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WO1999006014A2 - Combinaisons d'ecrans solaires et compositions les contenant - Google Patents

Combinaisons d'ecrans solaires et compositions les contenant Download PDF

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Publication number
WO1999006014A2
WO1999006014A2 PCT/EP1998/004518 EP9804518W WO9906014A2 WO 1999006014 A2 WO1999006014 A2 WO 1999006014A2 EP 9804518 W EP9804518 W EP 9804518W WO 9906014 A2 WO9906014 A2 WO 9906014A2
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WO
WIPO (PCT)
Prior art keywords
compound
group
combination
formula
hydrogen
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Application number
PCT/EP1998/004518
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English (en)
Other versions
WO1999006014A3 (fr
Inventor
Giuseppe Raspanti
Alverio Malpede
Original Assignee
3V Sigma S.P.A.
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 3V Sigma S.P.A. filed Critical 3V Sigma S.P.A.
Priority to AU89778/98A priority Critical patent/AU736477B2/en
Publication of WO1999006014A2 publication Critical patent/WO1999006014A2/fr
Publication of WO1999006014A3 publication Critical patent/WO1999006014A3/fr

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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
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/29—Titanium; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/35—Ketones, e.g. benzophenone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37—Esters of carboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/4946—Imidazoles or their condensed derivatives, e.g. benzimidazoles
    • 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
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/4966—Triazines or their condensed derivatives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/86—Polyethers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/59—Mixtures

Definitions

  • the present invention relates to combinations of sunscreens and to the compositions containing them.
  • sun radiations ranging from 280 to 400 nm are noxious for human skin; in particular those with a wavelength from 280 to 320 nm, the so-called UV-B radiation, cause erythema and cutaneous sunburns, whose severity depends on the kind of the skin and on the duration of the exposition to sunlight.
  • UV-A radiations which were considered innocuous and only responsible of skin tanning, are, as a matter of fact, harmful, in that they can cause damages to elastine and collagene, with consequent ageing of the skin as well as a number of phototoxic and photoallergic reactions.
  • anti UV-A and anti UV-B sunscreens have been proposed in the attempt to prevent the photodegradation of the first ones, for example combinations of benzylidenecamphor derivatives or cyanocrylates (anti UV-B sunscreens) and dibenzoylmethane derivatives (anti UV-A sunscreens) are reported in GB 2,198,944, WO 91/11989 and WO 94/04131, and synergistic compositions of anti UV-B sunscreens are described in EP 0,689,828 and EP 0,685,224.
  • sunscreens and the amounts at which they are used, alone or in mixtures, are selected depending on the intended protection, as well as on the above mentioned remarks.
  • an index of this protection is the so-called sun protection factor, (SPF), which is expressed as the ratio of the time of irradiation necessary to reach the erythematogenic threshold in the presence of the UV filter to the time necessary to reach the erythematogenic threshold in the absence of the UV filter.
  • SPDF sun protection factor
  • an object of the present invention are combinations of sunscreens for the protection from ultraviolet radiations, which comprise: a) at least one compound of formula I:
  • R is a straight or branched (C ⁇ _ 8 ) alkyl group, ( c _ 2 ⁇ cycloalkyl, optionally substituted with one or more straight or branched (C 1 _ 4 ) alkyl groups;
  • X is an oxygen atom or the group -NH-;
  • R ⁇ has the same meanings as R, or is hydrogen, a monovalent metal ion, a quaternary ammonium group, or a group of formula II
  • A is a straight or branched (C ⁇ _ 8 ) alkyl, (C ⁇ _ 12 ) cycloalkyl, or (Cg_ 10 ) aryl optionally substituted with one or more straight or branched ( c ⁇ _4) alkyl groups;
  • R3 is hydrogen or methyl;
  • n is an integer from 1 to 10;
  • R 2 has the same meaning as R when X is -NH-, or has the same meanings as R ⁇ when X is oxygen; in combination with at least one or more sunscreens selected from the following classes of compounds: b) benzylidenecamphor derivatives of formula Til:
  • R ⁇ is hydrogen, or the group SO3M, in which M is hydrogen, or a monovalent metal ion, or a quaternary ammonium group, and R ⁇ is hydrogen, methyl, a group SO M wherein M is defined as above, or a group of formula IV or V
  • g and - are selected independently from hydrogen, straight or branched (C * Q ) alkyl and straight or branched (C ⁇ _g) alkoxy; d) alkoxycinnamic acid esters of formula VII
  • ⁇ - is a straight or branched (C ⁇ _ ⁇ .) alkyl group
  • R q is selected from hydrogen, a straight or branched
  • R , R * and E are def ined as above f or f or mula
  • R- is hydrogen or the group SO3Q, in which Q is hydrogen, a monovalent metal ion or a quaternary ammonium group, and R ⁇ 2 is hydrogen, hydroxy or straight or branched (C ⁇ _ ⁇ ) alkoxy; y) diphenylcyanoacrylates of formula X
  • alkyl group a benzyl group optionally substituted with a straight or branched ( c ⁇ _ ⁇ ) alkyl group, a 3,3,5- trimethylcyclohexyl residue, both as a racemate and as any optically active forms, or the group HN ⁇ CR ⁇ CR ⁇ OH ⁇ ; i) benzimidazolesulfonic acid derivatives of formula XII
  • G is hydrogen, or a monovalent mo Lai ion, or a quaternary ammonium group; j) p-aminobenzoic acid (PABA) derivatives of formula
  • R-,r and ⁇ g are independently hydrogen or a straight or branched ( C ⁇ Q ) alkyl group, optionally substituted with a hydroxyl group, and R ⁇ is selected from hydrogen, a straight or branched ( c ⁇ _ ⁇ o) alkyl group, a monovalent metal ion and a quaternary ammonium group, or R ⁇ g is the group -(CH -CH2 ⁇ ) ⁇ H, R ⁇ g is the group -(CH 2 -CH 2 0) H and R 17 is the group -CH 2 -CH 2 -(OCH 2 -
  • the combinations of the present invention are, at least, binary combinations of a component as defined in a) with one of the components as defined in the classes b) to k).
  • two or more thereof can also be selected within the same class, provided at least one of the components present in the combination is as defined in a).
  • the choice of the components of the combinations depends on the desired type and degree of protection, as well as on the chemico-physical and photostability characteristics of the selected components . Examples of alkyl group are methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl and isomers thereof.
  • cycloalkyl group examples include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl.
  • substitutions with alkyl groups are methyl, ethyl, propyl, butyl and isomers thereof at one or more positions of the cycloaliphatic ring.
  • Examples of monovalent metal ions are the sodium, potassium, lithium ions.
  • Examples of aryl group are phenyl and naphthyl, optionally bearing one or more alkyl groups, such as methyl, ethyl, propyl, butyl and isomers thereof.
  • alkoxy group examples include methoxy, ethoxy, propoxy, butoxy and isomers thereof.
  • the preferred components of formula I are those in which R is methyl, 2 ,4,4-trimethyl-pent-2-yl, isopropyl or tert-butyl, R ⁇ is 2-ethyl-hexyl, isopropyl or n- tetradecyl, R 2 is isopropyl or 2-ethyl-hexyl, and X is 0 or -NH-.
  • Particularly preferred is the component in which R is tert-butyl, ⁇ and R 2 are both 2-ethyl-hexyl and X is oxygen, which will be referred to as component a) in the disclosure and examples. These components are described in EP 0,570,838.
  • Sunscreens of the classes b) to k) are anti UV-A sunscreens and/or anti UV-B sunscreens well-known in literature; many of them being commercial products.
  • Preferred components of the class b) are the compounds of formula III in which R ⁇ is hydrogen and Rg is methyl or the group of formula IV, which are known under the trade names EUSOLEXTM 6300 and MEXORY TM SO, respectively, and those in which R * is the group SO3M, wherein M is hydrogen or a monovalent metal ion and R is the group of formula V in which R ⁇ is defined as above , known under the trade name MEXORYLTM SX .
  • Preferred components of the class d) are those compounds of formula VII, in which Rg is methyl and R g is 2-ethyl-hexyl or the group + NH 2 (CH 2 CH 2 OII)2 , known under the trade names PARSOLTM MCX and BERNELTM HYDRO, respectively.
  • the preferred component of the class e) is the compound of formula VIII in which all of R, R ⁇ and 2 are 2-ethyl-hexyl, known under the trade name UVINULTM T
  • Preferred components of the class f) are those compounds of formula IX in which R ⁇ Q is hydrogen or methyl, R ⁇ is hydrogen or the group SO3Q, in which Q is hydrogen or a monovalent metal ion, and R ⁇ is hydrogen, known under the trade names UVASORBTM 2QH
  • the preferred component of the class g) is the compound of formula X in which R ⁇ 3 is 2-ethyl-hexyl, known under the trade name UVINULTM N-539.
  • Preferred components of the class h) are those compounds of formula XI in which R 14 is 2-ethyl-hexyl, the residue ( + )-3 , 3, 5-trimethylcyclohexyl or the group
  • Preferred components of the class i) are those compounds of formula XII in which G is hydrogen or a monovalent metal ion, known under the trade name
  • UVINULTM P25 UVINULTM
  • Preferred components of the class k) are titanium dioxide (Ti0 2 ) and zinc oxide (ZnO). These oxides are preferably used in micronized form, in which the particles have a size not higher than about 100 nm as for Ti0 2 , and ranging from about 15 to about 300 nm as for ZnO. Most preferably, the size of the Ti0 o particles ranges from about 5 to about 50 nm. Titanium dioxide can have an anatase, rutile or amorphous structure. For the purposes of the invention, these micronized metal oxides can be used either as they are or coated with other agents, such as A1 2 0 3 or aluminium salts with C30-I8 aliphatic fatty acids. They are easily commercially available products.
  • micronized i0 2 is marketed under the trade name P25 (Degussa), whereas Ti0 2 coated with aluminium stearate is marketed as MT100T (Tayka Corp.), and that coated with A1 2 0 3 is known as UFTR (Miyoshi).
  • Micronized ZnO is, in its turn, available as Z-COTETM ( sunSMART ) or as SPECTRAVEILTM (Tioxide) .
  • a preferred aspect of the present invention relates to sunscreens synergistic combinations which contain the component a) in combination with at least one or more of the sunscreens belonging to the classes b) to k) and defined above as the preferred ones.
  • the components in addition to component a), can be selected from any of the different classes b) to k), or within the same class.
  • an acidic sunscreen is used as a component : the combination can contain a mixture of the filter in the acidic form and in the ⁇ alified form with a monovalent metal, or with a quaternary ammonium group.
  • Representative examples of these preferred combinations of sunscreens are those combinations which comprise the component a) with:
  • the combinations of sunscreens of the present invention can be used both in the protection of human body from the harmful effects of UV radiations, and in the stabilization of the various compositions containing them, for example, cosmetic or dermatological compositions.
  • This stabilizing effect has also been observed when including the above mentioned combinations in photosensitive compositions different from the cosmetic and dermatological ones, such as polymers.
  • the combination used comprises at least one component a) in amounts ranging from about 0.05 to about 20% of the composition total weight, and at least one of the other components b) to k) in amounts ranging from about 0 to about 30%, calculated on the composition total weight, with the proviso that at least one of the components b) to k) is present in a percent amount different from zero.
  • the amount of the desired combination present in the composition ranges from about 0.1 to about 35% of the composition total weight.
  • the choice of the components of the combinations will depend on the desired type and degree of protection and stabilization, as well as on the chemico-physical and photostability characteristics of the selected components. The above indicated percentages and those reported in the following are percent by weight, and they are calculated on the composition total weight.
  • compositions are the cosmetic compositions, which, therefore, are a further object of the present invention.
  • the cosmetic compositions comprise a combination of sunscreens according to the invention in cos etically acceptable excipients, such as oil-in-water , water-in-oil, oil-water-oil, water-oil-water emulsions, oily solutions, lipid fusions, hydro-alcoholic or anhydrous aqueous gels, alcoholic or hydro-alcoholic solutions, and analogues.
  • sunscreens according to the invention in cos etically acceptable excipients, such as oil-in-water , water-in-oil, oil-water-oil, water-oil-water emulsions, oily solutions, lipid fusions, hydro-alcoholic or anhydrous aqueous gels, alcoholic or hydro-alcoholic solutions, and analogues.
  • this substance is a compound advantageously selected from: i) hydrocarbons, such as paraffin, mineral oils, and analogs; ii) oils, butters and natural waxes, such as avocado oil, sunflower oil, almond oil, apricot-stone oil, karite butter, evening primrose oil, black currant oil, borage oil, jojoba oil, safflower oil, wheat germ oil, macadamia oil, rice bran oil, sesame oil, castor oil, coconut oil; unsaponifiable oils of olive, avocado, soya; cocoa butter, bees-wax, candelilla wax, carnauba wax, and analogs; iii) silicones oils such as dimethicones, cyclomethicones, dimethiconols, alkyldimethicones, and analogs;
  • esters of (C ⁇ -g)alkyl ethers such as diethylene glycol butyl ether acetate, propylene glycol methylether acetate, and analogs.
  • the substances i) to ix which are all easily commercially available, can be used either singularly or as mixtures thereof, such as the wax mixtures commercially known under the name CUTINA( R ) (Henkel).
  • the oily component is used in amounts ranging from about 0.5 to 95% of the composition total weight.
  • a preferred group of oily components are the esters of saturated or unsaturated, straight or branched aliphatic acids, or of aromatic or alkylaromatic acids, having 1 to 25 carbon atoms, said acids being optionally hydroxylated and/or ethoxylated, with mono- or polyhydroxylated aliphatic alcohols, saturated or unsaturated, straight or branched, having 1 to 25 carbon atoms .
  • N,N-diethyl-methylbenzamides and ethyl l-(N-acetyl-N- butyl )-propionate N,N-diethyl-methylbenzamides and ethyl l-(N-acetyl-N- butyl )-propionate.
  • a third preferred group of oily components are the mixtures of esters of saturated or unsaturated, straight or branched aliphatic acids, or of aromatic or alkylaromatic acids, having 1 to 25 carbon atoms, said acids being optionally hydroxylated and/or ethoxylated, with mono- or polyhydroxylated aliphatic alcohols, saturated or unsaturated, straight or branched, having 1 to 25 carbon atoms, such as N,N-diethyl-methylbenzamides and/or ethyl l-(N-acetyl-N-butyl )-propionate .
  • a fourth preferred group of oily components are the silicones oils.
  • the cosmetic compositions which comprise emulsions can also include one or more conventional, commercially available emulsifier.
  • emulsifiers such as soaps of fatty acids with alkali metals (for example, potassium stearate), alkaline-earth metals or aliphatic amines; alkylsulfate salts, such as sodium cetylstearyl sulfate (LANETTETM E, Henkel); alkylphosphates salts, optionally ethoxylated, such as potassium cethylphoshate (AMPHISOLTM K, Givaudan); condensates of fatty acids with protein hydrolysates (LAMECREMETM LPM, Henkel); mono- and diglycerides anionic esters (GRINDTEKTM CA-P, Grindsted Products Ltd), and analogs.
  • alkali metals for example, potassium stearate
  • Amphoteric emulsifiers can be used as well, for example phospholipids such as lecithin, or also non ionic emulsifiers.
  • the latter are, for example, ethoxylated compounds of natural oil derivatives, such as hydrogenated castor oil (7)OE (ARLACELTM 989, ICI); mono- and diglycerides of fatty acids, optionally ethoxylated, such as glyceryl stearate (CUTINATM GMS,
  • ICI and CRILLTM, Croda polyglycerol esters with fatty acids, such as triglyceryl diisostearate (LAMEFORMTM TGI, Henkel) and triglyceryl distearate (CITHROLTM 2623, Croda); glucose, methylglucose and saccharose esters with ethoxylated and non-ethoxylated fatty acids, such as methylglucose dioleate (GLUCATETM DO, Amerchol) and methylglucose ( 20 )OE sesquistearate (GLUCAMATETM SS E-20.
  • LAMEFORMTM TGI triglyceryl diisostearate
  • CITHROLTM 2623 triglyceryl distearate
  • glucose, methylglucose and saccharose esters with ethoxylated and non-ethoxylated fatty acids such as methylglucose dioleate (GLUCATETM DO, Amerchol) and
  • ethers of glucose and of its oligomers optionally esterified with (C 1Q - 3Q )aliphatic acids, such as triglycerylmethylglucose distereate (TegoCare' R ' 450, Goldschmidt) and methyl glucose sesquistearate (TegoCare( R) PS, Goldschmidt), or cetylstearyl glucoside (MONTANOVTM 68, Seppic ) ; ethoxylated fatty acids (MYRJTM, ICI); ethoxylated fatty alcohols (BRIJTM, ICI); lanolin and ethoxylated and non-ethoxylated derivatives, such as lanolin (30)OE (AQUALOSETM L 30.
  • C 1Q - 3Q )aliphatic acids such as triglycerylmethylglucose distereate (TegoCare' R ' 450, Goldschmidt) and methyl glucose sesquistearate (TegoCare
  • alkylglycols/polyethylene glycols copolymers such as the copolymer PEG-45/dodecylglycol (ELFACOSTM ST 9, Akzo); silicone emulsifiers (Silicone Fluid 3225 C, Dow Corning; ABILTM W508 and Th. Goldschmidt AG); fluorinated emulsifiers (FOMBLIN( R ) - Ausimont); polymers of hydroxystearic acid esterified or etherified with polyethyleneglycols (PEG), polypropylene glycols (PPG) or copoly ers PEG/PPG; and analogs.
  • PEG polyethyleneglycols
  • PPG polypropylene glycols
  • copoly ers PEG/PPG copoly ers
  • cross-linked copolymers can also advantageously be used, selected from a) cross- linked copolymers formed by i) acrylic or methacrylic acid, ii) vinyl esters of highly branched trialkylacetic acids of formula XIV
  • ⁇ g, ⁇ g and 2Q are straight alkyl residues, at least one them being methyl, the total sum of the carbon atoms of the acyl residue being preferably 10, and iii) a cross-linking agent such as pentaerythritol triallylether (STABYLEN 30, 3V SIGMA - Bergamo, Italy), and b) cross-linked copolymers formed by i) acrylic or methacrylic acid, ii) acrylates or inethacrylate ⁇ of alkanol ⁇ , iii) a cross-linking agent like, for instance, the allyl ethers of saccharose or pentaerythritol, as an example, the products known under the trade name PEMULEN( R ) (B.F. Goodrich).
  • PEMULEN( R ) B.F. Goodrich
  • the amount of emulsifiers which can be used vary from about 0.1 to about 20% of the composition total weight. They can be used singularly or as mixtures thereof. Some of these emulsifiers can advantageously be employed as solvents for the combinations according to the invention.
  • the cosmetics compositions of the invention can also comprise one or more vitamins, or their precursors, or their analogs.
  • the vitamins, or their precursors, or their analogs, which can advantageously be employed are selected from the group consisting of: i) vitamins of A group, including vitamin A 2 and retinal, and their possible esters with straight or branched, saturated or unsaturated (C 2 _2 0 )aliphatic onocarboxylic acids or ( c 3_i2 ) a lipha ic di- or tri- carboxyilic acids, said acids being optionally hydroxylated or alkoxylated with PEG, PPG, or copolymers PEG/PPG; or esters with nicotinic acids; ii) ⁇ - and ⁇ -carotene; iii) vitamins of the B group; iv) vitamin C, and its possible esters with straight or branched, saturated or unsaturated (C _ 2 o) a liP nat c monocarboxylic acids or (C _ ⁇ 2 )aliphatic di- or tri- carboxylic acids, said
  • compositions comprising one or more of the above vitamins represent a further object of the present invention.
  • the cosmetic compositions of the invention can also comprise other conventional components, for example emulsion stabilizers such as sodium chloride or citrate, magnesium sulfate and analogs, in amounts ranging from about 0.1 to about 5% of the composition weight; wetting agents, such as glycerin, propylene glycol or 1,3- butylene glycol, in amounts from about 0.1 to about 30% of the composition weight; thickening agents, such as modified celluloses or acrylic acids polymers or copolymers, in amounts not above 4% of the composition weight; sequestering agents, such as EDTA salts, in amounts not higher than 1% of the composition weight; antioxidizers, such as tocopherols and the esters thereof, hydroxytoluene butoxide or butyl hydroxyanisol, in amounts not above 2% of the composition weight; emollients, such as mineral oils, polysiloxanes, almond oil, vaseline, isopropyl yristate or fatty acids triglycerids,
  • compositions of the invention can also contain artificial tanning agents such as dihydroxyacetone (DHA) and its derivatives, optionally in the presence of a iron salt, as described in EP-A- 0,688,203, in order to provide a less yellowish tan than that given by DHA alone.
  • DHA dihydroxyacetone
  • iron salt as described in EP-A- 0,688,203
  • compositions of the invention can be prepared according to the procedures known to those skilled in the art.
  • the two phases should preferably be prepared separately, dissolving or dispersing in any of them the desired components/lipophilic or hydrophilic ingredients, and subsequently mixed.
  • compositions are sun-creams, day creams, moisturizing creams, sun-oils, ointments, lipsticks, solutions, lotions, gels, transparent gels, aerosol, foams and analogs. They contain a selected combination of the present invention together with the other ingredients in the above mentioned weight ratios, as well as any other compatible ingredient conventionally used in cosmetics. Generally speaking, said compositions will comprise a selected combination of the present invention so as to provide an SPF not lower than 2. The combinations of sunscreens of the present invention have often shown a synergistic effect.
  • the component a) is the compound of formula I in which R is tert-butyl , R ⁇ and R 2 are both 2-ethyl-n.hexyl and X is oxygen.
  • the amounts of the single components are expressed as weight percentages on the composition total weight.
  • a face day-cream is prepared from
  • a fluid oil-in-water emulsion is prepared from
  • STABYLEN 30 polymeric emulsifier 0.25 - 3V SIGMA, Bergamo, Italy
  • phase A The mixture of components 1 to 4 is heated to 60"C then components 5 and 6 are added (phase A).
  • component 8 is dispersed in about 90% of water, at 60 ⁇ C, under stirring (phase B).
  • phase A is added to phase B in a homogenizer.
  • Component 9 is dissolved in the residual water at room temperature
  • phase C pH is adjusted to 7 with sodium hydroxide and phase C is added to phase A+B.
  • the mixture is cooled to room temperature, then propylene glycol, preservatives and perfume are added.
  • An anhydrous ointment is prepared from
  • a high-protection water-in-oil cream is prepared front 1.
  • phase A The mixture of components 1 to 5 is melted at 60"C and, components 6, 7 and 8 are added, under stirring (phase A) .
  • Components 9 and 10 are subsequently dispersed in this phase in a homogenizer. Separately, about 90% of water is heated to 60°C and added to phase A in a homogenizer. Then, cooling is started.
  • Component 12 is dissolved in the re ⁇ idual water at room temperature, and the resulting solution is neutralized with 13 (phase C).
  • Phase C Phase C is added to the above prepared emulsion, which is then cooled to room temperature and added with preservatives, glycerin and perfume.
  • a fluid oil-in-water emulsion is prepared from 1. Stearic acid (100)OE 2.0 2. Cetylstearyl alcohol 1.0
  • phase A The mixture of components 1 to 6 is melted at 70°C and components 8, 9 and 10 are added, under strong stirring (phase A). Separately water is heated to 70°C and first component 12, then component 13 are dispersed, under stirring (phase B). Phase A is added to phase B in a homogenizer, and the resulting mixture is then neutralized (pH 7) with component 14. The mixture is cooled to room temperature and added with preservatives, glycerin, collagene and perfume.
  • An oil-in-water cream is prepared from
  • phase A component 14 is dispersed in water at 70"C, under stirring (phase B).
  • Phase A is then added to phase B in a homogenizer, and the resulting mixture is then neutralized (pH 7) with component 15.
  • the mixture is cooled to room temperature and added with preservatives, butylene glycol and perfume.
  • a water-in-oil cream is prepared from
  • Methylglucose dioleate 5.0 2. Copolymer PEG-45/dodecyl glycol 3.0
  • a silicon water-in-oil emulsion is prepared from 1. Cetyl Dimethicone Copolyol 3.0
  • phase A A mixture of components 1 to 6 is prepared, components 7 , 8 and 9 are dissolved therein and subsequently, in the resulting mixture, component 10 is dispersed, at room temperature (phase A).
  • Components 12 to 15 are dissolved in water, at room temperature (phase B), then phase B is slowly added to phase A, under stirring. Finally, the emulsion is made homogeneous in a homogenizer .
  • a sun-oil is prepared from
  • An oil-in-water cream is prepared with
  • phase A Separately, component 10 is dispersed into the water, previously heated to 70 ⁇ C, and the resulting dispersion is added with components 11 and 12 (phase B).
  • phase A is added to phase B in a homogenizer, the obtained mixture is cooled at room temperature, subsequently neutralized with component 13, and finally added with components 14 to 16.
  • An oil-in-water milk is prepared with
  • phase A The mixture of components 1 to 7 is heated to 70 °C and, under stirring, is added with components 8 and 9 (phase A). Separately, compound 11 is dispersed into the water, previously heated to 70°C, and the resulting dispersion is added with component 12 (phase B). Then phase A is added to phase B in a homogenizer, the obtained mixture is cooled to room temperature, subsequently neutralized with component 13, and finally added with components 14 to 17.
  • An oil-in-water cream is prepared with 1. PEG-100 Stearate 2.00
  • Titanium dioxide MT100T (Taika Corp.) - component k) 4.00
  • component 10 is dispersed at room temperature in components 11 and 12, and the resulting dispersion is added to the hot mixture of components 1 to 8 (phase A).
  • Component 15 is dispersed into the water, previously heated to 70°C, and the resulting dispersion is added with component 14 (phase B).
  • Phase A is added to phase B in a homogenizer, the resulting mixture is cooled to room temperature and subsequently added with components 16 to 20.
  • An oil-in-water cream is prepared with

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Abstract

L'invention porte sur des combinaisons d'écrans solaires qui comprennent au moins un composé de la formule (I) en combinaison avec au moins un autre écran solaire sélectionné parmi des dérivés de benzylidènecamphor, de dibenzoylméthane, d'acide alcoxycinnamique, de triazinoaniline, de benzophénone, des diphénylcyanoacrylates, des dérives d'acide salicylique, d'acide benzymidazol-5-sulfonique, d'acide p-aminobenzoïque, des oxydes métalliques ayant un nombre atomique compris entre 11 et 40. L'invention porte également sur des compositions contenant ces composés, notamment des compositions cosmétiques pouvant avoir un facteur de protection solaire issu des rayons ultraviolets égal ou supérieur à 2.
PCT/EP1998/004518 1997-07-30 1998-07-21 Combinaisons d'ecrans solaires et compositions les contenant WO1999006014A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU89778/98A AU736477B2 (en) 1997-07-30 1998-07-21 Combinations of sunscreens and compositions containing them

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT001823 IT1293508B1 (it) 1997-07-30 1997-07-30 Associazione di filtri solari e composizioni che le contengono
ITMI97A001823 1997-07-30

Publications (2)

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WO1999006014A2 true WO1999006014A2 (fr) 1999-02-11
WO1999006014A3 WO1999006014A3 (fr) 1999-04-22

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PCT/EP1998/004518 WO1999006014A2 (fr) 1997-07-30 1998-07-21 Combinaisons d'ecrans solaires et compositions les contenant

Country Status (3)

Country Link
AU (1) AU736477B2 (fr)
IT (1) IT1293508B1 (fr)
WO (1) WO1999006014A2 (fr)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0950396A1 (fr) * 1998-04-18 1999-10-20 Beiersdorf Aktiengesellschaft Compositions cosmetiques ou dermatologiques stables sous forme d'émulsions E/H contenant des dérivés de triazine substitués asymètriquement
WO1999053895A1 (fr) * 1998-04-18 1999-10-28 Beiersdorf Ag Utilisation de derives de triazine substitues de façon asymetrique dan des preparations cosmetiques ou dermatologiques en vue de conserver l'acide urocanique sur la peau
WO1999053894A1 (fr) * 1998-04-18 1999-10-28 Beiersdorf Ag Preparations cosmetiques et dermatologiques ayant une teneur en derives de triazine substitues de façon asymetrique et une action de protection contre la lumiere, ces preparations etant resistantes a l'eau et se presentant sous forme d'emulsions huile/eau
EP0996412A1 (fr) * 1997-05-20 2000-05-03 Soltec Research Pty. Ltd. Produit antisolaire
EP1074241A2 (fr) * 1999-08-05 2001-02-07 Beiersdorf Aktiengesellschaft Compositions cosmétique ou dermatologique sans huile contenant des dérivés asymétriques de triazines substituées et des substances fluides filtrant l'UV
WO2001072935A3 (fr) * 2000-03-28 2002-02-14 Basf Ag Melange absorbant les uv, a affinite pour les fibres textiles
DE10113053A1 (de) * 2001-03-15 2002-09-19 Beiersdorf Ag Selbstschäumende oder schaumförmige Zubereitungen mit anorganischen Gelbildnern und organischen Hydrololloiden
DE10113050A1 (de) * 2001-03-15 2002-09-19 Beiersdorf Ag Selbstschäumende oder schaumförmige Zubereitungen organischen Hydrokolloiden
DE10113051A1 (de) * 2001-03-15 2002-09-19 Beiersdorf Ag Selbstschäumende oder schaumförmige Zubereitungen mit anorganischen Gelbildnern und partikulären hydrophoben und/oder hydrophobisierten und/oder ölabsorbierenden Festkörpersubstanzen
DE10113048A1 (de) * 2001-03-15 2002-09-19 Beiersdorf Ag Selbstschäumende oder schaumförmige Zubereitungen mit partikulären hydrophoben und/oder hydrophobisierten und/oder ölabsorbierenden Festkörpersubstanzen
DE10113047A1 (de) * 2001-03-15 2002-09-26 Beiersdorf Ag Selbstschäumende oder schaumförmige Zubereitungen mit anorganischen Gelbildnern
DE10113054A1 (de) * 2001-03-15 2002-09-26 Beiersdorf Ag Selbstschäumende oder schaumförmige Zubereitungen mit anorganischen Gelbildnern, organischen Hydrokolloiden und partikulären hydrophoben und/oder hydrophobisierten und/oder ölabsorbierenden Festkörpersubstanzen
DE10113046A1 (de) * 2001-03-15 2002-09-26 Beiersdorf Ag Selbstschäumende schaumförmige Zubereitungen mit organischen Hydrokolliden und partikulären hydrophobisierten und/oder ölabsorbierenden Festkörpersubstanzen
EP1300137A2 (fr) * 2001-10-02 2003-04-09 3V SIGMA S.p.A Combinations d'agents anti-solaires
WO2006131159A1 (fr) * 2005-06-06 2006-12-14 Unilever Plc Lingette cosmetiques
EP1046387B2 (fr) † 1999-04-20 2010-06-02 L'oreal Composition foisonnée, son procédé de fabrication et son utilisation notamment comme composition cosmétique
EP2345456A1 (fr) 2009-12-11 2011-07-20 L'Oréal Composition filtrante fluide anhydre comprenant une phase huileuse, un filtre triazine particulier et un agent rheologique epaississant ou gelifiant d'huile
US11357714B2 (en) 2020-07-21 2022-06-14 Chembeau LLC Diester cosmetic formulations and uses thereof

Family Cites Families (13)

* Cited by examiner, † Cited by third party
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ES2170846T3 (es) * 1996-04-09 2002-08-16 3V Sigma Spa Composiciones cosmeticas con filtros solares.
FR2750335B1 (fr) * 1996-07-01 1998-07-31 Oreal Compositions comprenant du 4-tert-butyl-4'- methoxydibenzoylmethane, un derive de 1, 3, 5-triazine et un (alpha-cyano)-beta, beta'-diphenylacrylate d'alkyle et utilisations
ES2185756T3 (es) * 1996-07-31 2003-05-01 3V Sigma Spa Composiciones protectoras solares que comprenden derivados de triacina.
EP0821937A1 (fr) * 1996-07-31 1998-02-04 3V SIGMA S.p.A Compositions photoprotectrices comprenant des dérivés de triazine
EP0821939A1 (fr) * 1996-07-31 1998-02-04 3V SIGMA S.p.A Compositions photoprotectrices comprenant des dérivés de triazine
DE69628292T2 (de) * 1996-07-31 2004-04-01 3V Sigma S.P.A. Triazinderivate enthaltendes Sonnenschutzmittel
EP0821941A1 (fr) * 1996-07-31 1998-02-04 3V SIGMA S.p.A Compositions photoprotectrices comprenant des dérivés de triazine
DE19643515A1 (de) * 1996-10-22 1998-04-23 Basf Ag Kosmetische Mittel enthaltend eine Kombination von UV-Absorbern
IT1286503B1 (it) * 1996-11-26 1998-07-15 3V Sigma Spa Composizioni cosmetiche antisolari comprendenti derivati del dibenzoilmetano dell'acido difenilcianoacrilico e della trianzina
IT1286504B1 (it) * 1996-11-26 1998-07-15 3V Sigma Spa Composizioni cosmetiche antisolari comprendenti derivati del dibenzoilmetano del benzofenone e della triazina
FR2757057A1 (fr) * 1996-12-17 1998-06-19 Oreal Compositions comprenant un derive de dibenzoylmethane, un derive de 1,3,5-triazine et un derive silicie a fonction benzalmalonate et utilisations
FR2757055B1 (fr) * 1996-12-17 1999-02-05 Oreal Compositions comprenant un derive de dibenzoylmethane, un derive de 1,2,3-triazine et un benzalmalonate de dialkyle et utilisations
IT1289511B1 (it) * 1996-12-23 1998-10-15 3V Sigma Spa Soluzioni concentrate di filtro solare derivato della 1,3,5- triazina e loro uso per la preparazione di composizioni cosmetiche

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0996412A1 (fr) * 1997-05-20 2000-05-03 Soltec Research Pty. Ltd. Produit antisolaire
EP0996412A4 (fr) * 1997-05-20 2000-09-06 Soltec Res Pty Ltd Produit antisolaire
US6267949B1 (en) 1997-05-20 2001-07-31 Soltec Research Pty Ltd. Sunscreen composition
EP0950396A1 (fr) * 1998-04-18 1999-10-20 Beiersdorf Aktiengesellschaft Compositions cosmetiques ou dermatologiques stables sous forme d'émulsions E/H contenant des dérivés de triazine substitués asymètriquement
WO1999053895A1 (fr) * 1998-04-18 1999-10-28 Beiersdorf Ag Utilisation de derives de triazine substitues de façon asymetrique dan des preparations cosmetiques ou dermatologiques en vue de conserver l'acide urocanique sur la peau
WO1999053894A1 (fr) * 1998-04-18 1999-10-28 Beiersdorf Ag Preparations cosmetiques et dermatologiques ayant une teneur en derives de triazine substitues de façon asymetrique et une action de protection contre la lumiere, ces preparations etant resistantes a l'eau et se presentant sous forme d'emulsions huile/eau
EP1559413A2 (fr) * 1998-04-18 2005-08-03 Beiersdorf AG Compositions cosmetiques ou dermatologiques stables sous forme d'émulsions E/H contenant des dérivés de triazine substitués asymètriquement
EP1559413A3 (fr) * 1998-04-18 2007-05-09 Beiersdorf AG Compositions cosmetiques ou dermatologiques stables sous forme d'émulsions E/H contenant des dérivés de triazine substitués asymètriquement
EP1046387B2 (fr) † 1999-04-20 2010-06-02 L'oreal Composition foisonnée, son procédé de fabrication et son utilisation notamment comme composition cosmétique
DE19936913A1 (de) * 1999-08-05 2001-02-22 Beiersdorf Ag Ölfreie kosmetische oder dermatologischen Zubereitungen mit einem Gehalt an unsymmetrisch substituierten Triazinderivaten und flüssigen UV-Filtersubstanzen
EP1074241A2 (fr) * 1999-08-05 2001-02-07 Beiersdorf Aktiengesellschaft Compositions cosmétique ou dermatologique sans huile contenant des dérivés asymétriques de triazines substituées et des substances fluides filtrant l'UV
EP1074241A3 (fr) * 1999-08-05 2003-05-14 Beiersdorf Aktiengesellschaft Compositions cosmétique ou dermatologique sans huile contenant des dérivés asymétriques de triazines substituées et des substances fluides filtrant l'UV
WO2001072935A3 (fr) * 2000-03-28 2002-02-14 Basf Ag Melange absorbant les uv, a affinite pour les fibres textiles
US7011772B2 (en) 2000-03-28 2006-03-14 Basf Aktiengesellschaft UV absorbing mixture with textile fiber affinity
DE10113054A1 (de) * 2001-03-15 2002-09-26 Beiersdorf Ag Selbstschäumende oder schaumförmige Zubereitungen mit anorganischen Gelbildnern, organischen Hydrokolloiden und partikulären hydrophoben und/oder hydrophobisierten und/oder ölabsorbierenden Festkörpersubstanzen
DE10113053A1 (de) * 2001-03-15 2002-09-19 Beiersdorf Ag Selbstschäumende oder schaumförmige Zubereitungen mit anorganischen Gelbildnern und organischen Hydrololloiden
DE10113047A1 (de) * 2001-03-15 2002-09-26 Beiersdorf Ag Selbstschäumende oder schaumförmige Zubereitungen mit anorganischen Gelbildnern
DE10113048A1 (de) * 2001-03-15 2002-09-19 Beiersdorf Ag Selbstschäumende oder schaumförmige Zubereitungen mit partikulären hydrophoben und/oder hydrophobisierten und/oder ölabsorbierenden Festkörpersubstanzen
DE10113051A1 (de) * 2001-03-15 2002-09-19 Beiersdorf Ag Selbstschäumende oder schaumförmige Zubereitungen mit anorganischen Gelbildnern und partikulären hydrophoben und/oder hydrophobisierten und/oder ölabsorbierenden Festkörpersubstanzen
DE10113046A1 (de) * 2001-03-15 2002-09-26 Beiersdorf Ag Selbstschäumende schaumförmige Zubereitungen mit organischen Hydrokolliden und partikulären hydrophobisierten und/oder ölabsorbierenden Festkörpersubstanzen
DE10113050A1 (de) * 2001-03-15 2002-09-19 Beiersdorf Ag Selbstschäumende oder schaumförmige Zubereitungen organischen Hydrokolloiden
EP1300137A2 (fr) * 2001-10-02 2003-04-09 3V SIGMA S.p.A Combinations d'agents anti-solaires
EP1300137A3 (fr) * 2001-10-02 2003-09-03 3V SIGMA S.p.A Combinations d'agents anti-solaires
WO2006131159A1 (fr) * 2005-06-06 2006-12-14 Unilever Plc Lingette cosmetiques
EP2345456A1 (fr) 2009-12-11 2011-07-20 L'Oréal Composition filtrante fluide anhydre comprenant une phase huileuse, un filtre triazine particulier et un agent rheologique epaississant ou gelifiant d'huile
US11357714B2 (en) 2020-07-21 2022-06-14 Chembeau LLC Diester cosmetic formulations and uses thereof
US11491092B2 (en) 2020-07-21 2022-11-08 Chembeau LLC Hair treatment formulations and uses thereof
US11801211B2 (en) 2020-07-21 2023-10-31 Chembeau LLC Hair treatment formulations and uses thereof
US12214065B2 (en) 2020-07-21 2025-02-04 Chembeau LLC Diester cosmetic formulations and uses thereof
US12285508B2 (en) 2020-07-21 2025-04-29 Chembeau LLC Hair treatment formulations and uses thereof

Also Published As

Publication number Publication date
AU8977898A (en) 1999-02-22
IT1293508B1 (it) 1999-03-01
WO1999006014A3 (fr) 1999-04-22
AU736477B2 (en) 2001-07-26
ITMI971823A1 (it) 1999-01-30

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