic formulations.
  • the cosmetic formulation is a sun screen formulation.
  • the electrostatically sprayable cosmetic formulation having the specific combination of components according to the invention preferably shows an specific electrical resistance of 15 to 100 G0hm mm 2 /m, more preferably of 20 to 85 G0hm mm 2 /m, it is even more preferred that the specific electrical resistance is not higher than 80, not higher than 60, not higher than 50 G0hm mm 2 /m, most preferably the electrostatic resistance is between 35 to 48 G0hm mm 2 /m, determined as described below (see measurement methods). This ensures that the formulation is good electrostatically sprayable and thus no undesired streaking effect on the skin occurs.
  • the formulation preferably has a surface tension of 15 to 50 mN/m, more preferably of 20 to 45 mN/m, 22 to 40 mN/m, more preferably 25 to 35 mN/m determined by the stamp method as described below (see measurement methods).
  • the relative permittivity of the cosmetic formulation according to the invention may be at least 2.0, preferably at least 2.3, more preferably at least 2.5, most preferably at least 2.6.
  • the relative permittivity of cosmetic formulation preferably is between 2.4 and 25.0, more preferably between 2.4 and 20.0, or between 2.4 and 10.0, most preferably between 2.4 and 5.0.
  • the measurement method for determining the relative permittivity according to the invention is described below (see measurement methods).
  • the cosmetic formulation of the invention may have a viscosity of from 0.65 mPa s to 5000 mPa s, preferably of from 1.0 to 1000 mPa s, 5.0 to 500 mPa s, more preferably of from 10.0 to 100 mPa*s, determined as described below (see measurement methods).
  • a good spraying behavior of the cosmetic formulation can be observed if the cosmetic formulation has a viscosity below 4.0 mPa s.
  • a cosmetic formulation having a viscosity of at least 8.0 mPa s shows a sufficient spraying behavior.
  • every electrostatic device known in the art can be used. However, it is preferred to use a device as described in DE 10 2017 108 610.2, which is further specified in DE 10 2017 108 612.9, DE 10 2017 108 613.7, DE 10 2107 108 614.5 and DE 10 2107 108 615.3.
  • the formulation comprises ethanol in a sufficient amount in combination with liquid polar emollients.
  • the sprayability of the emollients and thus of the total cosmetic formulation can be positively influenced by the presence of ethanol in the formulation.
  • the highly viscous IIV-B filter octocrylene shows a worse electrostatic sprayability in particular at low voltages.
  • the spraying quality can be improved (see results of Table 1 below).
  • the spraying test was carried out such that the distance from a spraying nozzles to the outer left side of a metal tube was 13 cm.
  • the pre-set voltage of three subsequent tests were 20, 30 and 40 kV, respectively.
  • For the fluid pump a voltage of 3.7 V was used.
  • the amount of ethanol present in the cosmetic formulation can be reduced, in case ethanol is used in combination with emollients and the film forming agent mixture as defined in the invention.
  • an ethanol content of 20 to 60 wt.-%, based on the total weight of the formulation is sufficient.
  • ethanol content is at least 25 wt.-%, at least 35 wt.-%, at least 40 wt.-%, more preferably at least 45 wt.-%, but not higher than 58 wt.-%, not higher than 55 wt.-%, more preferably not higher than 52 wt.-%, based on the total weight of the formulation.
  • the ethanol content is between 40 and 55 wt.-%, based on the total weight of the formulation. In another preferred embodiment, the ethanol content is between 38 and 48 wt.-% or between 40 and 46 wt.-%, based on the total weight of the composition.
  • the emollients (cosmetic oil) of the invention are emollients which are usually used in cosmetic products such like sun screen formulations, i.e. substance that provide a layer of protection that helps prevent moisture (water) loss from the skin as described above. It is further required that the emollients are liquid at 20 °C and polar.
  • n-octanol/water partition coefficient K ow or P
  • the partition-coefficient refers to the ratio of concentrations of the compounds in the mixture of these two immiscible phases at equilibrium. Hence, the partition coefficient measures how hydrophilic ("water-loving") or hydrophobic ("water-fearing") the tested compound is. In most of the cases the n- octanol/water partition coefficient is stated as decade logarithms log K ow or log P. The determination of the n-octanol/water partition coefficient is described for example in J. Sangster, “Octanol-Water Partition Coefficients: Fundamentals and Physical Chemistry’, Vol. 2 of Wiley Series in solution chemistry, John Wiley & Sons, Chichester, 1997.
  • the log K ow of the emollients which are suitable for the cosmetic formulation of the invention, is between 2.0 to 10.0, preferably between 2.5 and 9.5, 3.0 and 8.5, or between 3.5 and 7.5.
  • emollient known in the prior art which fulfills the above discussed requirements is suitable for the cosmetic formulation of the invention.
  • 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.
  • the cosmetic formulation of the invention comprises at least two but not more than 6, preferably not more than 4 different emollients.
  • the cosmetic formulation comprises phenoxyethyl caprylate, dibutyl adipate, dicaprylyl carbonate and combinations thereof as emollients.
  • the cosmetic formulation of the invention comprises a mixture consisting of these three emollients.
  • the different emollients are used in different or equal amounts in the formulation so that the total amount of emollients is between 5 to 50 wt.-%, based on the total weight of the formulation.
  • the total amount of emollients present in the formulation is from 8 to 40 wt.-%, 10 to 35 wt.-%, 11 to 25 wt.-%, 12 to 20 wt.-%, based on the total weight of the formulation.
  • the cosmetic formulation of the invention shows a sufficient sun screen protection. This property is indicated by the so-called sun protection factor (SPF).
  • SPDF sun protection factor
  • the SPF is a measure of the fraction of sunburn producing UV radiation that reach the skin. For example, “SPF 15” means that 1/15 th of the burning radiation will reach the skin, assuming sunscreen is applied evenly at a thick dosage of 2 milligrams per square centimeter.
  • SPDF 15 means that 1/15 th of the burning radiation will reach the skin, assuming sunscreen is applied evenly at a thick dosage of 2 milligrams per square centimeter.
  • the cosmetic formulation of the invention has a SPF of at least 15, preferably of at least 20, of at least 25, of least 30, more preferably of at least 50 or higher, measured according to ISO 24444:2010 (E).
  • Sun screen formulations which have a SPF of 60 and higher are indicated as SPF 50+ sun screen formulations.
  • the ability to protect the subject from harmful radiation of the sun depends inter alia on the amount of IIV-A and IIV-B filters present in the cosmetic formulations.
  • a mixture of IIV-A and IIV-B filters are used.
  • the cosmetic formulation comprises IIV-A and/or IIV-B filters in an amount of 10 to 55 wt.-%, preferably of 12 to 50 wt.-%, 15 to 45 wt.-%, 20 to 40 wt.-%, more preferably between 16 and 42 wt.-% or between 25 and 35 wt.-%, based on the total weight of the formulation.
  • the IIV-A and/or IIV-B filters have a log K ow of between 2.0 to 7.0, preferably between 2.5 and 6.5, more preferably between 3.0 and 6.0.
  • IIV-A and IIV-B filters are used in sun screen formulations.
  • the cosmetic formulation of the invention whereby the amount of IIV-A and IIV-B filters can be equal or different.
  • concentrations of the IIV-A and B filters used in the cosmetic formulation of the invention are in accordance with the requirements according to Regulation (EC) No. 1223/2009 on cosmetic products, Annex VI.
  • the cosmetic formulation comprises at least 3, at least 4 but not more than 10, preferably not more than 6 different UV-filters which can be IIV-A and/or UV-B filters.
  • UV filters Any UV-filter known in the prior art and which does not negatively influence the electrostatic sprayability of the formulation can be used in the invention. Suitable UV filters are disclosed in Regulation (EC) No. 1223/2009 on cosmetic products, Annex VI. Some of these examples are: phenylene-1 ,4-bis-(2-benzimidazyl)-3,3'-5,5'-tetrasulfonacid salts; phenylbenzimidazole sulfonic acid; 2-phenylbenzimidazole-5-sulfonic acid salts; 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) sulfonic acid salts; 2,2'- methylene-bis- (6-(2H-benzotriazol-2-yl
  • the UV-filters are selected from the group consisting of homosalate, butyl methoxydibenzoylmethane, octocrylene, diethylhexyl butamido triazone, ethylhexyl salicylate, bis-ethylhexyloxyphenol methoxyphenyl triazine, diethylamino hydroxy benzoyl hexyl benzoate and combinations thereof.
  • the cosmetic formulation comprises a mixture of IIV-A and UV-B filters which consists of butyl methoxydibenzoylmethane, octocrylene, ethylhexyl salicylate and homosalate.
  • the cosmetic formulation in order to ensure the sprayability of the cosmetic formulation the cosmetic formulation has to comprise a film forming agent mixture that comprises at least one polyalkyleneoxy terminated polyamide and at least one acrylate. Furthermore, the use of the film forming agent mixture according to the invention allows the SPF to be increased without the need of increasing the amount of UV filters present in the formulation and thus to maintain the good sprayability of the formulation.
  • polyalkyleneoxy terminated polyamide Every known polyalkyleneoxy terminated polyamide, as for example described in US 2014/0212363, can be used in the present invention.
  • the polyalkyleneoxy terminated polyamide is a condensation product of dilinoleic acid, ethylenediamine and polypropylene glycol diamine end-capped with polyethylene glycol- poylpropylene glycol (PEG-PPG)-32/10 aminopropyl methyl ether.
  • the polyalkyleneoxy terminated polyamide is selected from the group consisting of a polyamide-3, a polyamide-4, and mixtures thereof, such as OleoCraft MP-30, OleoCraft MP-32, OleoCraft HP-31 , OleoCraft HP-33, SYLVASOL 80, SYLVACLEAR AF1900V, SYLVACLEAR PE1800V, SYLVACELEAR PA1200V and SYLVACLEAR WF1500V available for instance from Arizona Chemical or Croda.
  • the polyalkyleneoxy terminated polyamide is polyamide-3.
  • the acrylate can be any one known in the art, such as for example acrylate/dimethicone copolymer, styrene acrylate copolymer or vinyl acetate (VA)/butyl maleate/isobornyl acrylate copolymer, it is preferred that the acrylate is an acrylate/amide copolymer. More preferably, the acrylate/amide copolymer is an acrylate/amide copolymer with alkyl groups having 6 to 16 carbon atoms. Most preferably, the acrylate/amide copolymer is an acrylates/octylacrylamide copolymer. This polymer comprises carboxyl groups attached to the polymer main chain and octyl side chains and is commercially available, for example under the trademark DERMACRYL 2.0 or DERMARYL 79 from AkzoNobel, DE.
  • the film forming agent mixture may contain as film forming agents monomer, copolymers, cross polymers and terpolymer of organ-silicone hybrid, biopolymer, abietic acid derivatives, polyolefins, silicone resins as known in the prior art, in particular vinyl acetates, maleates, alkyl esters, long chain and short chain carboxylic acids, polyamides, ethanol (and) crotonic acid/vinyl Cs-12 esters/VA/bis-vinyldimethicone crosspolymer, isododence (and) acrylate/dimethicone copolymer, acrylates/dimethicone copolymer (and) cyclopentasiloxane, methyl di hydroabietate, hydrogenated polycyclopentadiene isoalkyl (and) isododecane, vinylpyrollidone (VP)/hexade
  • film forming agents monomer, copolymers, cross polymers and terpolymer
  • the cosmetic formulation of the invention comprises the polymeric film forming agent mixture in an amount of 0.5 to 15 wt.-%, based on the total weight of the formulation; preferably, in an amount of between 0.7 and 13 wt.-%, between 1 and 10 wt.- %, between 2 and 8 wt.-%, between 3 and 7 wt.-% and more preferably between 4 and 6 wt.-%, based on the total weight of the formulation.
  • the amount of the polyalkyleneoxy terminated polyamide and the amount of the acrylate present in the film forming agent mixture can be equal or different.
  • the cosmetic formulation comprises the polyalkyleneoxy terminated polyamide in an amount of 0.5 to 10 wt.-%, preferably in an amount of 1 to 8 wt.-%, more preferably in an amount of 2 to 6 wt.-%, based on the total weight of the formulation.
  • the same amounts are suitable for the acrylate present in the composition as film forming agent.
  • the cosmetic formulation comprises the polyalkyleneoxy terminated polyamide and the acrylate in equal amounts, preferably each component in an amount of 2 wt.-%, based on based on the total weight of the formulation.
  • the cosmetic formulation of the invention provides an improved caring effect.
  • the increase of the water content of the skin is a crucial factor regarding the extent of caring effect of a cosmetic formulation.
  • the skin hydration can be determined by the so-called Corneometer method as described in detailed in paragraph “Measurement methods” below. In this method, the fact is used that water differs markedly from most substances as far as its dielectric constant is concerned.
  • a quantitative proof of changes to the water content of the skin can thus be achieved by means of capacity measurements in a non-invasive manner.
  • a measuring capacitor reacts to the capacity changes of the samples. These capacity changes are registered by the measuring head capacitor and the data are processed automatically by the Corneometer to a digital measured value.
  • the values measured by the Corneometer method specify the degree of moisture of the skin surface, i.e. the difference of water content before and after skin treatment with the cosmetic formulation.
  • the numbers given by the Corneometer are no absolute value and may be varied depending on the Corneometer used for measurement. However, Corneometer changes which are ascertained by a relative examination do not depend on the type of Corneometer. Thus, according to the invention, not percentage changes, but changes in Corneometer Units [C.U.] are analyzed.
  • the C.U. values of the invention refer to the difference of the initial value, i.e. the skin hydration value before the application of the cosmetic formulation (initial value), and the value measured within a certain time period after application of the cosmetic formulation.
  • a C.U. value between 0.5 to 2, preferably between 1 and 1.8 within a certain time period after application of the cosmetic formulation indicates that no increase in skin hydration is obtained.
  • the use of the cosmetic formulation of the invention results into a C.U. value of at least 8, preferably of at least 10, at least 15, more preferably of at least 18 within one hour after single application of the formulation to the skin.
  • the C.U. value is not higher than 40, not higher than 35, or not higher than 25, within one hour after single application of the cosmetic formulation.
  • the C.U. value within a time period of 6 hours after the single application of the cosmetic formulation to the skin is constant. Additionally, it is preferred that after 6 hours of the single application the C.U. value is about 15, about 18 or more preferred about 20. Additionally, it is preferred that after 24 hours of the application of the cosmetic formulation the C.U. is between 2 and 8, more preferably between 3 and 5.
  • the cosmetic formulation of the invention comprises a relative high amount of cosmetic additives in comparison to the amount of additives usually present in electrostatically sprayable cosmetic formulation.
  • the relative high amount of cosmetic additives is more than 4.0 wt.-%, preferably more than 4.05, more than 4.2 wt.-%, more than 5.0, more than 5.5 wt.-%, or more than 6.0 wt.-% but not higher than 8.0 wt.-%, preferably not higher than 7.0 wt.-%, based on the total weight of the cosmetic formulation.
  • the amount of cosmetic additive present in the cosmetic formulation of the invention is between 4.05 and 7.5 wt.-%, 4.1 and 7.0 wt.-%, or more preferred between 4.1 and 6.8 wt.-%, based on the total weight of the formulation.
  • the cosmetic additives according to the invention comprises at least one moisture agent, preferable at least two various moisture agents, which differ from each other and the polar emollients as described above.
  • the cosmetic additives comprises three various moisture agents that differ from each other and the emollients used in the cosmetic formulation.
  • moisture agents that can be used in the cosmetic formulation of the present invention are described above.
  • the moisture agents are selected from the group consisting of fructose, glucose, glycerin, glycerol polymers, linolenic acid, hyaluronic acid, beeswax, hydrogenated starch hydrolysate, acetylate lanolin alcohol, ceramides, ceresin, collagen, collagen, algae extract, sweet almond oil, aloe barbadensis, aloe-barbadensis extract, aloe barbadensis gel, avocado oil, canola oil, Calendula officinalis extract, hydrogenated palm kernel oil, and jojoba oil.
  • the moisture agents are selected from the group consisting of glycerin, aloe barbadensis, aloe-barbadensis extract, aloe barbadensis gel, jojoba oil and mixtures thereof.
  • the cosmetic additives comprises in any case a mixture of aloe-barbadensis extract and jojoba oil.
  • the amount of each of the above listed moisture agents present in the cosmetic formulation is between 0.5 and 3.5 wt.-%, between 1.0 and 2.5 wt.-%, more preferably between 1.5 and 2.0 wt.-%, based on the total weight of the cosmetic formulation.
  • the cosmetic additives and thus the cosmetic formulation of the invention comprises in addition to the above mentioned moisture agents further compounds such as cosmetically acceptable carriers, oils, sterols, amino acids, powders, colorants, pigments, dyes, pH adjusters, perfumes, essential oils, vitamins E, pro-vitamins, essential fatty acid, sphingolipids, self-tanning compounds, etc. and combinations thereof.
  • further compounds such as cosmetically acceptable carriers, oils, sterols, amino acids, powders, colorants, pigments, dyes, pH adjusters, perfumes, essential oils, vitamins E, pro-vitamins, essential fatty acid, sphingolipids, self-tanning compounds, etc. and combinations thereof.
  • the additives are selected from the group consisting of perfumes, vitamins and/or pro-vitamins such as tocopherol and/or tocopheryl acetate, and combinations thereof.
  • the amount of water present in the cosmetic formulation of the invention is less than 5 wt.-%, preferably less than 3 wt.-%, less than 1 wt.-%, more preferably less than 0.1 wt.-%, based on the total weight of the formulation. It is preferred that the water content of the formulation of the invention is not higher than 2.5 wt.-%, more preferably not higher than 0.5 wt.-%. In particular, it is preferred that the cosmetic formulation of the invention is water free, i.e. the water content of the cosmetic formulation of the invention is zero.
  • water free includes that each compound used in the cosmetic formulation contains no residues of water, for example it is preferred that denaturized ethanol, which does not contain water, and water free glycerin (Glycerin Ph. Eur. 99%), is used in the cosmetic formulation of the invention.
  • the formulation of the invention since the compounds used in the cosmetic formulation of the invention, in particular the active compounds such as UV-filters, are completely soluble in the formulation of the invention, the formulation of the invention has an improved stability, in particular with respect to storage, and thus there is no need to use thickening agents as described for example in WO 01/12139 in the cosmetic formulation of the invention.
  • Thickening agents are for example silicones, waxes, clays, silicas, salts, natural and synthetic esters, fatty alcohols, and mixture thereof.
  • the electrostatically sprayable cosmetic formulation comprises a) 35 to 55 wt.-% ethanol; b) 8 to 20 wt.-% emollients, which are liquid at 20 °C and have a log K ow of 2.0 to 10; c) 16 to 45 wt.-% of UV-A/UV-B filter mixture; d) 2 to 5 wt.-% of a polymeric film forming agent mixture comprising at least one polyalkyleneoxy terminated polyamide and at least one acrylate; and e) 4.1 to 7.0 wt.-% of cosmetic additives, based on the total weight of the formulation; wherein at least one compound of the cosmetic additives is a moisture agent, which is selected from the group consisting of glycerin, aloe barbadensis, aloe-barbadensis extract, aloe barbadensis gel, and jojoba oil; the water content present in the formulation is less than 1 wt.-%
  • the electrostatically sprayable cosmetic formulation comprises a) 35 to 55 wt.-% ethanol; b) 8 to 20 wt.-% emollient mixture consisting of phenoxyethyl caprylate, dibutyl adipate and dicapryic carbonate; c) 16 to 45 wt.-% of UV-A/UV-B filter mixture consisting of butyl methoxydibenzylmethane, octocrylene, ethylhexyl salicylate and homosalate; d) 2 to 5 wt.-% of a polymeric film forming agent mixture consisting polyamide 3 and acrylate/octylacrylamide copolymer; and e) 4.1 to 7.0 wt.-% of cosmetic additives, based on the total weight of the formulation; wherein the cosmetic additives comprises a mixture of at least two moisture agents selected from the group consisting of glycerin, aloe barb
  • the cosmetic formulation consists of the mixtures of compounds as defined above and the cosmetic formulation is water free.
  • the electrostatically sprayable cosmetic formulation consists of a) 40 to 50 wt.-% ethanol; b) 10 to 14 wt.-% emollient mixture consisting of 3.0 to 4.5 wt.-% of phenoxyethyl caprylate, 3.5 to 5.0 wt.-% adibutyl adipate and 3.5 to 4.5 wt-% dicapryic carbonate; c) 25 to 42 wt.-% of UV-A/UV-B filter mixture consisting of 2.0 to 4.0 wt.-% butyl methoxydibenzylmethane, 8.0 to 12.0 wt.-% octocrylene, 3.0 to 8.0 wt.-% ethylhexyl salicylate and 12.0 to 18.0 wt.-% homosalate; d) 2 to 5 wt.-% of a polymeric film forming agent mixture consisting of 1 to 2.5
  • the specific electrical resistance was determined by the means of an Electrospray Paint Test Meter of DCA Electronic Ltd. The measuring current was between 85 pA and 100 pA or higher. The measuring range was 10 kOhm up to 5 MOhm. The measured electrical resistance was approximately conversed to the specific electrical resistance according to ASTDM D5682-08.
  • the surface tensions of the formulations as described herein were 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 invention, the stamp method was used to determine the surface tension of these cosmetic formulations.
  • the metal stamp can be used to determine the surface tension of liquids and highly viscous media (e.g. polymer melt or adhesives).
  • the liquid is applied to the stamp, which forms an entire surface and a drop on the stamp.
  • the stamp material has no influence on the measurement result.
  • the surface tension of the liquid can be calculated from the drop contour and the density of the liquid using the SCA 20 software (www.dataphysics-instruments.com, DATAPhysics OCA20) and the Young-Laplace equation (see Figure 6).
  • the dynamic surface tension of the formulations in liquids can be determined. This method is carried out by using the tensiometer SITA pro line t15 (www.sita-messtechnik.de), wherein an air stream is lead into the sample liquid through a robust capillary and the pressure development necessary for the bubble generation is measured at room temperature (automatic mode: bubble lifetime from 0.02 to 20 s. It is preferred to indicate the surface tension s [mN/m] at a bubble lifetime of 20 s.
  • the relative permittivity was determined by the means of a High Frequency Liquid Dielectric Constant Meter (Time Domain Reflection) “ALPHA TDR-5000” of Zadow Electronics (ww.zadow-electronics.de) having two parallel wire sensors that have a length of 5 cm.
  • the measurement method was carried out such that the TDR-500 periodically sends voltage pulses with times (250 ps) onto the sensor cable to determine the dielectric constant (K) of the formulations:
  • the electrical conductivity was measured by means of Sartorious PT-20, hand-held conductivity meter, measuring cell PY-CL1 (www.sartorius.de). Measurement at room temperature.
  • the viscosity was determined by means of a Universal Dynamic spectrometer “Physica UDS 200” at shear rates of 1 to 3000 s' 1 and 22 °C.
  • the conditions for all test setups were the same.
  • the tested cosmetic formulations were sprayed by using an IONIQ spraying system, which is described in detail in DE 10 2017 108 610.2, DE 10 2017 108 612.9, DE 10 2017 108 613.7, DE 10 2107 108 614.5 and. DE 10 2107 108 615.3.
  • the tested cosmetic formulations were sprayed on the forearms of 3 and 4, respectively, subjects.
  • the spraying time was 0.75 s (scale 1.5) and the voltage of the pump for spraying was 2.6 V.
  • After spraying the IONIQ system was cleaned with denaturized alcohol. The formulations were leak to soak for 30 minutes without further treatment or massage.
  • the SPF was determined according to the International standard ISO 24444:2010(E); all measurement conditions as indicated in this International standard were considered.
  • the skin hydration was determined by using a Corneometer CM 825 hydrometer with MDD4 (Multi Display Device, Courage + Khazaka electronic GmbH).
  • the face of the sensor was coated with a special glass, which allowed axial movement and it had a range of at least 3 mm.
  • the principle of measurement reguires that the surface of the measuring device sits evenly at a constant pressure on the skin. To ensure that this is as reproducible as possible, the face of the measuring head was very small with an area of 7 x 7 mm 2 .
  • the inner movable part - the active face- was pressed onto the skin with a pressure of 3.5 N by means of a spring. This guarantees standardized measurements, irrespective of the investigator.
  • the measuring head was pressed onto the reguired part of the skin. After one second the measured value was recorded and processed by the computer.
  • the value measured by the Corneometer specifies the degree of moisture of the skin surface, e.g. the difference before and after skin treatments with the cosmetic formulation.
  • test formulations were applied to the test areas, in order to document the initial situation (tO).
  • initial situation tO
  • the test formulations were applied once (2 mg/cm 2 ) on the assigned test areas by a technician.
  • an untreated area and an area treated with a positive standard were used.
  • Subjects were advised not to treat the test areas in any way (including washing) until final measurement time.
  • Corneometer measurements were carried out at defined intervals during a defined time period (tO; t1h, t2h; t3h, t4h; t5h; t6h; and t24h).
  • All used raw materials are cosmetic qualities and commercially available.
  • the used ethanol was denaturized quality (denaturant: isopropyl and tert.-butanol; Ethanol 96%), the used glycerin was Glycerin Ph. Eur. 99.8%, the used aloe barbadensis extract was aloe barbadensis herbasol extract IPM 201100.02.2 from Lipoid GmbH and the jojobal oil was Ewanol Jo from Wagner. These compounds are widely used in cosmetic products, which should be water free. The components of each formulation were mixed together such that a homogeneous mixture of the formulation was obtained.
  • the cosmetic formulation according to the invention is indicated as Formulation SPF 50.
  • the comparative formulation indicated as Formulation SPF 30 is a formulation according to EP 19 197 645.
  • compositions of the formulations are given in Table 2 below.
  • Spraying test 1 was carried out with the cosmetic formulations according to the invention (SPF50) and the comparative formulation (SPF 30).
  • Figure 4 shows the spraying results of the Formulation SPF 50 according to the invention.
  • Figure 5 shows the spraying result of the Formulation SPF 30.
  • UVA images clearly show that both formulations provide a homogeneous distribution on the skin.
  • the SPF of the Formulation according to the invention and of the formulation of comparative example was determined.
  • the Formulation of the invention has an SPF of 51.50
  • the formulation of the comparative example has a SPF of 39.5.
  • the Formulation of the invention shows as similar (sufficient) water resistance as the Formulation SPF 30.
  • the cosmetic formulation includes moisture agents in relative high amounts that show worse electrostatic sprayability properties, in order to obtain in combination with ethanol, polar emollients, UV-filters and film forming agents according to the invention the electrostatic sprayability is comparable to an electrostatically sprayable cosmetic formulation as known in the prior art.

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Emergency Medicine (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical & Material Sciences (AREA)
  • Dermatology (AREA)
  • Cosmetics (AREA)

Abstract

La présente invention concerne une formulation cosmétique pulvérisable électrostatiquement qui a un facteur de protection solaire, une résistance à l'eau et un effet de soin suffisants, et qui permet d'obtenir une couverture suffisante, c'est-à-dire presque intégrale, de la surface de la peau, lorsque la formulation est appliquée sur la surface de la peau par pulvérisation électrostatique.
PCT/EP2021/085472 2020-12-16 2021-12-13 Formulation cosmétique pulvérisable électrostatiquement WO2022128908A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US202063126167P 2020-12-16 2020-12-16
US63/126,167 2020-12-16
EP20214423.4A EP4015045A1 (fr) 2020-12-16 2020-12-16 Formulation cosmétique pulvérisable électrostatiquement
EP20214423.4 2020-12-16

Publications (1)

Publication Number Publication Date
WO2022128908A1 true WO2022128908A1 (fr) 2022-06-23

Family

ID=78851084

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2021/085472 WO2022128908A1 (fr) 2020-12-16 2021-12-13 Formulation cosmétique pulvérisable électrostatiquement

Country Status (1)

Country Link
WO (1) WO2022128908A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994011119A1 (fr) 1992-11-18 1994-05-26 Unilever Plc Systeme d'application de cosmetiques
WO2001012139A1 (fr) 1999-08-18 2001-02-22 The Procter & Gamble Company Compositions topiques stables a pulverisation electrostatique
US20100116897A1 (en) 2006-06-26 2010-05-13 Battelle Memorial Institute Handheld sprayer with removable cartridge and method of using same
US20140212363A1 (en) 2011-09-09 2014-07-31 Croda International Plc Polyamide compositions for personal care
DE102013215831A1 (de) * 2013-08-09 2015-02-12 Beiersdorf Ag Gelförmiges, alkoholisches Sonnenschutzmittel
WO2018194086A1 (fr) * 2017-04-18 2018-10-25 花王株式会社 Procédé de production d'un film de revêtement de protection contre les rayonnements ultraviolets

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994011119A1 (fr) 1992-11-18 1994-05-26 Unilever Plc Systeme d'application de cosmetiques
WO2001012139A1 (fr) 1999-08-18 2001-02-22 The Procter & Gamble Company Compositions topiques stables a pulverisation electrostatique
US20100116897A1 (en) 2006-06-26 2010-05-13 Battelle Memorial Institute Handheld sprayer with removable cartridge and method of using same
US20140212363A1 (en) 2011-09-09 2014-07-31 Croda International Plc Polyamide compositions for personal care
DE102013215831A1 (de) * 2013-08-09 2015-02-12 Beiersdorf Ag Gelförmiges, alkoholisches Sonnenschutzmittel
WO2018194086A1 (fr) * 2017-04-18 2018-10-25 花王株式会社 Procédé de production d'un film de revêtement de protection contre les rayonnements ultraviolets

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
"Suncare compositions (13) ED - Darl Kuhn", IP.COM, IP.COM INC., WEST HENRIETTA, NY, US, 24 May 2017 (2017-05-24), XP013175041, ISSN: 1533-0001 *
"UTILITY OF ALCOHOLS AND OTHER OH CONTAINING INGREDIENTS TO MODIFY VISCOSITY OF SUNSCREEN GELS CONTAINING SPECIALTY POLYMERS ED - Darl Kuhn", IP.COM, IP.COM INC., WEST HENRIETTA, NY, US, 24 August 2011 (2011-08-24), XP013147129, ISSN: 1533-0001 *
ANONYMOUS ED - DARL KUHN: "Gelled Ethanol Sunscreen and Ethanol Based Continuous Spray Sunscreen Formulary Information", IP.COM, IP.COM INC., WEST HENRIETTA, NY, US, 13 July 2011 (2011-07-13), XP013147464, ISSN: 1533-0001 *
CAS , no. 288254-16-0
J. SANGSTER: "Wiley Series in solution chemistry", vol. 2, 1997, JOHN WILEY & SONS, article "Octanol-Water Partition Coefficients: Fundamentals and Physical Chemistry"

Similar Documents

Publication Publication Date Title
WO2021052779A1 (fr) Formulation cosmétique pulvérisable électrostatiquement
EP2345456B2 (fr) Composition filtrante fluide anhydre comprenant une phase huileuse, un filtre triazine particulier et un agent rhéologique épaississant ou gélifiant d'huile
US20090035234A1 (en) Continuous spray sunscreen compositions
BRPI0909005A2 (pt) composições de proteção solar
EP2630990B1 (fr) Préparation cosmétique légère et résistante à l'eau
KR20160123249A (ko) 썬스크린 조성물
CA2719978A1 (fr) Particules s'obtenant par sechage d'une dispersion aqueuse de nano-urees
JP2018526427A (ja) Ｕｖａ日焼け止め活性薬剤の改良された耐水性を有する日焼け止め組成物
US20020146438A1 (en) Preparations of the w/o emulsion type with an increased water content, and comprising cationic polymers
KR20200055589A (ko) 수용분산성 폴리우레탄을 포함하는 자외선 차단용 화장료 조성물
JP2022531954A (ja) ４つの日焼け止め物質からなる光防護システム
EP4015045A1 (fr) Formulation cosmétique pulvérisable électrostatiquement
US20220183954A1 (en) Electrostatically sprayable cosmetic formulation
FR3090371A1 (fr) Composition cosmétique à effet matifiant
KR20150023866A (ko) 자외 방사선-흡수 폴리에스테르를 함유하는 썬스크린 조성물
CN111542299B (zh) 护肤组合物
WO2022128908A1 (fr) Formulation cosmétique pulvérisable électrostatiquement
MX2014013914A (es) Petrolato de fuente vegetal.
CN116270312A (zh) 一种防晒棒和该防晒棒的制备方法
KR101944236B1 (ko) 화장 조성물
US20240252407A1 (en) Electrostatically sprayable tanning formulation
CN114746064A (zh) 双相防晒组合物
US20210030648A1 (en) Cosmetic composition for preconditioning the skin
EP4101436A1 (fr) Formulation de soin de la peau pulvérisable électrostatiquement
JP4741109B2 (ja) 油性化粧料

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21824405

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21824405

Country of ref document: EP

Kind code of ref document: A1