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EP1778175A1 - Nitriles alpha-benzoyl-cinnamiques constituant de nouveaux absorbeurs uv - Google Patents

Nitriles alpha-benzoyl-cinnamiques constituant de nouveaux absorbeurs uv

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Publication number
EP1778175A1
EP1778175A1 EP05775888A EP05775888A EP1778175A1 EP 1778175 A1 EP1778175 A1 EP 1778175A1 EP 05775888 A EP05775888 A EP 05775888A EP 05775888 A EP05775888 A EP 05775888A EP 1778175 A1 EP1778175 A1 EP 1778175A1
Authority
EP
European Patent Office
Prior art keywords
hydrogen
alkyl
cosmetic
acid
alkoxy
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Withdrawn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
EP05775888A
Other languages
German (de)
English (en)
Inventor
Oskar Koch
William Johncock
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.)
Symrise AG
Original Assignee
Symrise AG
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Filing date
Publication date
Application filed by Symrise AG filed Critical Symrise AG
Publication of EP1778175A1 publication Critical patent/EP1778175A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/40—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by doubly-bound oxygen atoms
    • 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
    • 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

Definitions

  • the invention relates to the use of certain novel ⁇ -benzoyl-cinnamonitriles as UV filters (UV absorbers) in cosmetic and dermatological formulations such as sunscreens, day and hair care products.
  • the invention further relates to corresponding cosmetic and dermatological formulations.
  • the invention also relates to the new ⁇ -benzoyl-cinnamonitriles themselves.
  • UV rays are subdivided according to their wavelength into UV-A rays (320-400nm) and UV-B rays (280-320nm).
  • UV-A rays 320-400nm
  • UV-B rays 280-320nm
  • Sunburn (erythema), is mainly caused by the UV-B radiation.
  • Sunscreen indispensable to cover this area in addition to the UV-B range by effective UV-A absorber is the 4-dimethylethyl-4'-methoxydibenzoylmethane (a dibenzoylmethane derivative) whose absorption maximum is 357 nm.
  • DE 196 34 229 discloses compounds that absorb in the UV-AI range and also with e.g. Octyl methoxycinnamate are compatible.
  • the disadvantage is that upon irradiation of these compounds an E / Z isomerism occurs, so that after only a few minutes in addition to the originally used E-isomer in about equal proportions, the Z-isomer is formed (equilibrium state).
  • this Z-isomer has an absorption in the UV-B range, so that the desired protective effect in the UV-A range substantially decreases.
  • UV-A filters which are photostable, form compatible cosmetic formulations with UV-B filters with respect to photostability, and moreover preferably UV with respect to their E / Z isomers on irradiation -A protection substantially retained.
  • R independently of one another hydrogen, C r C 8 alkyl or C 8 alkoxy
  • R 4 is hydrogen or C r C 8 alkyl
  • R 5 -R 7 are independently hydrogen, dC 8 alkyl or C r C 8 alkoxy, as UV-A filters in cosmetic or dermatological formulations.
  • each formula image encompasses all possible configuration isomers of the stated compound and mixtures thereof;
  • the possible E / Z isomers (and mixtures thereof) are included, in the case of
  • Presence of chiral centers are each encompassed by the R and S enantiomers (as well as mixtures thereof).
  • the use according to the invention corresponds to a process for the preparation of a cosmetic or dermatological formulation, wherein an effective amount of one or more compounds of the formula I (as defined above) is mixed with other ingredients of a cosmetic or dermatological formulation.
  • the use according to the invention also corresponds to a method for protecting skin or hair against UV radiation, in particular UV-A radiation, wherein an effective amount of one or more compounds of the formula I (as defined above) in the form of a cosmetic or dermatological formulation, the contains other ingredients applied to the skin or hair.
  • the compounds of the formula I to be used according to the invention are suitable, in particular, for combination with UV filters from the group of the methoxycinnamate derivatives and / or dibenzoylmethane derivatives (see the examples of the photostability test below); such combinations have proven to be surprisingly photostable.
  • the invention therefore also relates to the use of compounds of the formula I (as defined above) for increasing the photostability of UV filters from the group consisting of methoxycinnamates and dibenzoylmethanes (with regard to preferred compounds of the formula I and with regard to preferred methoxycinnamates and dibenzoylmethanes, see below).
  • DE 10 87 902 A1 relates only to the technical UV protection, so that with regard to the respective subject area and the respective needs clear
  • the incorporation (and fixation) of a technical UV filter into plastics, films, fibers or the like is something quite different than the incorporation into a cosmetic formulation (eg an O / W emulsion), which is applied to the skin and - dependent from the chemical structure of the UV filter can lead to skin penetration.
  • a cosmetic formulation eg an O / W emulsion
  • R 1 is C 1 -C 8 -alkoxy, preferably para-position Ci -C 8 -alkoxy-Al, and R 2, R 3 is hydrogen and or
  • R 5 -R 7 is hydrogen or
  • R 6 and R 7 are hydrogen and R 5 is Ci-C 8 alkyl, preferably para-permanent and or
  • R 4 is hydrogen
  • R 1 is para-C 1 -C 4 -alkoxy
  • R 2 and R 3 are hydrogen
  • R 4 is hydrogen
  • R 5 is hydrogen or para-substituted d-alkyl (ie methyl) as well as
  • R 6 and R 7 are hydrogen
  • UV filters for the UV-A range, the following compounds are particularly preferred (see also Examples 1-4 below):
  • E-isomers crystalline compounds which have a high extinction in the UV-A range, are particularly preferred. Also preferred are E / Z isomer mixtures of the compounds shown, in particular those having a UV-A content of the total UV absorption (280-400 nm) greater than or equal to 50%.
  • the ⁇ -benzoyl cinnamonitrile compounds to be used according to the invention can be used as UV filters (UV absorbers) in cosmetic or dermatological formulations, in particular for protection against acute (sunburn) and chronic (premature skin aging) skin damage, especially in sunscreens, day care products and hair care products.
  • UV filters UV absorbers
  • ⁇ -benzoyl-cinnamonitrile compounds to be used according to the invention can be used individually or as a mixture in the corresponding formulations (preparations); You can also use them in combination with UV absorbers of other classes of substances or with these in any mixtures with each other.
  • a cosmetic or dermatological formulation according to the invention is provided.
  • Preparation comprises one or more compounds of the formula I as defined above (having the general or preferred meaning of the substituents, wherein the above information on preferred isomers continue to apply), as a UV absorber.
  • a preferred cosmetic or dermatological formulation further comprises: one or more further UV absorbers, in particular from the group of methoxycinnamate derivatives (p-methoxycinnamate) and / or dibenzoylmethane derivatives and / or coated or uncoated pigments of metal oxides.
  • one or more further UV absorbers in particular from the group of methoxycinnamate derivatives (p-methoxycinnamate) and / or dibenzoylmethane derivatives and / or coated or uncoated pigments of metal oxides.
  • the UV absorbers or pigments used are preferably selected and coordinated in their respective amounts so that they interact in such a way that the sun protection factor of the formulation is synergistically increased.
  • the UV absorbers used are particularly advantageously selected and coordinated in their respective amounts such that the critical wavelength of the formulation is ⁇ crit > 380 nm.
  • the critical wavelength is the wavelength at which the integral of the spectral absorption curve reaches 90% of the 290-400 nm integral.
  • UV absorbers may be mentioned, with which the compounds of the formula I can be combined in a particularly advantageous manner: • p-aminobenzoic acid
  • menthyl Neo Heliopan ® MA
  • 2- (4-diethylamino-2-hydroxybenzoyl) benzoate Uvinul ® A Plus
  • polymer-bound or polymeric UV absorbers in formulations according to the invention, in particular those as described in WO-A-92/20690.
  • ⁇ -benzoyl cinnamonitrile compounds to be used in the present invention with finely divided inorganic and organic pigments, e.g. titanium dioxide,
  • Zinc oxide and iron oxide or Tinosorb ® M in sunscreen and day care products with UV protection possible.
  • the enumeration of said UV filter which can be used in the context of the present invention in combination with the ⁇ -benzoyl-cinnamonitrile of the formula I, is of course not exhaustive.
  • the total amount of all (singly or multiply) sulfonated water-soluble UV filter substances in the finished cosmetic or dermatological formulations for example phenylene-bis-benzimidazyl-tetrasulfonic acid dinatrium salt or salts thereof and / or the corresponding disulfonic acid or salts thereof and / or 2 Phenylbenzimidazole-5-sulfonic acid or its salts and / or 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid or salts thereof and / or 4- (2-oxo-3-bomylidenemethyl) -benzenesulfonic acid or salts thereof and / or or 2-methyl-5- (2-oxo-3-bomylidene-methyl) -benzenesulfonic acid or its salts and / or benzene-1, 4-di- (2-oxo-3-bomylidenemethyl) -10-sulfonic acid or their salts, is advantageously selected from the range
  • the total amount of oil-soluble UV filter substances (including the compounds of the formula I) in the finished cosmetic or dermatological formulations, for example 4,4 ', 4 "- (1,3,5-triazine-2,4,6-triyltriimino) tris benzoic acid tris (2-ethylhexyl) and / or 4-tert-butyl-4'-methoxy-dibenzoyl methane and / or 4-methylbenzylidenecamphor and / or octyl dimethyl p-aminobenzoic acid and / or Mexoryl XL ® and / or Uvasorb HEB ® and / or Tinosorb ® S and / or benzophenone-3 and / or Parsol ® SLX and / or Neo Heliopan MA ® is advantageously chosen from the range of 0.1 to 10.0 wt .-%, preferably 0.5 to 6.0% by weight, based on the total weight of the formulations, if the presence of
  • the total amount of 2-ethylhexyl-p-methoxy-cinnamaten and / or p-Methox- cimt yarn in the finished cosmetic or dermatological preparations is advantageously from the range of 0.1 to 15.0 wt .-%, preferably 0.5 to 7.5% by weight, based on the total weight of the formulations, if the presence of these substances is desired.
  • the total amount of ethylhexyl 2-cyano-3,3-diphenylacrylate in the finished cosmetic or dermatological formulations, if the presence of this substance is desired, is advantageously from the range of 0.1 to 15.0% by weight, preferably 0 , Selected from 5 to 10.0 wt .-%, based on the total weight of the formulas.
  • the total amount of one or more salicylic acid derivatives in the finished cosmetic or dermatological formulations is in many cases advantageously selected from the range from 0.1 to 15.0% by weight, preferably 0.5 to 10.0% by weight on the total weight of the formulations.
  • ethylhexyl salicylate it is advantageous to choose its total amount from the range of 0.1 to 5.0% by weight.
  • homomenthylsalicylate it is advantageous to choose its total amount from the range of 0.1 to 10.0% by weight.
  • the particularly preferred combinations of (a) p-methoxycinnamate esters (methoxycinnamates) and / or dibenzoylmethanes and (b) compounds of the formula I can be formulated in a light-stable manner by using e.g. 0.1 to 5% by weight, preferably 1 to 3% by weight of 4-tert-butyl-4'-methoxydibenzoylmethane, 0.1 to 10% by weight, preferably 1 to 7.5% by weight p-methoxycinnamic acid ethylhexyl or isoamyl ester and at least 0.2% by weight, preferably 1 to 6% by weight, of the compounds of the formula I to be used according to the invention.
  • a ratio is preferably set in the range of 1 part of dibenzoylmethane derivative, 2.5-3.5 parts of p-methoxycinnamic acid ester and 1.0-2.5 parts of the ⁇ -benzoylcinnamonitrile compounds to be used according to the invention.
  • Particular preference is given to the combination of 1 part of dibenzoylmethane derivative, 3 parts of p-methoxycinnamate and 1 part of the ⁇ -benzoyl cinnamonitrile compounds to be used according to the invention.
  • a surprisingly synergistic increase in the sun protection factor is achieved in cosmetic or dermatological formulations by the use of ⁇ -benzoyl cinnamonitrile compounds of the formula I in combination with other UV filters.
  • Examples of a synergistic increase in the sun protection factor are cosmetic or dermatological emulsions which comprise both a compound of the formula I and ethylhexyl methoxycinnamate or octocrylene, or a combination of a compound of the formula I with ethylhexyl methoxycinnamate and 2-phenylbenzimidazole sulfonic acid, or ethylhexyl methoxycinnamate and methyl benzylidene camphor, or ethylhexyl -methoxycinnamat and 4-t-butyl-4'-methoxydibenzoylmethane, or Neo Heliopan AP ® and Ethylhexylmethoxy- cin
  • UV filter combinations are given here by way of example only; a synergistic effect also occurs when combined with other UV filters.
  • ⁇ -benzoylcinnamonitrile compounds of the formula I to be used according to the invention are (crystalline) solids under standard conditions (25 ° C., 1013 mbar) and must therefore be sufficiently dissolved in cosmetic formulations in order to avoid the problem of recrystallization after a prolonged storage period.
  • a sufficient amount of the oil components usually used in cosmetic formulations liquid oil-soluble UV absorbers or alcohols are used, for. As ethanol, isopropanol or 1-butanol.
  • the total amount used of all components of the oil phase in cosmetic emulsions with compounds of the formula I is preferably in the range of 0.5 to 30%, preferably 2 to 15%. All the above-mentioned oil components or liquid oil-soluble UV filters are excellent solvents for all crystalline oil-soluble UV absorbers.
  • UV absorbers on garments leave no more washable stains.
  • UV-A absorber tert-butylmethoxydibenzoylmethane that it does not produce more washable stains on textiles.
  • This disadvantage does not have the ⁇ -benzoyl-cinnamonitrile according to the invention to use, since any stains on textiles are very easy to wash out.
  • Sunscreen products should be waterproof, so that a sufficient UV protection for the user, especially children, while swimming or bathing is guaranteed.
  • the compounds to be used according to the invention meet these requirements to a particular extent.
  • 97% substantivity of the UV absorber was measured after washing and 95% in a W / O emulsion.
  • UV absorbers according to the invention may also be of considerable advantage to use the UV absorbers according to the invention with chelating substances, as described, for example, in US Pat. in EP-A 496 434, EP-A 313 305 and WO-94/04128 or to combine with polyaspartic acid and ethylenediamine tetramethyl-phosphonic acid salts.
  • the total amount of UV filter substances (UVA, UVB and / or broadband filters) in cosmetic or dermatological formulations according to the invention is advantageously in the range from 0.1 to 30 Wt .-%, preferably 0.1 to 10.0 wt .-%, in particular 0.5 to 5.0 wt .-%, based on the total weight of the formulations.
  • Cosmetic and dermatological formulations according to the invention also advantageously contain, although not necessarily, inorganic pigments based on finely dispersed metal oxides and / or other sparingly soluble or insoluble metal compounds, in particular the oxides of titanium (1102), zinc (ZnO), iron (eg Fe 2 O 3 ), zirconium (ZrO 2 ). Silicon (SiO 2 ). Manganese (eg MnO), aluminum (Al 2 O 3 ), Cers (eg Ce 2 O 3 ), mixed oxides of the corresponding metals and mixtures of such oxides. These pigments are X-ray amorphous or non-X-ray amorphous. Particular preference is given to pigments based on TiO 2 .
  • inorganic pigments based on finely dispersed metal oxides and / or other sparingly soluble or insoluble metal compounds in particular the oxides of titanium (1102), zinc (ZnO), iron (eg Fe 2 O 3 ), zirconium (ZrO 2 ). Silicon (S
  • X-ray amorphous oxide pigments are metal oxides or semimetal oxides which show no or no recognizable crystal structure in X-ray diffraction experiments. Often, such pigments are obtainable by flame reaction, for example, by reacting a metal or semimetal halide with hydrogen and air (or pure oxygen) in a flame. In cosmetic, dermatological or pharmaceutical formulations, X-ray amorphous oxide pigments are used as thickening and thixotroping agents, flow aids for emulsion and dispersion stabilization and as a carrier substance (for example for increasing the volume of finely divided powders or powders).
  • X-ray amorphous oxide pigments are, for example, high-purity silica.
  • BET active surface area
  • the silica pigments are recognizable as loose, white powders.
  • Silicon dioxide pigment are marketed commercially under the name Aerosil ® (CAS -No. 7631-85-9) or Carb-O-Sil
  • Aerosil ® types for example, Aerosil ® 0x50. Aerosil ® 130, Aerosil ® 150, Aerosil ® 200, Aerosil ® 300, Aerosil ® 380, Aerosil ® MQX 80. Aerosil ® MOX 170 Aerosil COK ® 84, Aerosil ® R 202, Aerosil ® R 805, Aerosil ® R 812, Aerosil ® R 972, Aerosil ® R 974, Aerosil ® R976.
  • Cosmetic or dermatological light protection formulations according to the invention advantageously contain from 0.1 to 20% by weight, advantageously from 0.5 to 10% by weight, very particularly preferably from 1 to 5% by weight, of X-ray amorphous oxide pigments.
  • the non-X-ray amorphous inorganic pigments are advantageously in hydrophobic form, ie they are surface-treated to repel water.
  • This surface treatment may consist in providing the pigments with a thin hydrophobic layer according to methods known per se.
  • One such method is, for example, that the hydrophobic surface layer after a reaction according to n TiO 2 + m (RO) 3 Si-R ' ⁇ n TiO 2 (surface). is generated, n and m are to be used at will stoichiometric parameters, R and R 'are the desired organic radicals.
  • RO n TiO 2 + m (RO) 3 Si-R ' ⁇ n TiO 2 (surface).
  • TiO 2 pigments may be mentioned, such as those sold under the trade name T805 by Degussa. Preference is also given to TiO 2 / Fe 2 O 3 mixed oxides, as are also available, for example, under the trade name T817 from Degussa.
  • the total amount of inorganic pigments, in particular hydrophobic inorganic micropigments, in the finished cosmetic or dermatological formulations is advantageously in the range from 0.1 to 30% by weight, preferably 0.1 to 10.0, in particular 0.5 to 6.0% by weight, based on the total weight of the formulations.
  • the cosmetic and / or dermatological formulations according to the invention can be composed as usual and serve for cosmetic and / or dermatological sun protection, furthermore for the treatment, care and cleansing of the skin and / or the hair and as a make-up product in decorative cosmetics.
  • the formulations according to the invention depending on their structure, can be used, for example, as skin protection cream, cleansing milk, sunscreen lotion, nutritive cream, day cream, etc. It may be possible and advantageous to use the formulations according to the invention as a basis for pharmaceutical formulations. Preference is given in particular to those cosmetic and dermatological formulations which are in the form of a skin care or make-up product.
  • Typical embodiments are creams, gels, lotions, alcoholic and aqueous / alcoholic solutions, emulsions or stick preparations.
  • These agents can also be used as further auxiliaries and mild surfactants, co-emulsifiers, superfatting agents, pearlescent, consistency, thickening agents, polymers, silicone compounds, fats, waxes, stabilizers, biogenic agents, Deowirk für, anti-dandruff agents, film formers, swelling agents, hydrotopes, Preservatives, insect repellents, browning agents, artificial self-tanning agents (eg, dihydroxyacetone), solubilizers, perfume oils, dyes, anti-sprouting agents, and the like.
  • the cosmetic and dermatological formulations according to the invention are applied to the skin and / or the hair in a sufficient amount in the manner customary for cosmetics.
  • cosmetic and / or dermatological formulations according to the invention which are in the form of a cosmetic agent for protecting the skin and hair.
  • these can advantageously contain at least one inorganic pigment, preferably an inorganic micropigment.
  • the cosmetic and / or dermatological formulations according to the invention may comprise cosmetic adjuvants conventionally used in such formulations, for example preservatives, bactericides, perfumes, foaming inhibitors, colorants, pigments which have a coloring effect, thickeners, moisturizing and / or thickening agents. or moisturizing substances, fats, oils waxes or other common ingredients of a cosmetic or dermatological formulation such as alcohols, polyols, polymers, foam stabilizers, electrolytes, organic solvents or silicone derivatives.
  • cosmetic adjuvants conventionally used in such formulations, for example preservatives, bactericides, perfumes, foaming inhibitors, colorants, pigments which have a coloring effect, thickeners, moisturizing and / or thickening agents.
  • moisturizing substances fats, oils waxes or other common ingredients of a cosmetic or dermatological formulation such as alcohols, polyols, polymers, foam stabilizers, electrolytes, organic solvents or silicone derivatives.
  • Non-ionic emulsifiers or dispersants in question the group that is formed come from polyglyceryl-2 dipolyhydroxystearate (Dehymuls ® PGPH), polyglyceryl-3-diiso-stearate (Lameform ® TGI), Polyglyceryl-4-isostearate (lsolan ® GI 34), polyglyceryl-3 oleate, Polyglyceryl-Diisostearyl-3-Diisostearate (lsolan ® PDI), Polyglyceryl-3 methyl glucose distearate (Tego Carey ® 450), Polyglyceryl-3 beeswax (Cera Bellina ®), Polyglyceryl-4 caprate (polyglycerol Caprate T2010 / 90), polyglyceryl-3 cetyl ether (Chimexane ® NL), Polyglyceryl-3-distearate (Cremophor ® GS 32), polyglyceryl-2-
  • antioxidants An additional content of antioxidants is generally preferred. According to the invention, all antioxidants which are suitable or customary for cosmetic and / or dermatological applications can be used as favorable antioxidants.
  • the antioxidants are selected from the group consisting of amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (eg urocanic acid) and their derivatives, peptides such as D, L-camosine, D-camosine, L-camosine and their derivatives (eg anserine), carotenoids, carotenes (eg a-carotene, b-carotene, lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and its derivatives (eg dihydrolipoic acid), aurothioglucose, propyl-thiouracil and other thiols (eg Thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitol,
  • the amount of the aforementioned antioxidants (one or more compounds) in the formulations is preferably 0.001 to 30 wt .-%, particularly preferably 0.05 to 20 wt .-%, in particular 1 to 10 wt .-%, based on the total weight of Formulation.
  • vitamin E and / or its derivatives represent the antioxidant (s)
  • vitamin A or vitamin A derivatives, or carotenes or derivatives thereof are the antioxidant or antioxidants, it is advantageous if their respective concentrations are in the range from 0.001 to 10% by weight, based on the total weight of the formulation, to choose.
  • oils such as triglycerides of capric or caprylic acid, furthermore natural oils, e.g. 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 fatty alcohols with alkanoic acids of low C number or with fatty acids; - alkyl benzoates;
  • oils such as dimethylpolysiloxane, diethylpolysiloxane, diphenylpoly- siloxane and mixed forms thereof.
  • the oil phases of the emulsions, oleogels or hydrodispersions or lipodispersions in the context of the present invention advantageously comprise substances from the group of esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a chain length of 3 to 30 carbon atoms and saturated and / or or unsaturated, branched and / or unbranched alcohols having a chain length of 3 to 30 carbon atoms, from the group of esters of aromatic carboxylic acids 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 chosen from the group isopropyl myristate, palmitate, stearate, oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isoctyl stearate, isononyl stearate, isononyl isononanate, 2-ethylhexyl palmitate, Ethyl hexyl laurate, 2-hexyl decyl stearate, 2-octyl dodecyl palmitate, oleyl oleate, oleyl erucate, erucyl oleate and also synthetic, semisynthetic and natural mixtures of such esters, eg. Jojoba oil.
  • the oil phase can 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, in particular the triglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a chain length of 8 to 24, in particular 12 to 18 carbon atoms.
  • the fatty acid triglycerides may be advantageously selected from the group of synthetic, semisynthetic and natural oils, e.g. Olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, palm kernel oil and the like.
  • the oil phase comprises one or more substances from the group selected from the group 2-ethylhexyl, Ocryldodecanol, isotridecyl isononanoate, isoeicosane, 2-ethylhexyl cocoate, C benzoate alkyl-2- i 5, caprylic capric triglyceride, dicapryl ether.
  • the oil phase can also advantageously have a content of cyclic or linear silicone oils, although it is preferred to use an additional content of other oil phase components in addition to the silicone oil or silicone oils.
  • cyclomethicone octamethylcyclotetrasiloxane
  • silicone oils are also advantageous for the purposes of the present invention, for example hexamethyl cyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane).
  • mixtures of cyclomethicone and Isotri ⁇ decylisononanoat and from cyclomethicone and 2-Ethylhexylisostearat are particularly advantageous.
  • the aqueous phase of the formulations according to the invention optionally advantageously contains alcohols, diols or polyols (lower alkyl), and their ethers, preferably ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, Diethylene glycol monomethyl or - monoethyl ether and analogous products, also alcohols (lower alkyl), for example ethanol, 1,2-propanediol, glycerol and in particular one or more thickeners, which or which can be advantageously selected from the group of silica, aluminum silicates, polysaccharides or their Derivatives, for example hyaluronic acid, xanthan gum, hydroxypropylmethylcellulose, particularly advantageously from the group of polyacrylates, preferably a polyacrylate from the group of the so-called Carbopol
  • the invention also relates to the novel compounds of the formula I itself.
  • Compounds according to the invention are those of the formula I.
  • R, R independently of one another are hydrogen, C 1 -C 8 -alkyl or C 1 -C 8 -alkoxy,
  • R 4 is hydrogen or C 1 -C 8 -alkyl
  • R-R independently of one another are hydrogen, C 1 -C 8 -alkyl or C 1 -C 8 -alkoxy.
  • Part A Heat to about 85 ° C.
  • Part B Weigh raw materials without Carbopol. Disperse Carbopol with Ultra Turrax. Heat to about 85 ° C. Give B to A.
  • Part C Add immediately to A / B and then homogenize hot (Ultra Tur- rax). Allow to cool while stirring.
  • Part D Add and mix.
  • Part A Heat to about 85 ° C.
  • Part B Weigh raw materials without Carbopol. Disperse Carbopol with Ultra Turrax. Heat to about 85 ° C. Give B to A.
  • Part C Add immediately to A / B and then homogenize hot (Ultra Tur- rax). Allow to cool while stirring.
  • Part D Add and mix.
  • Part A Heat to 80-85 0 C.
  • Part B Heat to 80-85 0 C, type B to part A with stirring part.
  • Part C Disperse Carbopol into the water and neutralize with stirring while stirring with NaOH.
  • Part D Add and mix.
  • Part A Heat to 80-85 0 C.
  • Part B Heat to 80-85 0 C, type B to part A with stirring part.
  • Part C Disperse Carbopol into the water and neutralize with stirring while stirring with NaOH.
  • Part D Add and mix.
  • Part A Dissolve UV absorber according to formula 1 in the oil or liquid UV filters (heating to about 70 ° C.). Cool read to about 30 0 C, remaining Bestand ⁇ share excluding Carbopol and Pemulen add and mix at room temperature (about 5 minutes stirring). Stir in Carbopol and Pemulen.
  • Part B Dissolve sol brole in phenoxyethanol with warming. Mix with water and glycerine, add to part A with stirring. Approximately Stir for 60 minutes.
  • Part C Add to A / B, homogenize with the Ultra Turrax.
  • Part A Heat to about 85 ° C.
  • Part B Heat to about 85 ° C (without zinc oxide, disperse zinc oxide with Ultra Turrax). Give B to A. Allow to cool with stirring, then homogenize.
  • Part A Heat to about 85 ° C.
  • Part B Heat to about 85 ° C (without zinc oxide, disperse zinc oxide with Ultra Turrax). Give B to A. Allow to cool while stirring.
  • Part C Add and then homogenize.
  • Part A Heat to about 85 ° C.
  • Part B Heat to about 85 ° C. Give B to A. Allow to cool while stirring.
  • Part C Add and then homogenize.
  • Part A Heat to 80 0 C.
  • Part B Heat to 80 0 C. Add to Part A with stirring.
  • Part C Disperse Carbopol in water and neutralize with sodium hydroxide solution. At 55 ° C add to part A / B.
  • Part A Dissolve Lara Care A-200 with stirring in the other ingredients of Part A.
  • Part B Weigh out all raw materials (without pemulen) and dissolve the crystalline substances by heating. Disperse pemulen. Add part B to part A and homogenize for 1 minute.
  • Part A Disperse Carbopol in water and neutralize with sodium hydroxide solution.
  • Part B Add to Part A with stirring.
  • Part C Crystalline components with heating (max. 40 ° C) in the other
  • Part A Heat to 80 0 C.
  • Part B Heat to 80 ° C. Add to Part A with stirring.
  • Part C Add at 40 0 C and cool to RT.
  • Part A Heat to 80-85 0 C.
  • Part B Heat to 80-85 0 C, type B to part A with stirring part.
  • Part C Disperse Carbopol into the water and neutralize with stirring while stirring with NaOH. Add part C at about 60 ° C with stirring.
  • Photostability tests were carried out with a Suntester of the company.
  • the irradiation intensity was 80 W / m 2 , based on the UV range of 290-400 nm.
  • the irradiation time was 4 hours in total, the photoabsorption of the UV filters after 2 and 4 hours of irradiation being measured by HPLC analyzes.
  • the irradiations of the UV filter mixtures were carried out in an isopropyl myristate solution. The percentage values refer to the measured value without irradiation (reduction of the concentration).
  • DDBM 4-dimethylethyl-4'-methoxydibenzoylmethane
  • DDBM 4-dimethylethyl-4'-methoxydibenzoylmethane
  • Compound A1 thus causes an increase in the photostability of the Co-UV filters used, which is a Methoxycinnamat derivative and a Dibenzoyl- methane derivative.
  • the other compounds of the formula I according to the invention increase the stability of methoxycinnamate derivatives and dibenzoylmethane derivatives.
  • the compounds of Examples 1-4 are particularly preferred.
  • UV-A content of total absorption between 280-400nm is 50%. So there was no unacceptable shift in the UV-B range.
  • UV-A content of total absorption between 280-400nm is only 20%.

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Abstract

L'invention concerne l'utilisation d'un composé de formule (I) comme filtre UV dans des formulations cosmétiques, notamment en association avec des filtres UV du groupe des dérivés de méthoxycinnamate et/ou des dérivés de dibenzoylméthane.
EP05775888A 2004-08-07 2005-07-29 Nitriles alpha-benzoyl-cinnamiques constituant de nouveaux absorbeurs uv Withdrawn EP1778175A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200410038485 DE102004038485A1 (de) 2004-08-07 2004-08-07 alpha-Benzoyl-zimtsäurenitrile als neue UV-Absorber
PCT/EP2005/053725 WO2006015954A1 (fr) 2004-08-07 2005-07-29 Nitriles alpha-benzoyl-cinnamiques constituant de nouveaux absorbeurs uv

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EP1778175A1 true EP1778175A1 (fr) 2007-05-02

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