EP2760423A2 - Oxydes de phosphane en tant qu'accélérateurs de réaction - Google Patents

Oxydes de phosphane en tant qu'accélérateurs de réaction

Info

Publication number
EP2760423A2
EP2760423A2 EP12755800.5A EP12755800A EP2760423A2 EP 2760423 A2 EP2760423 A2 EP 2760423A2 EP 12755800 A EP12755800 A EP 12755800A EP 2760423 A2 EP2760423 A2 EP 2760423A2
Authority
EP
European Patent Office
Prior art keywords
propan
tert
hydroxy
methoxyphenyl
butylphenyl
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP12755800.5A
Other languages
German (de)
English (en)
Inventor
René Peter SCHEURICH
Sylvia EISENBERG
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
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
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Publication of EP2760423A2 publication Critical patent/EP2760423A2/fr
Withdrawn legal-status Critical Current

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
    • A61K8/35—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
    • A61K8/55—Phosphorus compounds

Definitions

  • the invention relates to the use of at least one phosphine oxide as accelerator for a photoinduced reaction of 3- (4-tert-butylphenyl) -3-hydroxy-1- (4-methoxyphenyl) -propan-1-one, 1 - (4-tert-butyl-phenyl) -3-hydroxy-3- (4-methoxyphenyl) -propan-1-one or a mixture of these compounds to avobenzone.
  • the invention further relates to mixtures or a preparation comprising at least one phosphine oxide and a method for stabilizing the UV absorption capacity of a preparation by means of a mixture of at least one phosphine oxide together with 3- (4-tert-butylphenyl) -3-hydroxy 1 - (4-methoxy-phenyl) -propane-1-one, 1- (4-tert-butylphenyl) -3-hydroxy-3- (4-methoxyphenyl) -propan-1-one or a mixture of these propan-1-one compounds, particularly preferably together with 3- (4-tert-butylphenyl) -3-hydroxy-1- (4-methoxyphenyl) propan-1-one.
  • UV radiation Radiation from the sun or radiation from artificial sources, in particular radiation of wavelengths from 280 to 400 nanometers, so-called UV radiation, can interact with constituents of preparations and with materials.
  • Such ingredients may be compounds such as pigments, UV filters, antioxidants or plastics, as well as polymers.
  • photochemical decomposition of ingredients usually results in undesirable deterioration of the formulation or material.
  • dyes for example, such photochemical degradation can lead to fading or loss of gloss, and in packaging materials, the contained plastic can become brittle and thus lose its protective function.
  • human skin is subject to certain aging processes, some of which are due to exogenous factors.
  • the exogenous factors include, in particular, sunlight or artificial radiation sources with a comparable spectrum, as well as compounds which can be formed by the radiation, such as undefined reactive photoproducts, which may also have a radical or ionic character.
  • both the skin and ingredients, as well as materials are exposed to some oxidative stress from the environment.
  • This oxidative stress leads to an oxidative degradation, which in turn can also lead to an undesirable deterioration of the materials or preparations and which can enhance the aging process of the skin.
  • UV filters and antioxidants are known that can absorb UV radiation and intercept free radicals. As a result, these UV filters and antioxidants are able to protect human skin.
  • the concentrations of the UV filter during use or use decreases continuously and thus the protection against the aggressive UV radiation also.
  • this effect can be counteracted by particularly stable UV filters, but these UV filters can also be subject to a certain photochemical degradation.
  • the stability of the respective UV filter is also dependent on the particular preparation, so that not every formulation has sufficient stability of the respective UV filter.
  • the present invention is now concerned with the problem of protection, in particular in / or by preparations, against sun or to improve sun-like light and / or against oxidative damage.
  • phosphine oxides of formula I as described below, as accelerators for a photo-induced reaction of 3- (4-tert-butyl-phenyl) -3-hydroxy-1- (4-methoxyphenyl) -propane 1-one or 1- (4-tert-butylphenyl) -3-hydroxy-3- (4-methoxyphenyl) propan-1-one can act.
  • photoinduced reaction is understood as meaning the conversion of, for example, 3- (4-tert-butyl-1-phenyl) -3-hydroxy-1- (4-methoxyphenyl) -propan-1-one to avobenzone upon irradiation with sunlight. or sun-like light, according to the following Reaction Scheme A.
  • Hydrogen is released, which is usually intercepted "in situ” by surrounding compounds.
  • an accelerator is thus understood to mean a compound, in particular of formula I, as described below which accelerates a reaction from a starting material to a product, so that the product is formed more rapidly in the presence of an accelerator than in the absence thereof.
  • a photoantioxidance is thus to be understood as meaning a compound which exhibits an antioxidant effect on irradiation, in particular with light having a wavelength of 280 to 400 nanometers.
  • a first subject of the invention is therefore the use of at least one compound according to formula I.
  • R, R and R are each independently an unsubstituted or substituted aryl group having 6 to 19 carbon atoms or an unsubstituted or substituted heteroaryl group having 5 to 10 carbon atoms and at least one N, O and / or S atom .
  • each aryl group may be independently, monosubstituted, disubstituted, trisubstituted, trisubstituted or trisubstituted by OH, NH 2 , a straight-chained or branched alkyl group having 1 to 10 carbon atoms or a straight-chained or branched alkoxy group having 1 to 10 carbon atoms, and where the heteroaryl group can be substituted by OH, OCH 3 , NH 2 or a straight-chain or branched alkyl group having 1 to 10 C atoms,
  • Another object of the invention is therefore the use of at least one compound of formula I.
  • R 1 , R 2 and R 3 each independently represent an unsubstituted or substituted aryl group having 6 to 19 C atoms or an unsubstituted or substituted heteroaryl group having 5 to 10 C atoms and at least one N, O and / or S atom,
  • each aryl group may be independently, monosubstituted, disubstituted, trisubstituted, trisubstituted or trisubstituted by OH, NH 2 , a straight-chained or branched alkyl group having 1 to 10 carbon atoms or a straight-chained or branched alkoxy group having 1 to 10 carbon atoms, and where the heteroaryl group can be substituted by OH, OCH 3 , NH 2 or a straight-chain or branched alkyl group having 1 to 10 C atoms,
  • Another object of the invention is therefore the use of at least one compound of formula I.
  • R 1 , R 2 and R 3 each independently represent an unsubstituted or substituted aryl group having 6 to 19 C atoms or an unsubstituted or substituted heteroaryl group having 5 to 10 C atoms and at least one N, O and / or S atom,
  • each aryl group may be independently, monosubstituted, disubstituted, trisubstituted, trisubstituted or trisubstituted by OH, NH 2, a straight-chained or branched alkyl group having 1 to 10 C atoms or a straight-chained or branched alkoxy group having 1 to 10 C atoms, and wherein the heteroaryl group may be substituted by OH, OCH 3 , NH 2 or a straight-chain or branched alkyl group having 1 to 10 carbon atoms, together with 3- (4-tert-butylphenyl) -3-hydroxy-1- (4 -methoxy-phenyl) -propan-1-one or 1- (4-tert-butylphenyl) -3-hydroxy-3- (4-methoxyphenyl) -propan-1-one or a mixture of these two propanes 1-on compounds in combination with at least one UV filter.
  • a straight-chain or branched alkyl group having 1 to 10 C atoms is, for example, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl or tert-butyl, furthermore pentyl, 1-, 2- or 3-methylbutyl, 1, 1, 1, 2 or 2, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or n-decanyl.
  • the straight-chain or branched alkyl group having 1 to 10 carbon atoms the straight-chain or branched alkyl group having 1 to 4 carbon atoms, i. Methyl, ethyl, isopropyl, propyl, butyl, sec-butyl or tert-butyl.
  • a straight-chain or branched alkoxy group having 1 to 10 C atoms is, for example, methoxy, ethoxy, isopropoxy, propoxy, butoxy, sec-butoxy, tert-butoxy, pentoxy, 1, 2 or 3-methylbutoxy, 1, 1, 1 , 2- or 2,2-dimethylpropoxy, 1-ethylpropoxy, n-hexoxy, n-heptoxy, n-octoxy, n-nonyloxy or n-decanyloxy.
  • the aryl group having 6 to 19 C atoms, each independently, single, double, triple, quadruple or five times by OH, NH 2) is a straight-chain or branched alkyl group having 1 to 10 C atoms or a straight-chain or branched alkoxy group having 1 to 10 carbon atoms may be substituted, for example, singly or as previously described multiply substituted 1-, 2-, 3-, 4-, 5- or 6-phenyl, 1-, 2- , 3-, 4-, 6-, 7- or 8-naphthyl, 1-, 2-, 3-, 4-, 6-, 7- or 8-phenanthrenyl or 1-, 2-, 3-, 4- , 5-, 6-, 7-, 8-, 9- or 10-anthracenyl.
  • Preferred aryl groups are phenyl or naphthyl which are unsubstituted or substituted simply by a straight-chain or branched alkyl group having 1 to 10 C atoms.
  • Preferred heteroaryl groups are pyridinyl, imidazolyl, pyrazinyl, pyrrolyl, furyl or thienyl which are unsubstituted or substituted by a straight-chain or branched alkyl group having 1 to 10 C atoms.
  • the substituents R 1 , R 2 and R 3 are each, independently of one another, unsubstituted or simply monosubstituted by a straight-chain or branched alkyl group having 1 to 4 C atoms.
  • the substituents R 1 , R 2 and R 3 are particularly preferably the same in each case.
  • this predetermined period t is selected from the time interval corresponding to a minimum erythema dose (MED) of 0.5 to 50 MED, more preferably from 0.5 to 30 MED, and most preferably from 0.5 to 20 MED.
  • MED minimum erythema dose
  • An absolute UV dose of 50 kJ / m 2 applied by solar radiation corresponds approximately to the erythema-weighted dose of 1 ⁇ M.
  • Another key aspect of the invention is the use of a mixture of at least one compound of the formula I as described above, together with 3- (4-tert-butylphenyl) -3-hydroxy-1- (4-methoxyphenyl) - Propan-1-one, 1- (4-tert-butyl-phenyl) -3-hydroxy-3- (4-methoxyphenyl) -propan-1-one or mixtures of these propan-1- ⁇ - compounds, in particular of 3- (4-tert-butylphenyl) -3-hydroxy-1- (4-methoxyphenyl) -propan-1-one, as a photoinduced antioxidant system. This is especially a non-therapeutic use.
  • the photoinduced antioxidative system is accordingly a mixture consisting of 3- (4-tert-butylphenyl) -3-hydroxy-1- (4-methoxyphenyl) propan-1-one, 1- (4-tert-butyl) Butyl-phenyl) -3-hydroxy-3- (4-methoxyphenyl) propan-1-one or the mixtures of these compounds, especially of 3- (4-tert-butyl-phenyl) -3-hydroxy-1 - (4-methoxy-phenyl) -propan-1-one, and at least one compound of formula I, as described above or described as preferred or described as individual compounds which upon irradiation, in particular with light having a wavelength of 280 to 400 nanometers, a Antioxidant effect unfolds.
  • Another object of the invention is therefore a mixture consisting of at least one compound of formula I, as described above or described as preferred or as individual compounds together with 3- (4-tert-butylphenyl) -3-hydroxy-1- (4-methoxyphenyl) propan-1-one, 1- (4-tert-butylphenyl) -3- hydroxy-3- (4-methoxyphenyl) -propan-1-one or the mixtures of these propan-1-o ⁇ -compounds.
  • This mixture is preferably used as a photoinduced antioxidant system as previously described.
  • the mixture consists of one or more compounds of the formula I as described above or described as being preferred or described as individual compounds, for example one or two compounds of the formula I and 3- (4-tert-butylphenyl) -3-hydroxy-1 - (4-methoxy-phenyl) -propan-1-one, 1- (4-tert-butylphenyl) -3-hydroxy-3- (4-methoxyphenyl) -propan-1-one or mixtures thereof propan-1-one compounds.
  • the mixture contains no further additives.
  • the mixture preferably consists of a compound of the formula I as described above or described as being preferred or a single compound selected from the individual compounds mentioned and 3- (4-tert-butylphenyl) -3-hydroxy-1- (4-methoxy- phenyl) -propan-1-one, 1- (4-tert-butylphenyl) -3-hydroxy-3- (4-methoxyphenyl) -propan-1-one or the mixtures of these propan-1-one Links.
  • the hydrogen equivalents are usually not released, but absorbed by surrounding compounds. Therefore, a mixture of 3- (4-tert-butylphenyl) -3-hydroxy-1- (4-methoxyphenyl) propan-1-one, 1- (4-tert-butylphenyl) -3 acts -hydroxy-3- (4-methoxyphenyl) -propan-1-one or the mixtures of these propan-1-one compounds, in particular of 3- (4-tert-butyl-phenyl) -3-hydroxy-1 (4-methoxy-phenyl) -propan-1-one, and avobenzone when irradiated antioxidant and thus photo-antioxidant. Without irradiation, no hydrogen equivalents are released.
  • Another object of the invention is therefore a mixture consisting of at least one compound of formula I, as described above or described as preferred or described as individual compounds, together with 3- (4-tert-butyl-phenyl) -3-hydroxy-1 (4-methoxy-phenyl) -propan-1-one, 1- (4-tert-butylphenyl) -3-hydroxy-3- (4-methoxyphenyl) -propan-1-one or the mixtures of these propane -1- ⁇ compounds and at least one UV filter.
  • the UV filter can be both inorganic and organic.
  • avobenzone itself is used as the organic UV filter. It is very particularly preferred if the added UV filter of avobenzone is different. In this arrangement, no avobenzone is initially included before the start of irradiation. By photoconversion but here additional absorption power is built up compared to the initial value.
  • Examples of photostable marketed as combinable organic UV filters are, for example, 2- (4-diethylamino-2-hydroxybenzoyl) -benzoeklahexylester, sold under the trade name Uvinul® A Plus from BASF SE, 2,2'-methylenebis (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol) under the name Tinosorb® M BASF SE or salts of 2,2 '- (1, 4-phenylene) bis) -1H-benzimidazole-4,6-disulfonic acid), for example, sold under the name Neo Heliopan® AP of Symrise, 2- (2H-Benzotriazol-2-yl) -4-methyl-6- (2-methyl-3- (1,3,3,3-tetramethyl-1- (trimethylsilyloxy) -disiloxanyl) -propyl) -phenol ( INCI drometriazole trisiloxanes), for example known
  • inorganic UV filters so-called particulate UV filters are titanium dioxides, such as coated titanium dioxide (for example Eusolex ® T-2000, Eusolex ® T-AQUA, Eusolex ® T-AVO, Eusolex ® T-OLEO), zinc oxides (eg Sachtotec® ® ), Iron oxides or else cerium oxides and / or zirconium oxides.
  • coated titanium dioxide for example Eusolex ® T-2000, Eusolex ® T-AQUA, Eusolex ® T-AVO, Eusolex ® T-OLEO
  • zinc oxides eg Sachtotec® ®
  • UV filters are also combinable, as described below.
  • the UV filter to be stabilized particularly preferably has an energy level of a first excited triplet state which, with a deviation of not more than five percent, corresponds to the energy level of the first excited triplet state of 3- (4-tert-butylphenyl) -3 -hydroxy-1- (4-methoxyphenyl) -propan-1-one or 1- (4-tert-butylphenyl) -3-hydroxy-3- (4-methoxyphenyl) -propan-1-one equivalent.
  • the mixture described as a photoinduced antioxidant system is used as a photoinduced avobenzone stabilizer.
  • the mass ratio of the at least one compound of the formula I in the entirety to the total of propane-1 -one compounds is 10: 1 to 1:20, preferably 5: 1 to 1: 5 and particularly preferably 2: 1 until 12.
  • Triphenylphosphanoxid 10 1 to 1: 20, preferably 5: 1 to 1: 5 and particularly preferably 2: 1 to 1 : 2nd
  • the molecules By irradiating molecules with UV rays, they can absorb the radiant energy.
  • the molecules are usually raised from a ground state S 0 to an excited first singlet state Si or a higher singlet state S x .
  • the molecules can change to a triplet state through "intersystem crossing" (ISC) and return to their ground state by thermal relaxation or radiation relaxation, for example Ground state S 0 is excited in a first singlet state Si, where it subsequently by "Intersystem Crossing (ISC)" in the first excited triplet state ⁇ changes and then by relaxation processes can fall back into the ground state So.
  • ISC Intersystem crossing
  • the mixture consisting of at least one compound of the formula I as described above or described as being preferred or described as individual compounds is preferably used together with 3- (4-tert-butylphenyl) -3-hydroxy-1- (4-methoxy) phenyl) -propan-1-one, 1- (4-tert-butylphenyl) -3-hydroxy-3- (4-methoxyphenyl) -propan-1-one or the mixtures of these propan-1-one Compounds and at least one UV filter used as a UV filter system, as described above.
  • Such a constant or increasing UV absorption capacity of such a UV filter system is a dynamic one Sun protection is possible, which ensures the skin or the respective, provided with such a UV filter system protection that ensures at least a constant UV absorption capacity over the predetermined period.
  • an increasing ultraviolet absorbing ability is particularly desired, since as the exposure of the radiation to the skin progresses, it is more likely to be irritated.
  • the skin also requires a higher protection with progressive radiation, which is advantageously made possible by such a sunscreen with such a UV filter system.
  • Such a UV filter system is able to intensify the protection of the skin with increasing irritation.
  • the skin gets the protection it needs compared to conventional sunscreen formulations, which usually show a decreasing UV absorption capacity as the radiation exposure progresses.
  • the mixture according to the invention comprises at least one propane-1-one compound, at least one compound of the formula I and at least one UV filter, then the mass ratio of the propan-1-olefin compounds to the sum of all UV filters is 1: 4 to 1:50 and the proportion of the formula I compound is calculated from the mass ratio to the at least one propan-1-one compound as previously described.
  • Another object of the invention is a preparation containing a compound of formula I, as described above or described as preferred.
  • Another object of the invention is a preparation containing the inventive mixture consisting of at least one compound of formula I, as described above or described as preferred or described as individual compounds, together with (4-tert-Butyl-phenyl) -3-hydroxy-1- (4-methoxyphenyl) -propan-1-one, 1- (4-tert-butyl-phenyl) -3-hydroxy-3- (4 -methoxy-phenyl) -propan-1-one or the mixtures of these propan-1-one compounds.
  • Another object of the invention is a preparation containing the inventive mixture consisting of at least one compound of formula I, as described above or described as preferred or described as individual compounds, together with 3- (4-tert-butyl-phenyl) -3- hydroxy-1- (4-methoxy-phenyl) -propan-1-one, 1- (4-tert-butyl-phenyl) -3-hydroxy-3- (4-methoxy-phenyl) -propan-1-one or the mixtures of these propan-1-one compounds and at least one UV filter.
  • the preparations are usually topically applicable preparations, for example cosmetic or cosmetic preparations
  • preparations contain a cosmetic or
  • dermatologically suitable carrier and as desired
  • the preparations in this case contain a pharmaceutically acceptable carrier and optionally further pharmaceutical active ingredients.
  • the preparations When dealing with medical devices, the preparations contain a carrier suitable for the medical device.
  • Preparation must be suitable, for example, on the skin
  • Preferred preparations are cosmetic preparations.
  • agent or formulation is used synonymously in addition to the term preparation.
  • the preparations may comprise or contain, consist essentially of or consist of said necessary or optional ingredients. All compounds or components in the
  • Preparations can be used, are either known and commercially available or can be synthesized by known methods.
  • the preparations according to the invention may preferably have at least one carrier suitable for cosmetic, pharmaceutical, dermatological preparations, medical products, household products or plastics.
  • the preparation according to the invention preferably contains 3- (4-tert-butylphenyl) -3-hydroxy-1- (4-methoxyphenyl) -propan-1-one or 1- (4-tert-butylphenyl) -3 -hydroxy-3- (4-methoxyphenyl) -propan-1-one or a mixture of these propan-1-one compounds, in particular 3- (4-tert-butylphenyl) -3-hydroxy-1- ( 4-methoxy-phenyl) -propan-1-one.
  • the inventive preparations may contain at least one organic or inorganic UV filter.
  • UV light-added filter of avobenzone is different and, moreover, preferably photostable, as described above.
  • photobeam-marketed UV-filters are, for example, hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate, marketed under the trade names Uvinul® A Plus from BASF SE, 2,2'-methylene bis ( 6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol) sold under the name Tinosorb® M by BASF SE or salts of 2,2 '- (1, 4-phenylene) bis) -1H-benzimidazole-4,6-disulfonic acid), for example sold under the name Neo Heliopan® AP from Symrise, 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-methyl-3- (1,3,3,3-tetramethyl-1- (trimethylsilyloxy) disiloxany
  • the added organic UV filter in the preparation according to the invention is avobenzone.
  • a preparation according to the invention during irradiation with solar or sun-like light within a predetermined period of time at most a UV-absorbing capacity deviating by +/- 5%.
  • Sun-like light is radiation in a spectral composition analogous to solar radiation or sunlight.
  • Such sun-like light can be generated for example by a solar simulator or used in solariums, wherein the spectral composition of the solar radiation does not exactly match the sunlight.
  • light which is similar to that of the sun should also be understood to mean at least partially the spectral composition of the sunlight or to produce a sunlight-like effect.
  • such a preparation has an increasing UV absorption capacity during irradiation with solar or sun-like light within a predetermined period of time.
  • Another object of the invention is a method for stabilizing the UV absorption capacity of a preparation by means of a mixture of at least one compound of formula I, as described above, together with 3- (4-tert-butyl-phenyl) -3-hydroxy-1 - (4-methoxyphenyl) propan-1-one or 1- (4-tert-butylphenyl) -3-hydroxy-3- (4-methoxyphenyl) - propan-1-one or the mixtures of these propan-1-one compounds, especially together with 3- (4-tert-butyl-phenyl) -3-hydroxy-1- (4-methoxyphenyl) -propane-1 on, wherein the mixture and the preparation are coordinated so that when irradiated with solar or sun-like light, the UV absorption capacity of the preparation in a predetermined period has a maximum deviation of +/- 5 percent or increases.
  • another object of the invention is a method for stabilizing the UV absorption capacity of a preparation by means of the photoinduced antioxidative system as described above, wherein the photoinduced antioxidative system and the preparation are coordinated with one another such that, when irradiated with solar radiation, or sun-like light, the ultraviolet absorptive capacity of the preparation has a maximum deviation of +/- 5 percent in a predetermined period of time.
  • Another object of the invention in other words, a method for stabilizing the UV absorption capacity of a preparation by means of the UV filter system, as described above, wherein the UV filter system and the preparation are coordinated so that when irradiated with solar or Sonnenumblenlichem Light the UV absorption capacity of the preparation in a predetermined period of time, a deviation of not more than +/- 5 percent or increases.
  • the invention also provides a process for preparing a preparation as described above, wherein at least one compound according to formula I, optionally together with 3- (4-tert-butyl-phenyl) -3-hydroxy-1 - (4-methoxy-) phenyl) -propane-1-one or 1- (4-tert-butylphenyl) -3-hydroxy-3- (4-methoxyphenyl) -propan-1-one or a mixture of these compounds, especially (4-tert-butyl-phenyl) -3-hydroxy-1- (4-methoxyphenyl) -propan-1-one, and mixed with a carrier and optionally with further active or auxiliary substances. Suitable carriers and other UV filters or active or auxiliary substances are described in detail in the following part.
  • at least one compound of formula I having the defined or specified as preferred
  • Preparations according to the invention typically in amounts of 0.05 to 10 wt .-%, preferably in amounts of 0.1 wt .-% to 5 wt .-% and particularly preferably in amounts of 0.5 to 5 wt .-%, used ,
  • the expert does not have any difficulty in making the quantities according to the intended effect of the preparation
  • Layer structure of the pigments is not limited.
  • the color pigment should be skin colored or brownish at a level of from 0.5 to 5% by weight.
  • the selection of a corresponding pigment is familiar to the person skilled in the art.
  • UV filters for example organic UV filters.
  • organic UV filters are, for example, the so-called hydrophilic or lipophilic sunscreen filters which are effective in the UVA range and / or UVB range (and / or IR and / or VIS range (absorber)).
  • UV filters for example organic UV filters.
  • hydrophilic or lipophilic sunscreen filters which are effective in the UVA range and / or UVB range (and / or IR and / or VIS range (absorber)).
  • UV filters are usually named according to the INCI nomenclature.
  • PABA para-aminobenzoic acid and its derivatives: PABA, ethyl PABA, ethyl dihydroxypropyl PABA, ethylhexyl dimethyl PABA, e.g. B. under the name "Escalol 507" from the company.
  • ISP glyceryl PABA, PEG-25 PABA, z. B. under the name "Uvinul P25” from BASF.
  • Salicylates Homosalates are sold under the name "Eusolex HMS” by Merck; Ethyl hexyl salicylates, e.g. B. under the name “Neo Heliopan OS” from the Fa. Symrise, Dipropylene glycol salicylate, z. B. under the name “Dipsal” from the company. Scher, TEA salicylate, z. B. under the name “Neo Heliopan TS” of the Fa. Symrise. ⁇ , ⁇ -diphenylacrylate derivatives: octocrylenes, e.g. For example, sold under the name "Eusolex® OCR” by Merck, "Uvinul N539” by BASF, Etocrylene, for example, marketed under the name "Uvinul N35” by BASF.
  • Benzophenone Derivatives Benzophenone-1, e.g. B. operated under the name "Uvinul 400"; Benzophenone-2, e.g. B. operated under the name “Uvinul D50”; Benzophenone-3 or oxybenzone, e.g. B. sold under the name “Uvinul M40” Benzophenone-4, z. B. operated under the name "Uvinul MS40"; Benzophenone-9, e.g. B. under the name "Uvinul DS-49" from the company. BASF, Benzophenone-5, Benzophe- none-6, z. B. operated under the name "Helisorb 11" from the Fa.
  • Benzophenone-8 e.g. B. under the name "SpectraSorb UV-24” from the company American Cyanamid, Benzophenone-12 n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate or 2-hydroxy-4-methoxybenzophenone, sold by Merck, Darmstadt under the name Eusolex® 4360.
  • Benzylidene camphor derivatives 3-benzylidenecamphor, e.g. B. under the name "Mexoryl SD” from the company. Chimex, 4-Methylbenzylidene- camphor, z. B. under the name “Eusolex 6300” from the company Merck, Benzylidenecamphorsulfonklare, z. B. under the name “Mexoryl SL” from the company Chimex, Camphor benzalkonium methosulfate, z. B. under the name "Mexoryl SO” from the company Chimex,
  • Terephthalylidenedicamphorsulfonic acid e.g. B. under the name "Mexoryl SX” from the Fa Chimex
  • Polyacrylamidomethylbenzylidene- camphor operated under the name "Mexoryl SW” from the company Chimex.
  • Phenylbenzimidazole derivatives phenylbenzimidazolesulfonic acid, e.g. B.
  • Phenylbenzotriazole derivatives Drometrizole trisiloxanes, e.g. B. under the name "Silatrizole” from the Fa. Rhodia Chimie, Methylenebis (benzotriazolyl) tetramethylbutylphenol in solid form, eg. B. under the name "MIXXIM BB / 100" from the company. Fairmount Chemical, or in micronized form as an aqueous dispersion, eg. B. marketed under the name "Tinosorb M" by the former company BASF.
  • Anthraniline derivatives menthyl anthranilates, e.g. B. operated under the
  • Imidazole derivatives ethylhexyldimethoxybenzylidenedioxoimidazoline propionate.
  • Benzalmalonate Derivatives Polyorganosiloxanes containing functional benzalmalonate groups, such as polysilicone-15, z. B. sold under the name "Parsol SLX" by Hoffmann LaRoche.
  • Benzoxazole derivatives 2,4-bis [5- (1-dimethylpropyl) benzoxazol-2-yl (4-phenyl) imino] -6- (2-ethylhexyl) imino-1,3,5-triazines, e.g. B. sold under the name Uvasorb K2A from the company. Sigma 3V and mixtures thereof containing.
  • Suitable organic UV-protective substances which are suitable as organic UV filters are preferably selected from the following list: ethylhexyl salicylate, phenylbenzimidazolesulfonic acid, benzophenone-3, benzophenone-4, benzophenone-5, n-hexyl 2- (4- diethylamino-2-hydroxybenzoyl) benzoates, 4-methylbenzylidenecamphor, terephthalylidenedicamphorsulfonic acid, disodium phenyldibenzimidazole etetrasulfonates, methylenebis (benzotriazolyl) tetramethylbutylphenol, ethylhexyl triazone, diethylhexyl butamido triazone, drometrizole trisiloxanes, polysilicone-15, 1, 1-dicarboxy (2,2 ').
  • organic UV filters are usually incorporated in formulations in an amount of from 0.01% to 20% by weight, preferably 1% to 10% by weight.
  • compositions according to the invention may also contain inorganic UV filters, so-called particulate UV filters.
  • coated titanium dioxide for example Eusolex ® T-2000, Eusolex ® T-AQUA, Eusolex ® T-AVO, Eusolex ® T-OLEO), zinc oxides (for example Sachtotec® ®),
  • Iron oxides or else cerium oxides and / or zirconium oxides are preferred.
  • pigmentary titanium dioxide or zinc oxide are also possible, the particle size of these pigments being greater than or equal to 200 nm, for example Hombitan® FG or Hombitan® FF-Pharma.
  • the preparations may further be preferred if the preparations contain inorganic UV filters which are prepared by customary methods, such as, for example, in US Pat
  • Lecithin phospholipids, sodium, potassium, zinc, iron or aluminum salts of fatty acids, polyethylenes, silicones, proteins (especially
  • Collagen or elastin alkanolamines, silica, alumina, other metal oxides, phosphates, such as sodium hexametaphosphate or glycerol.
  • Preferably used particulate UV filters are:
  • untreated titanium dioxides e.g. the products Microtitanium Dioxide MT 500 B from Tayca; Titanium Dioxide P25 from Degussa,
  • micronized titanium dioxides with aluminum oxide and / or aluminum stearates / laurate aftertreatment such as Microtitanium Dioxide MT 100 T from Tayca, Eusolex T-2000 from Merck,
  • micronized titanium dioxides with iron oxide and / or iron stearates aftertreatment such as, for example, the product "Microtitanium Dioxide MT 100 F" from Tayca,
  • Alumina and silicone aftertreatment such as e.g. the product
  • micronised titanium dioxides with sodium hexametaphosphates e.g. the product "Microtitanium Dioxide MT 150 W” from Tayca.
  • the treated micronized titanium dioxides used for combination may also be post-treated with:
  • Octyltrimethoxysilane such as. the product Tego Sun T 805 from Degussa,
  • silica such as. the product Parsol T-X from DSM, alumina and stearic acid; such as. the product UV titanium
  • Aluminum and glycerin such as. the product UV titanium of the Fa.
  • Aluminum and silicone oils e.g. the product UV-Titan M262 of the company Sachtleben,
  • Polydimethylsiloxanes e.g. the product 70250 Cardre UF Ti02SI3 "from the company Cardre,
  • Untreated zinc oxides such as the product Z-Cote from BASF (Sunsmart), Nanox from the company Elementis
  • Post-treated zinc oxides such as the following products:
  • mixtures of various metal oxides e.g. Titanium dioxide and cerium oxide with and without aftertreatment, e.g. the product Sunveil A of the company Ikeda.
  • mixtures of alumina, silica, and silicon aftertreated titanium dioxide may also be used.
  • Zinc oxide mixtures such. the product UV titanium M261 of the company Sachtleben in combination with the
  • UV protectants according to the invention are used.
  • inorganic UV filters are incorporated usually in an amount of 0.1 weight percent to 25 weight percent, preferably 2 wt .-% - 10 wt .-%, in the preparations.
  • Preferred preparations may also comprise at least one further cosmetic active ingredient, for example selected from
  • Antioxidants anti-aging ingredients, anti-cellulite ingredients,
  • Agents "Antioxidants,” “Dermo-relaxing or dermo-decontracting agents,” “Anti-glycation agents,” “Agents for stimulating the synthesis of dermal and / or epidermal macromolecules, and / or for,” Agents for stimulating fibroblast or keratinocyte proliferation and / or keratinocyte differentiation, agents promoting the maturation of the horny envelope, NO-synthase inhibitors, peripheral benzodiazepine receptor (PBR) antagonists, agents for increasing the activity of the sebaceous "glands”, “agents for stimulating the energy metabolism of cells”, “tensioning agents”, “fat-reducing agents”, “sliming agents”, “agents for promoting the cutaneous microcirculation”, “calmatives or anti-irritants", “Sebo -regulating or anti-seborrhoic agents ",” astringents ",” cicatrizing agents “,” anti-inflammatory agents ",” antiacne agents ".
  • PBR
  • antioxidants there are many known and proven substances in the literature that can be used as antioxidants, e.g. Amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles, peptides such as DL-carnosine, D-carnosine, L-carnosine and their derivatives (eg anserine), carotenoids, carotenes (eg ⁇ -carotene, ⁇ -carotene , Lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and its derivatives (eg dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols (eg thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl) , Ethyl, propyl, amyl, butyl and lauryl, palmito
  • Thiodipropionic acid and its derivatives esters, ethers, peptides, lipids, nucleotides, nucleosides and salts
  • sulfoximine compounds eg buthionine sulfoximines, homocysteinsulfoximine, buthionine sulfones, penta, hexa, heptathionine sulfoximine
  • very low tolerated dosages eg pmol to ⁇ / kg
  • furthermore (metal) chelators eg, hydroxyfatty acids, palmitic acid, phytic acid, lactoferrin
  • ⁇ -hydroxy acids e.g., citric acid, lactic acid, malic acid
  • Vitamin E acetate
  • vitamin A and derivatives e.g., vitamin A palmitate
  • benzoic acid coniferyl benzoate rutinic acid and its derivatives
  • ⁇ -glycosylrutin ferulic acid
  • furfurylidene glucitol carnosine
  • zinc and its derivatives eg ZnO, ZnSO 4
  • selenium and its derivatives eg selenium methionine
  • stilbenes and their derivatives eg stilbene oxide, trans-stilbene oxide
  • Suitable antioxidants are also compounds of the formulas A or B.
  • R1 is selected from the group -C (0) CH 3l -C0 2 R 3, -C (0) NH2, and -C (0) N (R 4) 2 can be selected,
  • X is O or NH
  • R 2 is linear or branched alkyl having 1 to 30 C atoms
  • R 3 is linear or branched alkyl having 1 to 20 C atoms
  • R are each independently of one another H or linear or branched alkyl having 1 to 8 C atoms
  • R 5 is H or linear or branched alkyl having 1 to 8 C atoms or linear or branched alkoxy having 1 to 8 C atoms and
  • R 6 denotes linear or branched alkyl having 1 to 8 C atoms, preferably derivatives of 2- (4-hydroxy-3,5-dimethoxybenzylidene) malonic acid and / or 2- (4-hydroxy-3,5-dimethoxybenzyl) - malonic acid, more preferably 2- (4-hydroxy-3,5-dimethoxybenzylidene) -malonic acid bis- (2-ethylhexyl) ester (for example Oxynex ST Liquid) and / or 2- (4-hydroxy-3,5-dimethoxybenzyl) -malonic acid-bis- (2-ethylhexyl) ester (example RonaCare ® AP).
  • R 1 to R 6 and X apply here only for the radicals of the formulas A and B and have no relation to the radicals of the formula I.
  • antioxidants are also suitable for use in the cosmetic preparations according to the invention.
  • Known and commercial mixtures mixtures are, for example comprising, as active ingredients, lecithin, L - (+) - ascorbyl palmitate and citric acid, natural tocopherols, L - (+) - ascorbyl palmitate, L - (+) - ascorbic acid and citric acid (for example Oxynex ® K LIQUID) , Tocopherol extracts from natural sources, L - (+) - ascorbyl palmitate, L - (+) - ascorbic acid and citric acid (eg Oxynex ® L LIQUID), DL-a-tocopherol, L - (+) - ascorbyl palmitate, citric acid and lecithin (eg Oxynex ® LM) or butylhydroxytoluene (BHT), L - (+) - ascorbyl palmitate and citric acid (eg Oxynex ® 2004).
  • Compounds of the invention in such compositions usually in weight percent ratios ranging from 1000: 1 to 1: 1000, preferably used in weight percent ratios of 100: 1 to 1: 100.
  • the flavonoids known mainly as plant dyes or
  • Bioflavonoids often have an antioxidant potential.
  • Quercetin (cyanidanol, cyanidolone 1522, meietin,
  • Sophoretine, ericin, 3,3 ', 4', 5,7-pentahydroxyflavone as a particularly effective antioxidant (e.g., CA. Rice-Evans, N.J. Miller,
  • Quercetin shows the highest activity of the investigated structures over the entire pH range.
  • Suitable anti-aging agents especially for skin care
  • Preparations are preferably so-called compatible solutes. These are substances that are involved in the osmoregulation of
  • osmolytes Plants or microorganisms are involved and can be isolated from these organisms. Under the generic term compatible solutes also the described in the German patent application DE-A-10133202 osmolytes are taken. Suitable osmolytes are, for example, the polyols, methylamine compounds and amino acids and in each case their precursors. As osmolytes are in the sense of the Germans
  • Patent application DE-A-10133202 in particular substances from the group of polyols, such as myo-inositol, mannitol or sorbitol and / or one or more of the following osmolytically active substances: taurine, choline, betaine,
  • Phosphorylcholine glycerophosphorylcholine, glutamine, glycine, a-alanine, glutamate, aspartate, proline, and taurine.
  • Precursors of these substances are, for example, glucose, glucose polymers, phosphatidylcholine,
  • Phosphatidylinositol inorganic phosphates, proteins, peptides and polyamic acids.
  • Precursors are z. B. compounds by
  • Metabolic steps are converted into osmolytes.
  • compatible solute substances are selected from the group consisting of Pyrimidincarbonklaren (such as ectoine and
  • hydroxyectoine proline
  • betaine glutamine
  • cyclic diphosphoglycerate N. acetylornithine, trimethylamine N-oxide di-myo-inositol phosphate (DIP), cyclic 2,3-diphosphoglycerate (cDPG), 1, 1-diglycerol phosphate (DGP), .beta.-mannosylglycerate (firoin), .beta.-mannosylglyceramide (firoin-A) or / and di-mannosyl-di-inositolphosphate (DMIP) or an optical isomer, derivative, eg an acid, a salt or ester of these compounds or
  • ectoine ((S) -1,5,6-tetrahydro-2-methyl-4-pyrimidinecarboxylic acid) and hydroxyectoine ((S, S) -1,4,5,6-tetrahydro-5 are among the pyrimidinecarboxylic acids hydroxy-2-methyl-4-pyrimidinecarboxylic acid) and their derivatives.
  • preparations according to the invention may contain at least one self-tanner as further ingredient.
  • Advantageous self-tanning agents which can be used include: 1,3-dihydroxyacetone, glycerolaldehyde, hydroxymethylglyoxal, ⁇ -dialdehyde, erythrulose, 6-aldo-D-fructose, ninhydrin, 5-hydroxy-1,4-naphthoquinone (juglone) or 2- Hydroxy-1, 4-naphthoquinone (Lawson).
  • very particular preference is the 1, 3-dihydroxyacetone, erythrulose or their
  • the preparations may also contain one or more further skin-lightening active ingredients or synonymously depigmenting or
  • skin-lightening active ingredients can be all active ingredients known to the person skilled in the art.
  • Hydroquinone Hydroquinone, kojic acid, arbutin, aloesin, vitamin C or rucinol.
  • the preparations to be used may contain vitamins as further ingredients.
  • vitamins and vitamin derivatives selected from vitamin A, vitamin A propionate, vitamin A palmitate, vitamin A acetate, retinol, vitamin B, thiamin chloride hydrochloride (vitamin Bi), riboflavin (vitamin B 2 ), nicotinamide, Vitamin C (ascorbic acid), vitamin D, ergocalciferol (vitamin D 2 ), vitamin E, DL-ct-tocopherol, tocopherol-E-acetate, tocopherol hydrogen succinate, vitamin ⁇ - ⁇ , esculin (vitamin P active ingredient), thiamine (vitamin B ⁇ , Nicotinic acid (niacin), pyridoxine, pyridoxal, pyridoxamine, (vitamin B 6 ), pantothenic acid, biotin, folic acid and cobalamin (vitamin Bi 2 ), particularly preferably vitamin A palmitate, vitamin C and its derivatives, DL- a-
  • the retinoids described are also effective anti-cellulite agents.
  • Another well-known anti-cellulite drug is caffeine.
  • the said constituents of the preparation can be incorporated in the usual way, by means of techniques which are well known to the person skilled in the art.
  • Suitable preparations for external use for example as a cream or milk (O / W, W / O, O / W / O, W / O / W), as a lotion or emulsion, in the form of oily-alcoholic, oily-aqueous or aqueous alcoholic gels or solutions can be sprayed onto the skin. They can be present as solid pens or be packaged as aerosol.
  • administration formulas such as capsules, dragees, powders, tablet solutions or solutions are suitable.
  • solutions solutions, suspensions, emulsions, PIT emulsions, pastes, ointments, gels, creams, lotions, powders, soaps, surfactant-containing cleaning preparations, oils, aerosols and sprays.
  • Preferred excipients come from the group of preservatives, stabilizers, solubilizers, colorants, odor improvers or thickeners.
  • Ointments, pastes, creams and gels may contain the usual excipients suitable for topical administration, e.g. animal and vegetable fats, waxes, paraffins, starch, tragacanth,
  • Cellulose derivatives Polyethylene glycols, silicones, bentonites, silicic acid, talc and zinc oxide or mixtures of these substances.
  • Powders and sprays may contain the usual excipients, for example lactose, talc, silicic acid, aluminum hydroxide, calcium silicate and polyamide powder or mixtures of these substances.
  • Sprays can additionally the usual volatile, liquefied propellants, eg Chlorofluorocarbons, propane / butane or dimethyl ether. Also, compressed air is advantageous to use.
  • Solutions and emulsions may contain the usual excipients such as solvents, solubilizers and emulsifiers, e.g. Water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzyl benzoate, propylene glycol, 1,3-butylglycol, oils, in particular cottonseed oil, peanut oil, corn oil, olive oil, castor oil and sesame oil, glycerol fatty acid esters, polyethylene glycols and fatty acid esters of sorbitan or mixtures contain these substances.
  • solvents e.g. Water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzyl benzoate, propylene glycol, 1,3-butylglycol, oils, in particular cottonseed oil, peanut oil, corn oil, olive oil, castor oil and sesame oil,
  • a preferred solubilizer in general is 2-isopropyl-5-methylcyclohexanecarbonyl-D-alanine methyl ester.
  • Suspensions may include the usual carriers such as liquid diluents, e.g. Water, ethanol or propylene glycol, suspending agents, e.g. ethoxylated isostearyl alcohols, polyoxyethylene sorbitol esters and
  • Soaps may contain the usual excipients such as alkali metal salts of fatty acids, salts of fatty acid monoesters, fatty acid protein hydrolysates, isothionates, lanolin, fatty alcohol, vegetable oils, plant extracts, glycerol, sugars or mixtures of these substances.
  • excipients such as alkali metal salts of fatty acids, salts of fatty acid monoesters, fatty acid protein hydrolysates, isothionates, lanolin, fatty alcohol, vegetable oils, plant extracts, glycerol, sugars or mixtures of these substances.
  • Surfactant-containing cleaning products may contain the customary carriers such as salts of fatty alcohol sulfates, fatty alcohol ether sulfates, sulfosuccinic monoesters, fatty acid protein hydrolysates, isothionates, imidazolinium derivatives, methyl taurates, sarcosinates, fatty acid amide ether sulfates, alkyl amidobetaines, fatty alcohols, fatty acid glycerides, fatty acid diethanolamides, vegetable and synthetic oils, lanolin derivatives, ethoxylated glycerol fatty acid esters or mixtures of these substances.
  • customary carriers such as salts of fatty alcohol sulfates, fatty alcohol ether sulfates, sulfosuccinic monoesters, fatty acid protein hydrolysates, isothionates, imidazolinium derivatives, methyl taurates, sarcosinates, fatty acid amide
  • Facial and body oils can be the usual carriers such as
  • oils such as fatty acid esters, fatty alcohols, silicone oils, natural oils such as vegetable oils and oily vegetable extracts, paraffin oils, lanolin oils or mixtures of these substances.
  • the preferred preparation forms include, in particular, emulsions.
  • Emulsions are advantageous and contain z.
  • Oils such as triglycerides of capric or caprylic, further natural oils such. Castor oil;
  • Fats, waxes and other natural and synthetic fats preferably esters of fatty acids with lower C-number alcohols, e.g. with isopropanol, propylene glycol or glycerol, or esters of
  • Silicone oils such as dimethylpolysiloxanes, diethylpolysiloxanes,
  • the oil phase of the emulsions, oleogels or hydrodispersions or lipodispersions in the context of the present invention is advantageously selected from the group of esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids
  • unsaturated, branched and / or unbranched alcohols having a chain length of 3 to 30 carbon atoms from the group of esters of aromatic carboxylic acid and saturated and / or unsaturated, branched and / or unbranched alcohols having a chain length of 3 to 30 carbon atoms.
  • ester oils can then advantageously be selected from the group isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononyl isononanoate, 2-ethylhexyl palmitate,
  • formulations of the invention may preferably contain excipients such as, for example, cosmetic oils (e.g., cosmetic oils (e.g.
  • Caprylic / capric triglycerides C12-15 alkyl benzoates, isopropyl myristate, arylalkyl benzoates such as e.g. Phenethylbenzoate (X-Tend 226) or
  • Cosmacol brand oil components such as dimyristyl tartrate, tri C14-C15 alkyl citrate, C12-C13 alkyl lactate, tridecyl salicylate, C12-C13 alkyl octanoate, C12-C13 alkyl maleate, C12-C13 alkyl citrate, C12-C13 alkyl tartrate), or polar protic auxiliaries (for example propylene glycol, glycerol, isopropanol, ethanol) or so-called solubilizers (eg butylphthalimides, isopropylphthalimides, dimethylisosorbides).
  • polar protic auxiliaries for example propylene glycol, glycerol, isopropanol, ethanol
  • so-called solubilizers eg butylphthalimides, isopropylphthalimides, dimethylisosorbides.
  • the oil phase may advantageously be selected from the group of branched and unbranched hydrocarbons and waxes, silicone oils, dialkyl ethers, the group of saturated or unsaturated, branched or unbranched alcohols, and fatty acid triglycerides, namely the triglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 8 to 24, in particular 12 to 18, carbon atoms.
  • the fatty acid glycerides can be advantageously selected from the group of synthetic, semi-synthetic and natural oils, e.g. For example, olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, palm kernel oil and the like.
  • any mixtures of such oil and wax components are also advantageous to use in the context of the present invention. It may also be advantageous, if appropriate, to use waxes, for example cetyl palmitate, as the sole lipid component of the oil phase.
  • the aqueous phase of the preparations to be used contains
  • alcohols, diols or polyols of low carbon number, and their ethers preferably ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, -monoethyl- or -monobutylether, diethylene glycol monomethyl or -monoethylether and analogous products, furthermore low C-number alcohols, e.g. As ethanol, isopropanol, 1, 2-propanediol, glycerol, and in particular one or more thickeners, which or which can be advantageously selected from the group
  • Silica aluminum silicates, polysaccharides or their derivatives, e.g. Hyaluronic acid, xanthan gum, hydroxypropylmethylcellulose, particularly advantageous from the group of polyacrylates, preferably a polyacrylate from the group of so-called Carbopols, for example Carbopols types 980, 981, 1382, 2984, 5984, each individually or in combination.
  • Carbopols for example Carbopols types 980, 981, 1382, 2984, 5984, each individually or in combination.
  • mixtures of the abovementioned solvents are used.
  • water can be another ingredient.
  • Emulsions are advantageous and contain z.
  • the preparations to be used contain hydrophilic surfactants.
  • the hydrophilic surfactants are preferably selected from the group of alkylglucosides, acyl lactylates, betaines and cocoamphoacetates.
  • the cosmetic and dermatological preparations can be in various forms. So they can z.
  • Oil-in-water (W / O / W) a gel, a solid stick, an ointment or even an aerosol.
  • Ectoine in encapsulated form, e.g. In collagen matrices and other common encapsulating materials, e.g.
  • wax matrices As encapsulated cellulose, in gelatin, wax matrices or liposomally encapsulated. In particular wax matrices as described in DE-A-43 08 282, have been found to be favorable. Preference is given to emulsions. O / W emulsins are especially preferred.
  • Emulsions, W / O emulsions and O / W emulsions are available in the usual way.
  • emulsifiers for example, the known W / O and O / W emulsifiers can be used. It is advantageous to use other conventional co-emulsifiers in the preferred O / W emulsions.
  • O / W emulsifiers are selected as co-emulsifiers, principally from the group of substances with HLB values of 11-16, very particularly advantageously with HLB values of 14.5-15.5, provided that the O / W Emulsifiers have saturated radicals R and R '. If the O / W emulsifiers have unsaturated radicals R and / or R ', or if isoalkyl derivatives are present, the preferred HLB value may be those of
  • Emulsifiers also lower or above.
  • fatty alcohol ethoxylates from the group of the ethoxylated stearyl alcohols, cetyl alcohols, cetylstearyl alcohols (cetearyl alcohols).
  • Polyethylene glycol (12) isostearate, polyethylene glycol (13) isostearate,
  • Polyethylene glycol (14) isostearate, polyethylene glycol (15) isostearate,
  • Polyethylene glycol (24) isostearate, polyethylene glycol (25) isostearate,
  • Polyethylene glycol (20) oleate As the ethoxylated alkyl ether carboxylic acid or its salt, the sodium laureth-11-carboxylate can be advantageously used. As the alkyl ether sulfate, sodium laureth-4 sulfate can be advantageously used.
  • polyethylene glycol glycerol fatty acid esters from the group consisting of polyethylene glycol (20) glyceryl laurate, polyethylene glycol (21) glyceryl laurate, polyethylene glycol (22) glyceryl laurate, polyethylene glycol (23) glyceryl laurate, polyethylene glycol (6) glyceryl caprate / citrate, polyethylene glycol (20). glyceryl oleate, polyethylene glycol (20) glyceryl isostearate, polyethylene glycol (18) glyceryl oleate (cocoate).
  • sorbitan esters from the group of polyethylene glycol (20) sorbitan monolaurate, polyethylene glycol (20) sorbitan monostearate, polyethylene glycol (20) sorbitan monoisostearate, polyethylene glycol (20) sorbitan monopalmitate, polyethylene glycol (20) sorbitan monooleate.
  • W / O emulsifiers can be used:
  • Fatty alcohols having 8 to 30 carbon atoms monoglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 8 to 24, in particular 12-18 C atoms, diglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids a chain length of 8 to 24, in particular 12-18 C-atoms, monoglycerol ethers of saturated and / or unsaturated, branched and / or unbranched alcohols
  • W / O emulsifiers are glyceryl monostearate, glyceryl, glyceryl monomyristate, glyceryl, diglyceryl monostearate, Diglycerylmonoisostearat, propylene glycol monostearate, propylene glycol monoisostearate, propylene glycol monocaprylate, propylene glycol, sorbitan, sorbitan, sorbitan, Sorbitanmonoisooleat, sucrose, cetyl alcohol, stearyl alcohol, arachidyl, behenyl, Isobehenyl alcohol, selachyl alcohol, chimyl alcohol, polyethylene glycol (2) stearyl ether (steareth-2), glyceryl monolaurate, glyceryl monocaprinate, glyceryl mono- caprylate or PEG-30 dipolyhydroxystearate.
  • the preparation may contain cosmetic adjuvants which are commonly used in this type of preparations, e.g.
  • Thickeners emollients, moisturizers,
  • surfactants such as soaps, emulsifiers, preservatives, antifoaming agents, perfumes, waxes, lanolin, propellants, dyes and / or pigments, and other ingredients commonly used in cosmetics.
  • dispersion or solubilizing agent an oil, wax or other fatty substance, a low monoalcohol or a low polyol or mixtures thereof.
  • preferred monoalcohols or polyols include ethanol, i-propanol, propylene glycol, glycerin and sorbitol.
  • a preferred embodiment of the invention is an emulsion which is present as a protective cream or milk and contains, for example, fatty alcohols, fatty acids, fatty acid esters, in particular triglycerides of fatty acids, lanolin, natural and synthetic oils or waxes and emulsifiers in the presence of water.
  • oily lotions based on natural or synthetic oils and waxes, lanolin,
  • Fatty acid esters in particular triglycerides of fatty acids, or oily alcoholic lotions based on a lower alcohol, such as ethanol, or a glycerol, such as propylene glycol, and / or a polyol, such as glycerol, and oils, waxes and fatty acid esters, such as triglycerides of
  • the preparation may also be in the form of an alcoholic gel comprising one or more lower alcohols or polyols, such as ethanol, propylene glycol or glycerin, and a thickener, such as silica.
  • the oily alcoholic gels also contain natural or synthetic oil or wax.
  • the solid sticks consist of natural or synthetic waxes and oils, fatty alcohols, fatty acids, fatty acid esters, lanolin and other fatty substances.
  • the customary propellants such as alkanes, are generally used.
  • MeO-MBM MeO-MBM
  • phosphine oxides in cosmetic oils such as DMI unexpectedly accelerates the formation of avobenzone by photoconversion of MeO-MBM.
  • Triphenylphosphanoxid conversion When using Triphenylphosphanoxid conversion can be increased by 42%. When using tri-ortho-tolylphosphane oxide, an increase of 62% can be achieved.
  • the following preparation examples may further contain the following stabilizers (0.1-10% in each individual component or in mixtures): benzotriazolyl dodecyl p-cresol (Tinoguard TL), butyloctyl salicylate, diethylhexyl 2,6-naphthalates, diethylhexyl Syringylidene malonate, polyester-8 (Polyacrylenes), bis-ethylhexyl hydroxydimethoxy benzyl malonates.
  • stabilizers 0.1-10% in each individual component or in mixtures: benzotriazolyl dodecyl p-cresol (Tinoguard TL), butyloctyl salicylate, diethylhexyl 2,6-naphthalates, diethylhexyl Syringylidene malonate, polyester-8 (Polyacrylenes), bis-ethylhexyl hydroxydimethoxy benzyl malonates.
  • Cyclopentasiloxanes 43,80 41, 30 41, 80 41, 3 41, 8 (Dow Corning 245) 0 0
  • phase A The components of phase A are combined at room temperature and stirred. Subsequently, phase B is mixed and added with stirring to phase B and stirred.
  • Tri-ortho-tolylphosphine oxide 2.0 1, 5 1, 0
  • Triphenylphosphine oxide 2.0 2.0 1, 5 1, 0
  • Vitamin E acetate 0.2 0.2 0.3 0.1 0.5

Abstract

L'invention concerne l'utilisation d'au moins un oxyde de phosphane en tant qu'accélérateur d'une réaction photo-induite de la 3-(4-tert-butyl-phényl)-3-hydroxy-1-(4-méthoxy-phényl)-propan-1-one, de la 1-(4-tert-butyl-phényl)-3-hydroxy-3-(4-méthoxy-phényl)-propan-1-one ou d'un mélange de ces composés de la propan-1-one pour donner de l'avobenzone. L'invention concerne en outre des mélanges ainsi qu'une préparation contenant au moins un oxyde de phosphane et un procédé pour stabiliser les facultés d'absorption des UV d'une préparation au moyen d'un mélange constitué d'au moins un oxyde de phosphane conjointement avec de la 3-(4-tert-butyl-phényl)-3-hydroxy-1-(4-méthoxy-phényl)-propan-1-one, de la 1-(4-tert-butyl-phényl)-3-hydroxy-3-(4-méthoxy-phényl)-propan-1-one ou un mélange de ces composés de la propan-1-οne, et de manière particulièrement préférée conjointement avec de la 3-(4-tert-butyl-phényl)-3-hydroxy-1-(4-méthoxy-phényl)-propan-1-one.
EP12755800.5A 2011-09-29 2012-08-30 Oxydes de phosphane en tant qu'accélérateurs de réaction Withdrawn EP2760423A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE201110115285 DE102011115285A1 (de) 2011-09-29 2011-09-29 Phosphanoxide als Reaktionsbeschleuniger
PCT/EP2012/003644 WO2013045016A2 (fr) 2011-09-29 2012-08-30 Oxydes de phosphane en tant qu'accélérateurs de réaction

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EP2760423A2 true EP2760423A2 (fr) 2014-08-06

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Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102015211792A1 (de) 2015-06-25 2016-12-29 Beiersdorf Ag Sonnenschutzmittel mit Ausgangsstoff für die Bildung von 4-(tert.-Butyl)-4'-methoxydibenzoylmethan
DE102015211793A1 (de) 2015-06-25 2016-12-29 Beiersdorf Ag Alkandiol-haltige Sonnenschutzmittel mit Ausgangsstoff für die Bildung von 4-(tert.-Butyl)-4'-methoxydibenzoylmethan
DE102015211790A1 (de) 2015-06-25 2016-12-29 Beiersdorf Ag Ethanolisches Sonnenschutzmittel mit Ausgangsstoff für die Bildung von 4-(tert.-Butyl)-4'-methoxydibenzoylmethan
DE102015216959A1 (de) 2015-09-04 2017-03-09 Beiersdorf Ag Parfümiertes Sonnenschutzmittel mit Ausgangsstoff für die Bildung von 4-(tert.-Butyl)-4'-methoxydibenzoylmethan
WO2017088950A1 (fr) * 2015-11-27 2017-06-01 Merck Patent Gmbh Bêta-hydroxy-cétone utilisée comme principe actif à usage topique pour la prévention ou le traitement de photodermatoses
DE102015225570A1 (de) 2015-12-17 2017-06-22 Beiersdorf Ag Allerneustes Sonnenschutzmittel mit Ausgangsstoff für die Bildung von 4-(tert.-Butyl)-4'-methoxy-di-ben-zoylmethan
DE102015225567A1 (de) 2015-12-17 2017-06-22 Beiersdorf Ag Neues Sonnenschutzmittel mit Ausgangsstoff für die Bildung von 4-(tert.-Butyl)-4'-methoxydibenzoylmethan
DE102015225568A1 (de) 2015-12-17 2017-06-22 Beiersdorf Ag Neustes Sonnenschutzmittel mit Ausgangsstoff für die Bildung von 4-(tert.-Butyl)-4'-methoxydibenzoylmethan
DE102016000800A1 (de) 2016-01-27 2017-07-27 Beiersdorf Ag Sonnenschutzmittel mit Tricyclodecanmethylisononanoat

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0083796A1 (fr) * 1982-01-11 1983-07-20 Bayer Ag Masses à mouler ignifuges à base de téréphtalate de polyéthylène, procédé de préparation et son utilisation pour la production d'articles
DE3532360A1 (de) * 1985-09-11 1987-03-19 Hoechst Ag Verfahren zur herstellung tertiaerer phosphanoxide
DE3925217A1 (de) * 1989-07-29 1991-01-31 Basf Ag Verfahren zur herstellung von octadienolen
TW197375B (fr) 1990-11-19 1993-01-01 Hayashibara Biochem Lab
FR2680683B1 (fr) 1991-08-29 1993-11-12 Oreal Composition cosmetique filtrante contenant un polymere filtre a structure hydrocarbonee et une silicone filtre.
DE4308282C2 (de) 1993-03-16 1994-12-22 Beiersdorf Ag Vorzugsweise in Form von Mikrosphärulen vorliegende galenische Matrices
DE10133202A1 (de) 2001-07-07 2003-01-16 Beiersdorf Ag Osmolyte enthaltende kosmetische und dermatologische Zubereitungen zur Behandlung und aktiven Prävention trockener Haut und anderer negativer Veränderungen der physiologischen Homöostase der gesunden Haut
DE102006019044A1 (de) * 2006-04-25 2007-10-31 Merck Patent Gmbh Antioxidantien
FR2926980A1 (fr) 2008-02-06 2009-08-07 Oreal Composition cosmetique contenant un derive de dibenzoylmethane et un derive ester d'aminioacide neutre n-acyle particulier ; procede de photostabilisation du derive de dibenzoylmethane
US20110212040A1 (en) * 2010-02-28 2011-09-01 Von Oppen Bezalel Lea Stabilized sunscreen compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2013045016A2 *

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WO2013045016A2 (fr) 2013-04-04
DE102011115285A1 (de) 2013-04-04

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