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WO2007017179A1 - Utilisation d'ecrans solaires ioniques contre les uv-a - Google Patents

Utilisation d'ecrans solaires ioniques contre les uv-a Download PDF

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Publication number
WO2007017179A1
WO2007017179A1 PCT/EP2006/007691 EP2006007691W WO2007017179A1 WO 2007017179 A1 WO2007017179 A1 WO 2007017179A1 EP 2006007691 W EP2006007691 W EP 2006007691W WO 2007017179 A1 WO2007017179 A1 WO 2007017179A1
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Prior art keywords
groups
group
sunscreen
formula
use according
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PCT/EP2006/007691
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English (en)
Inventor
Katja Berg-Schultz
Christine Mendrok-Edinger
Alexander Poschalko
Horst Westenfelder
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Dsm Ip Assets B.V.
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Publication of WO2007017179A1 publication Critical patent/WO2007017179A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/57—Nitriles
    • 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
    • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4926—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having six membered rings
    • 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 present invention relates to certain uses of 1 ,4-dihydropyridine derivatives, in particular in cosmetic or dermatological sunscreen compositions containing these derivatives, but also in other compositions. Some of these 1 ,4-dihydropyridine derivatives and some of the compositions are novel, and the present invention also relates to those novel compounds and compositions.
  • UV-A absorber should have excellent UV filter activity, good photostability, toxicological and dermatological acceptability, excellent heat stability, very good solubility in cosmetic solvents, in particular in oil or water, compatibility with cosmetic bases, pH stability in the range of 4 to 9, processability into cosmetic formulations, compatibility with other ingredients of cosmetic formulations and with other UV-sunscreens e.g. such as dibenzoylmethane derivatives and with the packaging materials, no staining of textiles, it should be free of color and of neutral or pleasant odor, and it should be free of tackiness and have a low volatility.
  • high requirements must be met, and the UV-absorber must adhere to the hair to provide sufficient protection.
  • an effective UV-A absorber should have its absorption maxima in the UV-A I range (far UV-A, 340-400nm) rather than in the UV-A Il range (320-340) in order to provide effective protection against UV-A induced skin and/ or hair damages.
  • Oil-soluble sunscreens which absorb in the UV-A range are disclosed e.g. in WO 03/068183.
  • a hydrosoluble UV-A sunscreen has the advantage that it can be incorporated into the water phase of usual oil- in-water or water-in-oil emulsions Since usually in those emulsions there is more water phase than oil phase, more sunscreen can be incorporated into the water phase than into the oil phase, which leads to compositions having a higher sunprotection factor and/or better UVA protection Furthermore, water-soluble UV-A sunscreens could be combined with known oil-soluble UV-A sunscreens in the oil phase of a two-phase emulsion, which again leads to an increased protection against UV-A induced skin and hair damages by increased sunprotection factor
  • Water-soluble UV-A sunscreens are disclosed e g in EP-A 669 323 which discloses both water-soluble and oil-soluble sunscreens
  • the water-soluble UV-A sunscreens disclosed in this document e g the compound disodium phenyldibenzimidazole tetrasulfonate have an absorption maximum at 335 nm, being rather a UV-A Il filter and having an extinction value E of only 745, which is relatively low
  • An absorption maximum between 350 to 370 nm would be preferable
  • it would be preferable to have UV-A sunscreens which are water-soluble and/or which advantageously adhere to hair which have a higher extinction E, which would improve the efficiency of the sunscreen E values of more than 900, preferably more than 1000, e g 1000 to 1200, would be very advantageous
  • UV-A sunscreens are also disclosed in DE 33 24 735, and some of the sunscreens disclosed in this document are also water-soluble
  • An example of such a water-soluble UV- A sunscreen is terephthalylidene dicamphorsulfonic acid, however, this compound has an extinction coefficient E of only 866 , and the absorption maximum is at 345 nm, also being rather a UV-A Il filter than a UV-A I filter
  • UV-A sunscreens in particular for cosmetic and dermatological use, which are water-soluble and/or adhere to hair which do not only meet the usual requirements for sunscreens but which also have an absorption maximum at rather high wavelength, preferably between about 350 to 370 nm, and thus being excellent UV-A I filters Additionally these sunscreens have excellent E values, preferably 900 or more, more preferably 1000 or more
  • UV-sunscreens A problem with many UV-sunscreens is that they tend to penetrate into the skin leading to an enhanced systemic exposure
  • polymeric sunscreen agents were developed as well as encapsulated sunscreen agents
  • Particulated inorganic sunscreen agents also avoid this problem
  • cosmetic and dermatological compositions often contain more than one sunscreen agent in order to improve the sun protective factor (SPF) or for various other reasons Therefore, there is still a need for UV-sunscreen agents, in particular monomeric, non-encapsulated organic sunscreen agents, which can preferably be used together with polymeric sunscreen agents and/or encapsulated sunscreen agents and/or particulated inorganic sunscreen agents m order to reduce the total penetration of sunscreen agents from a sunscreen composition into the skin of a person and thus also reduce systemic exposure caused by skin penetration of sunscreen agents
  • dibenzoyl methane derivatives are well known to have a limited photostability whereas the amino substituted hydroxybenzophenones are claimed to be completely photostable when formulated into cosmetic or dermatological compositions
  • dibenzoylmethane derivatives are well known to be stabilized to a certain extend by the addition of other UV-filters, especially UV-B filters, an efficient stabilization can only be achieved by the addition of a suitable triplet quencher having a triplet energy in the order of 55-60 kcal/mol such as 4-methylbenzyl ⁇ dene camphor, octocrylene or polysl ⁇ cone-15
  • UV-A sunscreens disclosed in PCT/EP2005/001379 when incorporated in cosmetic or dermatological compositions have some particular advantageous uses which were not known in the prior art
  • the present inventors found some UV-A sunscreens which are not explicitly disclosed in PCT/EP2005/001379 and compositions containing these UV-A sunscreen agents
  • UV-A sunscreens to which the present invention relates and which are disclosed in PCT/EP2005/001379 are compounds of the general formula (I)
  • R 1 and R 2 are identical or different electron-withdrawing groups or one of R 1 and
  • R 2 is hydrogen and the other of R 1 and R 2 is an electron-withdrawing group
  • R 3 , R 4 , R 5 and R 6 are independently selected from hydrogen atoms, C 1 -C 10 alkyl groups, C 2 -C 10 alkenyl groups, C 2 -C 10 alkynyl groups, C 3 -C 10 cycloalkyl groups, C 6 -C 10 aryl groups, the above groups being unsubstituted or optionally substituted by one to three substituents selected from C 1 -C 6 alkyl groups, halogen, hydroxy and C 1 -C 6 alkoxy groups, or R 3 and R 5 and/or R 4 and R 6 taken together with the carbon atoms to which they are attached form a 5- or 6-membered ring which is optionally substituted with one to four substituents selected from C 1 -C 6 alkyl groups, C 3 -C 6 cycloalkyl groups, C 1 -C 6 alkoxy groups, hydroxy or halogen,
  • X is a hydrocarbon group containing 1 to 20 carbon atoms and optionally 1 to 10 hetero atoms and comprising at least one group which is positively or negatively charged and
  • the term "electron-withdrawing group” refers to groups containing a multiple bond, such as a cyano or nitrilo group (-CN group), which is preferred, or a -COOR 8 , -COR 8 or -CONR 8 2 group, wherein each R 8 is independently hydrogen, C 1 -C 21 alkyl (preferably C 1 -C 6 alkyl), C 2 -C 21 alkenyl (preferably C 2 -C 6 alkenyl), C 2 -C 21 alkynyl (preferably C 2 -C 6 alkynyl), C 3 -C 21 cycloalkyl (preferably C 3 -C 8 cycloalkyl) or C 6 -C 10 aryl (preferably phenyl), each of those groups or preferred groups being unsubstituted or optionally substituted by one to three substituents selected from C 1 -C 6 alkyl groups, halogen, hydroxy and C 1 -C 6 alkoxy groups
  • R 3 , R 4 , R 5 and R 6 are independently selected from hydrogen atoms Ci-C 10 alkyl groups, C 2 -C 10 alkenyl groups, C 2 -C 10 alkinyl groups, C 3 -C 10 cycloalkyl groups and C 6 -C 10 aryl groups Each of these groups can be unsubstituted or substituted by one to three substituents selected from C 1 -C 6 alkyl groups, halogen, hydroxy and C 1 -C 6 alkoxy groups Alternatively, it is also possible that R 3 and R 5 and/or R 4 and R 6 taken together with the carbon atoms to which they are attached form a 5- or 6-membered ring which is optionally substituted with one to four substituents selected from C 1 -C 6 alkyl groups, C 3 -C 6 cycloalkyl groups, C 1 -C 6 alkoxy groups, hydroxy or halogen
  • R 3 , R 4 , R 5 and R 6 are independently selected from hydrogen atom
  • R 3 , R 4 , R 5 and R 6 are hydrogen atoms and the other groups R 3 , R 4 , R 5 and R 6 are C 1 -C 6 alkyl groups or C 2 -C 6 alkenyl groups Most preferably R 3 and R 4 are hydrogen atoms and R 5 and R 6 are C 1 -C 6 alkyl groups or C 2 -C 6 alkenyl groups, more preferably C 1 -C 3 alkyl groups
  • the alkyl groups can be branched or straight chain Preferred examples of C 1 -Ci 0 alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, pentyl, neopentyl, hexyl, 2-ethylhexyl and octyl groups
  • C 3 -C 10 cycloalkyl groups are cyclopropyl, cyclobutyl cyclopentyl cyclohexyl, cycloheptyl and cyclooctyl groups
  • Preferred examples of C 2 -C 6 alkenyl groups are ethenyl and n-propenyl groups.
  • C 6 -C 10 aryl groups are phenyl and naphthyl groups.
  • X is a linear, branched, cyclic or aromatic hydrocarbon group containing 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms and optionally 1 to 10 hetero atoms, preferably 1 to 6 hetero atoms.
  • a hydrocarbon group containing hetero atoms can also contain functional groups such as hydroxyl groups.
  • the hetero atoms are preferably selected from O, N, S and P atoms, it is important for the invention that residue X comprises at least one group, preferably one, two or three groups, which is positively or negatively charged.
  • X is an alkyl, aryl, alkyl aryl or alkylcycloalkyl group containing 1 to 20 carbon atoms and optionally 1 to 10 hetero atoms and comprising at least one group which is positively or negatively charged.
  • alkyl aryl or alkylcycloalkyl refers to an aryl or a cycloalkyl group which contains one or more alkyl substituents. Since the group X comprises at least one group which is positively or negatively charged, it will usually contain at least one hetero atom which bears the positive or the negative charge.
  • residue X contains 1 to 6 hetero atoms, and the hetero atoms are preferably selected from nitrogen, oxygen, sulfur and phosphor atoms.
  • residue X is positively charged, it contains preferably at least one nitrogen atom which is positively charged, and thus the group which bears the positive charge is a quaternary ammonium group. Such compounds comprising a quaternary ammonium ion are particularly preferred for hair applications. If residue X contains a negatively charged group, the group which bears the negative charge is preferably an acid residue such as a residue of phosphoric acid or sulfuric acid or carboxylic acid.
  • residue X contains 1 to 4 unsaturated carbon-carbon bonds, preferably double bonds.
  • Each carbon atom in residue X can optionally be substituted by a functional group, in particular by a hydroxyl or an amino group, preferably by a hydroxyl group.
  • Preferably not more than three, more preferably not more than two carbon atoms of the residue X are substituted as defined above.
  • residue X and residue Y together form a zwitter ion structure.
  • residue X carries preferably a single negative charge and is most preferably an acid residue such as a group -0-SO 3 , -COO , -0-PO 3 H , -0-PO 3 2 , -SO 3 , -PO 3 H or -PO 3 2 Most preferred is group -O-SO 3 ' , -SO 3 and a group -O-PO 3 H
  • residue X which comprise at least one group which is negatively charged are alkylene groups which are optionally substituted by a cycloalkyl group or an aryl group or which is interrupted by a cycloalkyl group or an aryl group and which contains an acid residue as defined above in a preferred embodiment the alkylene group is interrupted by one to three hetero atoms, preferably selected from oxygen and nitrogen atoms
  • the alkylene group contains preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms If the alkylene
  • a preferred example of a residue X having a single negative charge is a residue
  • each R 9 is independently hydroxy or defined as residue R 8 above and preferably is a hydrogen atom, hydroxy or a C 1 -C 3 alkyl group
  • V and U are independently of each other a hetero atom, preferably an oxygen atom or a nitrogen atom (which carries a further group R 8 as defined above), more preferably an oxygen atom
  • n is an integer of O to 6 (preferably 1 to 6)
  • m is O or 1
  • o is an integer of O to 6 (preferably 1 to 6)
  • p is O or 1
  • q is an integer of O to 6 (preferably 1 to 6)
  • W is the residue bearing a negative charge, preferably an acid residue as defined above, most preferably a residue -0-PO 3 H , a residue -SO 3 or a residue -O-SO 3 , with the proviso that the total number of carbon atoms is 20 or less, preferably 10 or less, most preferably 1 to 6 and with the proviso that the total number of hetero atom
  • residue X having a single negative charge is a residue
  • wnerein Ar is an aromatic group, preferably a C 6 -C 10 aromatic group, e g a phenylene or naphthylene group or a heterocyclic group, preferably a ring with 4 to 10 members, of which one or more, preferably 1 or 2, members are hetero atoms, preferably N, O or S atoms
  • the heterocyclic group can be saturated or unsaturated and hetero aromatic groups such as a pyridinylene group are also encompassed W is as defined above
  • residue X is preferably a residue of the formula
  • each R 10 is independently hydrogen or R 11 and each R 11 is independently defined as residue R 8 above, preferably is hydrogen, a C 1 -C 10 , preferably C 1 -C 6 alkyl group which may be interrupted by 1 to 4 hetero atoms, preferably by 1 or 2 hetero atoms, preferably by oxygen atoms and which may be substituted by 1 to 3 substituents selected from hydroxy groups, amino groups and Ci-C 6 alkyl, preferably C 1 -C 3 alkyl groups, and index r is an integer from 1 to 10, preferably from 1 to 6, with the proviso that the total number of carbon atoms in residue X is 20 or less, preferably 1 to 10, and that the total number of hetero atoms including the nitrogen atom and all hetero atoms of functional groups is 1 to 10, preferably 1 to 6, more preferably 1 to 4 Compounds comprising at least one quaternary ammonium ion as defined above are particularly useful for hair applications such as hair care products, shampoo, hair sprays, etc.
  • residue XY is a zwitter ion having a positive charge and a negative charge, the number of carbon atoms, heteroatoms and functional groups being as defined above Tne exact structure of residue X is not relevant, as long as it contains at least one positive or negative charge which makes the molecule water-soluble and/or which provides good adhesiveness to hair
  • X contains one, two or three positive or negative charges
  • Residue Y is a counterion which should balance the charge of residue X
  • the exact chemical nature of the counterion Y is not important for the invention, as long as counterion Y does not negatively interfere with the advantageous properties of the UV-A absorbent and in particular as long as Y is dermatologically and cosmetically acceptable
  • residue Y is preferably a quaternary ammonium ion, an alkali metal or an earth alkali metal ion, more preferably a sodium, potassium, calcium or magnesium ion, but it is also possible that residue Y is a positively charged organic residue, e g an ammonium ion such as a triethanol ammonium ion, an aminomethyl propanol ion or a tromethamine ion
  • residue Y contains a further counterion which balances the additional charge or more than one residue X is balanced by one residue Y
  • residue Y can be
  • M s+ is an ion with s positive charges and A is an ion with a s single negative charge, e g a halogen atom, and s is 1 to 3, preferably 1 or 2, more preferably 1
  • residue Y is negatively charged and preferably residue Y is a halogen atom, such as a chlorine, bromine or iodine atom If residue Y has more negative charges than residue X has positive charges, residue Y contains a further counterion which balances the additional charge or more than one residue X is balanced by
  • residue Y can be — (M s ) or M s (A + ) s 1 , wherein M s is an ion s with s negative charges and A + is an ion with one positive charge, e g an alkali metal ion, and s is 1 to 3, preferably 1 or 2, more preferably 1
  • residue X carries more than one charge
  • more than one counterion Y can be present or residue Y carries more than one countercharge It is important that residue Y is selected so that the total molecule of the formula I is not charged
  • X and Y are chemically bonded together, such as in moieties as -(CH 2 ) r N + (R 11 ) 2 -(CH 2 )rS ⁇ 3 , with r is as defined above and t is an integer of 1 to 10, preferably 1 to 5, e.g. 2.
  • residues X and Y together form a zwitter ion structure.
  • residues R 1 to R 6 , X and Y are selected so that the molecule has a water- solubility of at least 10 g/l, preferably at least 50 g/l, more preferably at least 100 g/l. If the water-solubility of a compound of formula I is not sufficiently high, the substitution pattern can be changed, e.g. the number of carbon atoms in residues R 3 to R 6 can be reduced, ary! or cycloalkyl residues which can reduce the water-solubility can be removed from some or all of the residues, and hydrophilic substituents such as hydroxy groups can be included.
  • Compounds which have a particularly high adherence to hair may have a lower water- solubility.
  • M + is a counterion, which is preferably selected from Na + , K + , Li + , NH 4 + and 0.5 equivalent of Mg 2+ and Ca 2+ .
  • M + is K + , Li + , NH 4 + or 0.5 equivalent of Mg 2 2 + + ⁇ o r r ⁇ Ca
  • the compounds of formula (I) can be prepared by methods known per se. Some methods are disclosed in the examples, and a skilled person can easily adapt these methods to prepare other compounds of formula (I).
  • Phosphate residues of the type -0-PO 3 2' can for example be prepared from the corresponding alcohol function using e.g. POCI 3 with a base as e.g. triethylamine [see e.g. M. -Z. Liu et al., Carbohydr. Res. 330 (3), 413-420 (2001)], with P 2 O 5 and H 3 PO 4 [see e.g. K. Buss et al., J. Med. Chem. 44 (19), 3166-3174 (2001 )] or by enzymatic methods.
  • a base as e.g. triethylamine
  • P 2 O 5 and H 3 PO 4 see e.g. K. Buss et al., J. Med. Chem. 44 (19), 3166-3174 (2001 )] or by enzymatic methods.
  • Sulfate residues of the type -0-SO 3 ' can for example be prepared from the corresponding alcohol function using e.g. SO 3 x pyridine [see e.g. W. J. Sanders et al., Tetrahedron 53 (48), 16391 -16422 (1997)], SO 3 x NEt 3 [see e g B Ferla et al , Tetrahedron 55 (32), 9867- 9880 (1999)], chlorosulfonic acid [see e g G Dekany et al , J Carbohydr Chem 16 (1), 1 1- 24 (1997)] or H 2 SO 4 [see e g S P Gaur et al , Indian J Chem Sect B 21 (1), 46-51 (1982)]
  • Residues R 1 and R 2 are both cyano groups
  • residues R 3 , R 4 , R 5 and R 6 are independently selected from hydrogen atoms and C 1 -C 6 alkyl groups
  • Y is a counterion which balances the charge of residue X, preferably an alkali metal ion or a halogen ion, depending on the charge of X, and
  • each R 9 is independently hydrogen, hydroxy or Ci-C 3 alkyl, V and U are an oxygen atom, n is an integer of 1 to 3, m is 0 or 1 , p is 0 or 1 , wherein at least one of m and p is 1 , o is an integer of 1 to 3, and q is an integer of 1 to 3, and W is a residue -0-PO 3 H or a residue -0-SO 3 , or
  • residues R 10 are independently selected from hydrogen atoms, hydroxyl groups and C 1 -C 3 alkyl groups
  • residues R 11 are independently selected from hydrogen atoms and CrC 6 alkyl groups which are optionally interrupted by 1 to 2 hetero atoms and which are optionally substituted by 1 to 3 hydroxyl groups
  • r is an integer of 1 to 6, or
  • each R 9 is independently hydrogen or methyl, V and U are an oxygen atom, n is an integer of 1 to 3, m is O or 1 , p is O or 1 wherein at least one of m and p is 1 , o is an integer of 1 to 3, and q is an integer of 1 to 3, and W is a residue O-PO 3 H or a residue -0-SO 3 , or
  • residues R 10 are independently selected from hydrogen atoms, hydroxy! groups and CrC 3 alkyl groups
  • residues R 11 are independently selected from hydrogen atoms and C 1 -C 6 alkyl groups which are optionally interrupted by 1 to 2 oxygen atoms and which are optionally substituted by 1 to 3 hydroxyl groups
  • r is an integer of 1 to 3, or
  • each R 9 is independently hydrogen or methyl
  • V is an oxygen atom
  • n is an integer of 1 to 3
  • m is 1
  • o is an integer of 1 to 3
  • W is a residue -0-PO 3 H " or a residue -0-SO 3 ' , or
  • residues R 10 are independently selected from hydrogen atoms and Ci-C 3 alkyl groups
  • residues R 11 are independently selected from C 1 -C 6 alkyl groups which are optionally interrupted by 1 to 2 hetero atoms and which are optionally substituted by 1 to 3 hydroxyl groups
  • r is an integer of 1 to 3, or
  • each R s is independently hydrogen, hydroxy or C 1 -C 3 alkyl, and n is an integer of 1 to 6, and W is a residue -0-PO 3 H or a residue -0-SO 3 , or
  • residues R 10 are independently selected from hydrogen atoms, hydroxyl groups and C 1 -C 3 alkyl groups, and two residues R 11 are C 1 -C 3 alkyl groups, and one residue R 11 is a C 1 -C 6 alkyl group which is interrupted by 1 or 2 oxygen atoms and which is optionally substituted by 1 to 3 hydroxyl groups, and r is an integer of 1 to 3 or the residues R 11 form together with the nitrogen atom a pyridinyl group which is unsubstituted or substituted with 1 to 5, preferably 1 to 3 substituent groups R 8 as defined above
  • compositions comprising a compound of formula (I) formulated into a suitable support or substrate
  • the compositions are adopted for protecting a material that is sensitive to ultraviolet radiation, in particular solar radiation, and comprises an effective photoprotective amount of at least one of the compounds of formula (I)
  • such compositions are suited for protecting the skin and/or hair against the deleterious effect of UV radiation
  • the compositions are cosmetic or pharmaceutical compositions which comprise a topically applicable, cosmetically or pharmaceutically acceptable vehicle and diluent as carrier
  • the compounds of formula (I) can be incorporated into a plastic substrate
  • the compounds of formula (I) may also be used to stabilize photosensitive ingredients in topical formulations particularly colorants, such as FD&C and D&C colorants, curcumin, riboflavin, lactoflavin, tartrazine, chinolinyellow, cochenille, azorubin, amaranth, ponceau 4R, erythrosine, indigotin, chlorophyll, chlorophyllin, caramel, Carbo medicinalis, carotenoids, bixin, norbixin, annatto, orlean, capsanthin, capsorubin, lycopin, xanthophyll, flavoxanthin, lutein, kryptoaxanthin, rubixanthin, violaxanthin, rhodoxanthin, canthaxanthin, betanin, anthocyans, vitamins such as vitamin A, vitamin K1 , vitamin C or other active ingredients, curcumin, riboflavin, lactoflavin, tartraz
  • the amount used of compounds of formula (I) for the protection of fragrances and perfumes is at least 0 01 %, preferably in the in the range of 0 05-2%, most preferred in the range of 0 05-1 % As used in this specification percentages and parts are by weight based on the total weight of the composition, if nothing else is explicitly mentioned or obvious
  • inks which are used e g for ink jet printing, pencils, markers or endorsing inks are dye-based or pigment based These inks and consequently e g inkjet prints made with these inks are susceptible to light fading as the colorants photodegrade upon irradiation, especially with UV light
  • the hydrosoluble compounds of formula (I) are especially suitable for inhibiting the photodegradation of dyes or pigments used in inks, preferred in aqueous-based inks leading to an increased lightfastness
  • the amount used of compounds of formula (I) for the protection of inks is at least 0 01 %, preferably in the in the range of 0 05-5%, most preferred in the range of 0 05-3%
  • the compounds of formula (I) may also be used to stabilize photosensitive ingredients such as colorants, dyes and pigments in hair dyes and cosmetics, in particular in decorative cosmetics
  • the amount used of compounds of formula (I) for the protection of photosensitive ingredients in inks is at least 0 01%, preferably in the in the range of 0 05- 5%, most preferred in the range of 0 05-3%
  • the same amounts and preferred amounts of the compounds of formula (I) can be used
  • a compound of formula (I) may be incorporated in auxiliary agents, e g a cosmetic base, which are conventionally used for such formulations
  • auxiliary agents e g a cosmetic base
  • other conventional UV-A and/or UV-B and/ or broadband UV-screening agents may also be added
  • the combination of UV filters may show a synergistic effect
  • the preparation of said light screening compositions is well known to the skilled artisan in this field
  • light screening composition includes all compositions or formulations which can be used for the protection of the skin and/ or hair against UV-radiation such as lotions, emulsions, cream, milk, powder, stick, ointments, gels, sprayable compositions, hairsprays, foams, mousses, conditioners, shampoos without being limited hereto
  • compositions contain the compound of formula (I) in an effective amount
  • effective amount means generally at least 0 1 % by weight of the light screening composition
  • the compositions contain the compound of formula (I) in an amount of 0 1 wt -% to 30 wt -%, more preferably 0 5 to 20 wt -%, still more preferably 1 to 10 wt -%, based on the total weight of the composition
  • the compounds of formula (I) are used in combination with one or more other hydrophilic and/or lipophilic sunscreen agents, e g another UV-A sunscreen agent, another UV-B sunscreen agent or a broad-band sunscreen agent or a combination of the above, the total amount of sunscreen agents in the compositions including the compound of formula (I) is not narrowly critical
  • the amounts of the additional sunscreen agents may vary from 0 1 % and higher, suitably between 0 1 wt -% to 30 wt -%, preferably 0 5 to 20 wt -% and more preferably 1 w
  • the amount of compounds of formula I and optionally an additional hydropM'C and/or lipophilic UV-A or UV-B or broadband screening agent other than the compounds of formula (I) may be in the range of from 0 5 to 12% by weight of the total composition
  • the relative amount of the compound of formula (I) in such a combination is at least 5% based on the total weight of the sunscreen agents of the composition
  • the relative amount of the compound of formula (I) on the total weight of the sunscreen agents of the composition is in the range of 10-60%, more preferable between 10-40%
  • the compound of formula I or a combination of sunscreen agents including a compound of formula (I) in the above ranges is preferably suitable to protect skin or hair against UV-radiation of 320 to 400 nm
  • UV-B or broad spectrum screening agents i e substances having absorption maximums between about 290 and 340 nm, which come into consideration for combination with the compounds of the present invention are for example the following organic and inorganic compounds
  • Acrylates such as 2-ethylhexyl 2-cyano-3,3-d ⁇ phenylacrylate (octocrylene, PARSOL® 340), ethyl 2-cyano-3,3-d ⁇ phenylacrylate and the like,
  • Camphor derivatives such as 4-methyl benzyhdene camphor (PARSOL® 5000), 3-benzyl ⁇ dene camphor, camphor benzalkonium methosulfate, polyacrylamidomethyl benzyhdene camphor, sulfo benzyhdene camphor, sulfomethyl benzyhdene camphor, therephthalidene dicamphor sulfonic acid and the like, 3-(4'-Tr ⁇ methylammon ⁇ um)benzyl ⁇ dene-bornan-2-on-methylsulfat (Mexoryl SK),
  • Cinnamate derivatives such as octyl methoxycinnamate (PARSOL® MCX), ethoxyethyl methoxycinnamate, diethanolamine methoxycinnamate (PARSOL® Hydro), isoamyl methoxycinnamate and the like as well as cinnamic acid derivatives bond to siloxanes,
  • p-Aminobenzoic acid derivatives such as p-aminobenzoic acid, 2-ethylhexyl p-dimethylaminobenzoate, N-oxypropylenated ethyl p-aminobenzoate, glyceryl p- aminobenzoate, ethoxylated ethyl-4-am ⁇ nobenzoate (PEG-25 PABA),
  • Benzophenones such as benzophenone-3, benzophenone-4, 2,2', 4, 4'- tetrahydroxy-benzophenone, 2,2'-d ⁇ hydroxy-4,4'-d ⁇ methoxybenzophenone and the like,
  • esters of Benzalmalonic acid such as d ⁇ -(2-ethylhexyl) 4- methoxybenzalmalonate
  • esters of 2-(4-ethoxy-an ⁇ l ⁇ nomethylene)propaned ⁇ o ⁇ c acid such as 2-(4- ethoxy an ⁇ l ⁇ nomethylene)propaned ⁇ o ⁇ c acid diethyl ester as described in the European Patent Publication EP 0895 776,
  • microparticulated refers to a particle size from about 5 nm to about 200 nm, particularly from about 15 nm to about 100 nm
  • the TiO 2 particles may also be coated by metal oxides such as e g aluminum or zirconium oxides or by organic coatings such as e g polyols, methicone, dimethicone, aluminum stearate, alkyl silane, silicium dioxide Such coatings are well known in the art
  • Imidazole derivatives such as e g 2-phenyl benzimidazole sulfonic acid and its salts (PARSOL ⁇ HS) Salts of 2-phenyl benzimidazole sulfonic acid are e g alkali salts such as sodium- or potassium salts, ammonium salts, morpholine salts salts of primary, sec and tert amines like monoethanolamine salts, diethanolamine salts and the like
  • Salicylate derivatives such as isopropylbenzyl salicylate, benzyl salicylate, butyl salicylate, octyl salicylate (NEO HELIOPAN OS), isooctyl salicylate or homomenthyl salicylate (homosalate, HELIOPAN) and the like
  • T ⁇ azine derivatives such as octyl triazone (UVINUL T-150), dioctyl butamido t ⁇ azone (UVASORB HEB), bis ethoxyphenol methoxyphenyl t ⁇ azine (Tinosorb S) and the like
  • Examples of broad spectrum or UV A screening agents i e substances having absorption maximums between about 320 and 400 nm, which come into consideration for combination with the compounds of the present invention are for example the following organic and inorganic compounds
  • Dibenzoylmethane derivatives such as 4-tert butyl-4'-methoxyd ⁇ benzoyl- methane (PARSOL® 1789), dimethoxydibenzoylmethane, isopropyldibenzoylmethane and the like,
  • Benzot ⁇ azole derivatives such as 2,2'-methylene-b ⁇ s-(6-(2H-benzotr ⁇ azole-2- yl)-4-(1 ,1 ,3,3,-tetramethylbutyl)-phenol (TINOSORB M) and the like,
  • Phenylene-1 ,4-bis-benzimidazolsulfonic acids or salts such as 2 2-(1 4- phenylene)b ⁇ s-(1 H-benz ⁇ m ⁇ dazol-4,6-d ⁇ sulfon ⁇ c acid) (Neohehopan AP), Amino substituted hydroxybenzophenones such as 2-(4-D ⁇ ethylam ⁇ no-2- hydroxy-benzoyl)-benzo ⁇ c acid hexylester (Uvmul A Plus) as described in the European Patent Publication EP 1046391 ,
  • microparticulated refers to a particle size from about 5 nm to about 200 nm, particularly from about 15 nm to about 100 nm
  • the particles may also be coated by other metal oxides such as e g aluminum, of calcinated alumina or zirconium oxides or by organic coatings such as e g polyols, methicone, dimethicone, aluminum stearate, alkyl silane, simethicone, t ⁇ methoxycaprylylsilane, triethoxy caprylylsilane and silicium dioxide
  • Such coatings are well known in the art Examples of such 'microparticulated' ZnO or TiO 2 are e g listed in EP 1 281 388 A1 Other examples are described in DE 103 33 029, EP 1 284 277, EP 0 988 853, US 5 756 788, EP-A 1 284 277, and US-A
  • microparticulated ZnO or TiO 2 and the like can be in the form of a powder or being pre- dispersed in oil and/ or water
  • conventional UV-A screening agent also refers to dibenzoylmethane derivatives such as e g PARSOL® 1789 stabilized by, e g ,
  • compositions containing a compound of formula (I) as defined above and in addition one or more non-penetrating UV screening agents are particularly preferred in order to reduce the systemic exposure to sunscreen agents
  • Non-penetrating UV screening agents generally are UV screening agents which (because of their size, molecular structure or for other reasons) do not penetrate into the skin of a person who uses the composition
  • Preferred non-penetrating UV screening agents are polymeric UV screening agents, and here in particular the compound Parsol SLX
  • Non-penetrating UV screening agents are inorganic UV screening agents such as titanium dioxide and zinc oxide, which preferably are microparticulated as is known in the art
  • the particles may also be coated by other metal oxides such as e g aluminum, of calcinated alumina or zirconium oxides or by organic coatings such as e g polyols, methicone, dimethicone, aluminum stearate, alkyl silane, simethicone, trimethoxycaprylylsilane, triethoxy caprylylsilane and silicium dioxide
  • Such coatings are well known in the art Examples of such 'microparticulated' ZnO or TiO 2 are e g listed in EP 1 281 388 A1
  • Other examples are described in DE 103 33 029, EP 1 284 277, EP 0 988 853, US 5 756 788, EP-A 1 284 277, and US-A 5,562,897 without being limited hereto
  • the particles may also
  • compositions containing a compound of formula (I) as defined above and titanium dioxide and/or zinc oxide are also preferred.
  • encapsulated UV screening agents such as the commercial products Eusolex UV pearls or other encapsulated agents
  • encapsulated UV sunscreen agent refers to a UV-absorbing molecule which is in the form of either discrete liquid particles or discrete solid particles which are coated by a suitable capsule wall material to form microcapsules of a core shell or a matrix type, preferably of a core-shell type
  • microcapsules may be prepared by various polymerization techniques known in the art such as the sol-gel method, an in situ- polymensation method or an emulsion polymerization method as e g described in FR 2642329, DE-A 195 37 415, EP-A 509 904, FR 2726760, FR 2687914, WO 00/71084, US-A 6,303,149, WO 98/31333, US-A 5,876,699, WO 00/72806, WO 2005/009604, WO 00/09652 and WO
  • compositions containing a compound of formula (I) as defined above and an encapsulated sunscreen as disclosed in one of the above documents or another encapsulated sunscreen are also particularly preferred.
  • compositions containing a compound of formula (I) as defined above and an encapsulated UV screening agent where the encapsulated UV screening agent is characterized in that the microcapsules have an average particle size D(v, 0 5) in the range from 3 ⁇ m to 8 ⁇ m, more preferably in the range from 3 to 5 ⁇ m and most preferably in the range from 3 to 4 ⁇ m
  • the compounds of formula I have an unexpectedly low skin penetration and thus lead to significantly reduced systemic exposure through the skin compared to the traditional organic UV-f ⁇ lters They are therefore particularly suitable for use in combination with other nonpenetrating UV-screening agents, in particular with the non-penetrating UV-screening agents as defined above in order to provide sunscreen compositions which despite comprising a monomeric, organic, non-encapsulated sunscreen agent have a very low systemic exposure
  • the present invention therefore also provides the use of the compounds of formula (I) in a cosmetic or dermatological sunscreen composition comprising at least one monomeric, non-encapsulated, organic UV sunscreen agent for reducing the systemic exposure of sunscreen agents by skin penetration This means that in such cosmetic or dermatological sunscreen compositions the skin penetration (and thus also the systemic exposure induced thereby) is lower than in the same composition containing another monomeric, non-encapsulated, organic sunscreen agent with UV-A screening activity, in particular Uvinul A plus instead of the compound of formula (I)
  • cosmetic formulations containing a compound of formula (I) and additionally at least one other non-penetrating UV-sunscreen are preferred.
  • cosmetic formulations containing a compound of formula (I) and additionally at least one nonpenetrating sunscreen selected from Parsol SLX , or microparticulated titanium dioxide or zinc oxide or an encapsulated UV screening agent or mixtures thereof are preferred.
  • compositions containing a combination of a sunscreen agent according to formula (I) above and a micronized organic UV-f ⁇ lter which also has a relatively low skin penetration such as methylene bis-benzotriazolyl tetramethylbutylphenyl (Tinosorb M)
  • compositions containing a combination of a sunscreen agent according to formula (I) above with an additional sunscreen agent which has a relatively high molecular weight and thus also a reduced skin penetration rate preferably a triazine derivative
  • Suitable triazine derivatives are e g Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine which is sold under the trade name Tinosorb S or Diethylbutamido t ⁇ azone which sold under the trade name Uvasorb HEB or Ethylhexyt ⁇ azone sold under the tradename Uvinul T 150
  • a reduced skin penetration rate in this connection means that the additional sunscreen agent such as the triazine derivative has a skin penetration rate which is not significantly higher than the skin penetration rate of the sunscreen agent of formula I which is also present in the composition
  • “Not significantly higher” means in this connection that the skin penetration rate of the additional sunscreen agent is not more than 20%, preferably not more than 10% above the skin penetration rate of the sunscreen agent of formula I which is present in the composition, most
  • UV sunscreen combinations as described above show synergistic effects reflected by a sun protection performance (SPF) which is significantly higher than expected when calculated from the addition of the SPFs of the single sunscreen agents This exceptional performance can be demonstrated by in vitro and/or in vivo SPF measurements
  • compositions with surprisingly high, synergistic SPFs can be obtained when compounds of formula (I) are combined with Parsol SLX and optionally a non penetrating sunscreen agent as defined above and/ or a triazine derivative and/ or a micronized organic particle
  • compounds of the formula (I) exhibit a synergistic effect when used together with traditional organic UV-absorbers such as ethylhexyl methoxycinnamate (Parsol MCX), octocrylene (Parsol 340), 4-methylbenzyl ⁇ dene camphor (Parsol 5000), phenylbenzimidazole sulfonic acid (Parsol HS), ethylhexyl salicylate (Parsol EHS), homosalate (Parsol HMS), microparticulated titanium dioxide (Parsol TX), benzophenone-3 (Uvinul M 40), ethylhexyl t ⁇ azone (Uvinul T 150).
  • organic UV-absorbers such as ethylhexyl methoxycinnamate (Parsol MCX), octocrylene (Parsol 340), 4-methylbenzyl ⁇ dene camphor (Parsol 5000), phenylbenzimidazole sulfonic acid (
  • UV sunscreen combinations of the compounds of formula (I) together with other UV-A screening agents show synergistic effect regarding the UV-A protection reflected by an UVA balance which is significantly higher than expected when calculated from the addition of the UVA balances of the single sunscreen agents This exceptional performance can be demonstrated by in vitro/in vivo SPF/UVA balance measurements using the German norm DIN 67502 (Characterization of UVA protection of dermal sun care products by measuring the transmittance with regard to the sun protection factor)
  • benzoic acid derivatives such as diethylamino hydroxybenzoyl hexyl benzoate (Uvinul A Plus) or triazine derivatives such as bis-ethylhexyloxyphenol methoxyphenyl triazine (Tinosorb S)
  • compositions can also contain usual cosmetic adjuvants and additives, such as preservatives/ antioxidants, fatty substances/ oils, water, organic solvents, silicones, thickeners, softeners, emulsifiers, additional sunscreens, antifoaming agents, moisturizers, fragrances, surfactants, fillers, sequestering agents, anionic, cationic, nonionic or amphoteric polymers or mixtures thereof, propellants, acidifying or basifying agents, dyes, colorants, pigments or nanopigments, in particular those suited for providing an additional photoprotective effect by physically blocking out ultraviolet radiation, or any other ingredients usually formulated into cosmetics, in particular for the production of sunscreen/ antisun compositions
  • the necessary amounts of the cosmetic and dermatological adjuvants and additives can, based on the desired product, easily be chosen by a skilled artisan in this field and will be illustrated in the examples, without being limited hereto
  • antioxidants/ preservatives are generally preferred Based on the invention all known antioxidants usually formulated into cosmetics can be used Especially preferred are antioxidants chosen from the group consisting of amino acids (e g glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazole (e g urocanic acid) and derivatives, peptides such as D,L-carnos ⁇ ne, D-carnosine, L-carnosine and derivatives (e g anserine), carotenoids, carotenes (e g ⁇ -carotene, ⁇ -carotene, lycopene) and derivatives, chlorogenic acid and derivatives, lipoic acid and derivatives (e g dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols (e g thioredoxin, glutathione, cysteine, cystine, cystamine and its glycosyl-, N
  • formulations also contain surface active ingredients like emulsifiers, solubihzers and the like
  • An emulsifier enables two or more immiscible components to be combined homogeneously Moreover, the emulsifier acts to stabilize the composition
  • Emulsifiers that may be used in the present invention in order to form O/W, W/O, O/W/O or W/O/W emulsions/microemulsions include sorbitan oleate, sorbitan sesquioleate, sorbitan isostearate, sorbitan trioleate, polyglyceryl-3-d ⁇ sostearate, polyglycerol esters of oleic/isostearic acid, polyglyceryl-6 hexa ⁇ cinolate, polyglyceryl-4-oleate, polygylceryi-4 oleate/PEG-8 propylene glycol cocoate, oleamide DEA, TEA my ⁇ state, TEA stearate,
  • oils such as triglycerides of caprinic acid or caprylic acid, preferable castor oil,
  • esters of fatty acids with alcohols e g isopropanol, propylene glycol, glycerin or esters of fatty alcohols with carbonic acids or fatty acids,
  • alkylbenzoates and/or
  • silicone oils such as dimethylpolysiloxane, diethylpolysiloxane, diphenylpolysiloxane, cyclomethicones and mixtures thereof
  • Exemplary fatty substances which can be incorporated in the oil phase of the emulsion, microemulsion, oleo gel, hydrodispersion or lipodispersion of the present invention are advantageously chosen from esters of saturated and/or unsaturated, linear or branched alkyl carboxylic acids with 3 to 30 carbon atoms, and saturated and/or unsaturated, linear and/or branched alcohols with 3 to 30 carbon atoms as well as esters of aromatic carboxylic acids and of saturated and/or unsaturated, linear or branched alcohols of 3-30 carbon atoms
  • Such esters can advantageously be selected from octylpalmitate, octylcocoate, octylisostearate, octyldodecylmy ⁇ state, cetearylisononanoate, isopropylmyristate, isopropylpalmitate isopropylstearate, isopropyloleate, n-buty
  • fatty components suitable for use in the formulation of the present invention include polar oils such as lecithins and fatty acid triglycerides, namely triglycerol esters of saturated and/or unsaturated, straight or branched carboxylic acid with 8 to 24 carbon atoms, preferably of 12 to 18 carbon-atoms whereas the fatty acid triglycerides are preferably chosen from synthetic, half synthetic or natural oils (e g cocoglyce ⁇ de, olive oil, sun flower oil, soybean oil, peanut oil, rape seed oil, sweet almond oil, palm oil, coconut oil, castor oil, hydrogenated castor oil, wheat oil, grape seed oil, macadamia nut oil and others), apolar oils such as linear and/ or branched hydrocarbons and waxes e g mineral oils, vaseline (petrolatum), paraffins, squalane and squalene, polyolefins, hydrogenated polyisobutenes and isohexadecanes, favored poly
  • fatty components which can advantageously be incorporated in formulations of the present invention are isoeikosane, neopentylglycoldiheptanoate, propyleneglycoldicaprylate/dicaprate, caprylic/cap ⁇ c/diglycerylsuccinate, butyleneglycol caprylat/caprat, Ci 2 -i 3 -alkyllactate, d ⁇ -C 12 -i 3 alkyltartrate, t ⁇ isostea ⁇ n, dipentaeryth ⁇ tyl hexacaprylat/hexacaprate, propyleneglycolmonoisostearate, tricaprylin, dimethylisosorbid Especially beneficial is the use of mixtures C 12 15-alkylbenzoate and 2- ethylhexyhsostearate, mixtures Ci 2 1 5 -alkylbenzoate and isot ⁇ decylisononanoate as well as mixtures of C 12 15 -alky
  • a moisturizing agent may be incorporated into a composition of the present invention to maintain hydration or rehydrate the skin Moisturizers that prevent water from evaporating from the skin by providing a protective coating are called emollients
  • emollients include mineral oils, lanolin, petrolatum, cap ⁇ c/caprylic triglyceraldehydes, cholesterol, silicones such as dimethicone, cyclomethicone, almond oil, jojoba oil, avocado oil, castor oil, sesame oil, sunflower oil, coconut oil and grape seed oil, cocoa butter, olive oil aloe extracts, fatty acids such as oleic and stearic, fatty alcohols such as cetyl and hexadecyl (ENJAY), dnsopropyl adipate, hydroxybenzoate esters, benzoic acid esters of ison
  • humectants Moisturizers that bind water, thereby retaining it on the skin surface are called humectants Suitable humectants can be incorporated into a composition of the present invention such as glycerin, polypropylene glycol, polyethylene glycol, lactic acid, pyrrolidone carboxylic acid, urea, phospholipids, collagen, elastin, ceramides, lecithin sorbitol, PEG-4, and mixtures thereof Additional suitable moisturizers are polymeric moisturizers of the family of water soluble and/or swellable/ and/or with water gelating polysaccharides such as hyaluronic acid, chitosan and/or a fucose rich polysaccharide which is e g available as Fucogel®1000 (CAS-Nr 178463-23-5) by SOLABIA S One or more humectants are optionally present at about 0 5 wt % to about 8 wt
  • the aqueous phase of the compositions can contain the usual cosmetic additives such as alcohols, especially lower alcohols, preferably ethanol and/ or isopropanol, low diols or polyols and their ethers, preferably propylene glycol, glycerin, ethylene glycol, ethylene glycol monoethyl- or monobutylether, propylene glycol monomethyl- or -monoethyl- or -monobutylether, diethylene glycol monomethyl-or monoethylether and analogue products, polymers, foam stabilizers, electrolytes and especially one or more thickeners Thickeners that may be used in formulations of the present invention to assist in making the consistency of a product suitable include carbomer, siliciumdioxide, magnesium and/ or aluminum silicates, beeswax, stearic acid, stearyl alcohol polysaccharides and their derivatives such as xanthan gum, hydroxypropyl cellulose polyacrylamides
  • the emulsions/ microemulsions of this invention may contain preferably electrolytes of one or several salts including anions such as chloride, sulfates, carbonate, borate and aluminate, without being limited thereto
  • suitable electrolytes can be on the basis of organic anions such as, but not limited to, lactate, acetate, benzoate, propionate, tartrate and citrate
  • cations preferably ammonium, alkylammonium, alkali- or alkaline earth metals, magnesium-, iron- or zinc- ions are selected
  • Especially preferred salts are potassium and sodium chloride, magnesium sulfate, zinc sulfate and mixtures thereof
  • Electrolytes can be present in an amount of about 0 01 wt % to about 8 wt % in the composition of the present invention
  • compositions are useful as compositions for photoprotecting the human epidermis or hair against the damaging effect of ultraviolet irradiation, as sunscreen compositions
  • Such compositions can, in particular, be provided in the form of a lotion, a thickened lotion, a gel, a cream, a milk, an ointment, a powder or a solid tube stick and can be optionally be packaged as an aerosol and can be provided in the form of a mousse, foam or a spray
  • the cosmetic composition according to the invention are provided for protecting the human epidermis against UV radiation or as sunscreen composition, they can be in the form of a suspension or dispersion in solvents or fatty substances, or alternatively in the form of an emulsion or microemulsion (in particular of O/W or W/O type, O/W/O or W/O ⁇ /V-type), such as a cream or a milk, a vesicular dispersion, in the form of an ointment, a gel, a solid tube stick or an
  • the compounds of formula (I) protect the skin and hair agamst dangerous UV-A radiation They can be complemented by other UV-A sunscreens in the organic phase thus giving rise to higher sun protection
  • the compounds can easily be incorporated into different cosmetic compositions, and they show protection against a longer wavelength than other known UV- A sunscreens and in particular than other commercial, water-soluble UV-A sunscreens, thus being a real UV-A filter and not an UV-A/UV-B gap filter and shielding the skin up to the visible rays without being colored
  • it is a significant advantage of the novel compounds of formula (I) that they show higher extinctions than other known water-soluble UV-A sunscreens and in particular even a better extinction than the present commercial water-soluble UV-A sunscreens, thus giving better protection
  • the compounds of formula (I) additionally show an excellent photostabihty
  • the compounds of formula (I) also stabilize emulsions and can therefore serve as co-emulsifiers for the compositions of the present invention, if these are in the form of
  • Parsol 1789 The chemical name of Parsol 1789 is 4-tert -butyl-4'-methoxyd ⁇ benzoylmethane
  • glycerin enhances the photostabihty of cosmetic or dermatological compositions containing compounds of formula (I)
  • a suitable amount of glycerin used is in the range of 1-40%, preferably in the range of 2- 20%, most preferred in the range of 2-10%
  • the sunscreen agents of formula (I) can also act as co-emulsifier for sunscreen compositions, and therefore, it is possible to reduce the amount of emulsifier in cosmetic and dermatological compositions This is particularly important, because emulsifiers (which are needed to provide stable emulsions) can have negative influence on the skin, in particular under UV radiation and relatively high amounts of emulsifiers are often required in order to provide a stable UV-sunscreen composition Thus, for sunscreen compositions it is of high importance to reduce the amount of emulsifier as much as possible
  • the present invention also provides the use of a combination of a sunscreen agent of formula (I) as defined above in an amount of 0 1 wt -% to 30 wt -%, preferably of 0 5 to 20 wt -%, particularly preferably of 1 0 to 15 wt -% in combination with a co-emulsifier in an amount of 0 1 -40%, preferably 0 1-20%, most preferred in an amount of 0 1-10
  • the preparation of cosmetic emulsions in the presence of salts or other ionic compounds can pose problems, in particular, if the ionic compound or the salt is a UV screening agent, because a rather high amount of a UV screening agent is required to provide sufficient UV protection
  • many ionic UV screening agents such as phenylbenzimidazolesulfonic acid or disodiumphenyldibenzimidazole tetrasulfonate cause problems regarding the stability of emulsions
  • O/W emulsions but also WVO emulsions containing the sunscreen agents of formula (I) are particularly stable if they are formulated together with certain thickening agents which are incorporated into the water phase These thickening agents provide stable gels even in the presence of high salt concentrations
  • the present invention also provides the use of a thickening agent for stabilizing a composition in form of an emulsion containing 0 1 wt -% to 30 wt -%, preferably 0 5 wt -% to 20 wt -%, particularly preferred 1 0 wt -% to 15 wt -% of a sunscreen agent of formula (I) as defined above, so that the emulsion is stable for at least three months (preferably for at least six months) at 43°C
  • the thickening agents can stabilize emulsions containing the sunscreen agents of formula (I) in a pH range of 4 to 9, particularly in a pH range of 5 to 7 With these thickening agents it became possible to formulate emulsions which were stable for at least six months at 43°C
  • the present invention also provides compositions comprising a sunscreen agent of formula (I) as defined above in combination with a thickening agent as defined above
  • Glyceryl Hydroxystearate Cetyl Palmitate, Microcrystalline Wax, Trihydroxystearin Unitina
  • Cetearyl Alcohol AEC Cetearyl Alcohol (A&E Connock (Perfumery & Cosmetics) Ltd )
  • Cetyl Palmitate Cutina CP (Cognis Corporation, Care Chemicals)
  • Ethyl Cellulose Brillance 515 (Gattefosse s a s)
  • Methylcellulose Methocel A (Amerchol Corporation)
  • Aerosil 130 (Degussa AG) c.2. Bentonite:
  • Pemulen TR-1 Polymer Noveon, lnc
  • Pemulen TR-2 Polymer Noveon, Inc
  • PVM/MA Decadiene Crosspolymer or Sodium PVM/MA Decadiene Crosspolymer
  • Aculyn 22 (Rohm and Haas Company, Inc) d.4. Polyethylene Glycols, Ethoxylated Carboxylic Acids and Ethoxylated Fatty
  • Polyethylene Glycol (5000) Polyox WSR N-80 (Amerchol Corporation) Polyethylene Glycol (9000) Alkox E-30G (Meisei Chemical Works, Ltd) Steareth-5 Stearate d.S. Self-emulsifying Polyacrylamides
  • thickeners are cellulose and cellulose derivatives as well as xanthan gum and its derivatives, pectin and its derivatives, agar and its derivatives, alginate and its derivatives, guar gum and its derivatives, starch and its derivatives, carrageenan and its derivatives, gelatin and its derivatives, silica and its derivatives, carbomers (such as Carbopols) and polyethylene glycols of different chain length
  • These thickening agents can be used alone or in combination with one another or with other thickeners
  • thickening agents which can be included within the oil phase and which provide stable emulsions even in the presence of high salt concentrations in the composition
  • Such thickeners are particularly natural and synthetic waxes such as beeswax, candelila wax, microcrystalline wax, etc , fatty alcohols such as cetyl alcohol, cetearyl alcohol, etc , fatty acid esters such as cetyl palmitate, etc , esters of glycerol with fatty acids such as glyceryl my ⁇ state, glyceryl stearate, etc , fatty acids such as stea ⁇ c acid, etc , hydrogenated fats such as hydrogenated castor oil, hydrogenated palm glyce ⁇ des, etc , mineral oil and further fractions of the oil distillation such as paraffin, paraffinum hquidum, petrolatum, ozokerite, etc
  • These stabilizers can be used alone or in combination with other stabilizers or with one another With these stabilizers it became possible to formulate emulsions containing
  • certain emulsifiers are particularly suitable for providing stable emulsions containing a sufficient amount of the sunscreen agents of formula (I) as defined above
  • the present invention thus also provides the use of an emulsifier for stabilizing a composition in form of an emulsion containing 0 1 wt -% to 30 wt -%, preferably 0 5 wt -% to 20 wt -%, particularly preferred 1 0 wt -% to 15 wt -% of a sunscreen agent of formula (I) as defined above in the emulsion so that the emulsion is stable for at least six months at 43°C
  • Cocamidopropyl Betaine lncronam 30 (Croda Chemicals Europe Ltd )
  • Anionic Surfactants b.1.
  • Oleic Acid Emersol 210 (Cognis Corporation)
  • Alkyl Sulfates (fatty alcohol sulfates) Sodium Lauryl Sulfate Texapon K 12 P (Cognis
  • Laneth Laneth-5 Polychol 5 (Croda Chemicals Europe, Ltd )
  • Sorbitan Sesquusostearate AEC Sorbitan Sesqunsostearate (A&E Connock (Perfumery &
  • Sorbitan Stearate Arlacel 60 (Uniquema Americas) d.3. Sucrose and Glucose derivatives like:
  • Methyl Glucose lsostearate lsolan IS (Degussa Care Specialties)
  • Cetearyl Glucoside Tego care CG 90 (Degussa Care Specialties) d.4. Alkanolamides like:
  • Sorbitan Oleate (and) Hydrogenated Castor Oil (and) Beeswax (and) Stearic Acid Arlacel
  • ionic emulsifiers and the salts thereof such as e g cetylphosphate, potassium cetylphosphate, t ⁇ laureth-4-phosphate, fatty acids and their salts such as stearic acid and polymeric emulsifiers such as e g stearate 21 , ceteareth-20, PEG-7, hydrogenated castor oil, PEG-45/dodecyl glycol copolymer
  • the emulsifiers can be used alone and in combination with one another
  • water-soluble UV-screening agents such as UV-screening agents which are ionic or in the form of pigments
  • sunscreen compositions with film forming agents for increasing the water resistance of the compositions
  • film forming agents for increasing the UV protecting efficiency of the compounds of formula (I) (UV-A boosting)
  • Particularly suitable are water- soluble (or dispersible) as well as fat-soluble film forming agents either alone or in combination with one another
  • Preferred water-soluble (or dispersible) film forming agents are e g polyurethanes (e g the Avalure ® Types of BF Goodrich), dimethicone copolyol polyacrylates (e g Silsoft Surface ® of Wi
  • Particularly preferred fat-soluble film forming agents are e g the film forming agents from the group of the polymers on the basis of polyvinylpyrrolidone
  • Particularly preferred are the copolymers of polyvinylpyrrolidone e g polyvinylpyrrolidone/hexadecen copolymer (e g Antaron V216), polyvinylpyrrolidone/eicosan copolymer (e g Antaron V220), butylated polyvinylpyrrolidone (e g Antaraon P-904) as well as the t ⁇ contanyl polyvinylpyrrolidone (e g Antaron WP-660) which are available from GAF Chemicals Cooperation or ISP
  • vinyl pyrrolidone/eicosane copolymers such as the compound Ganex V-220 of the company ISP and Stearoxy Dimethicone (Abil Wax 2434), Behenoxy Dimethicone (Abil
  • compositions containing a compound of formula (I) in addition with so-called “boosters” which enhance the activity of UV sunscreen agents are e g sunspheres (SunSpheres LCG and SunSpheres PGL polymers), hollow spheres, UV-latex particles, naphthalate etc and it can be referred to SOFW Journal (2002), 128(9), 36, 38-40
  • compositions of the present invention can be in the form of W/O or O/W emulsions, in the form of cosmetic or dermatological sticks, in the form of a foundation or a make-up of powders, of spray formulations, of gels or of a mousse
  • a particularly preferred cosmetic composition is a composition for tanning skin
  • Part A is heated in a reactor to 85°C.
  • Part B is slowly added within 10 minutes, followed by addition of KOH, cooling and degassing of the emulsion.
  • Cetyl Alcohol Cetyl Alcohol 2 00
  • Carbopol 981 ( 1 % sol )
  • Carbomer 10 00
  • Viscosity (Brookfield RVT, 25°C, spindle 6, 10 rpm) approx 12350 cP
  • Part A Add the ingredients in the order shown under agitation Charge in adequate containers with part B
  • Jojoba Oil Simmondsia Chinensis (Jojoba) 1 00
  • Carbopol 980 Carbomer 1 00
  • Viscosity (Brookfield RVT 1 25°C, spindle 7, 10 rpm) approx 175000 cP
  • Pemulen TR-2 Aery lates/C 10-30 Alky Acrylate 0 60
  • Viscosity (Brookfield RVT, 25°C, spindle 6, 10 rpm) approx 24100 cP
  • Viscosity (Brookfield RVT, 25°C, spindle 5, 10 rpm) approx 13700 cP
  • Phenonip Phenoxyethanol & Methylparaben & 0 50
  • Viscosity (Brookfield RVT, 25°C, spindle 7, 10rpm) approx 5240OcP
  • Viscosity (Brookfield RVT, 25°C, spindle 5, 10rpm) approx 17000 cP
  • My7itor3T8 ⁇ aprylic/Cap ⁇ c triglyceride 5 00 5 00 5 00
  • Carbopol ETD 2050 Car 0 20 ⁇ ⁇ 0 20
  • Ke ⁇ trol f Xan ⁇ han Gum "" 0 20 0 20 0 20
  • the photostabihty of a standard O/W emulsions containing the UV screening agents in the indicated concentrations was determined according to G Berset & H Gonzenbach (COLIPA Task force), Proposed protocol for determination of photostabihty Part I cosmetic UV-f ⁇ lters, lnt J Cosmet Sci 18, 167-188 (1996)

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  • Chemical & Material Sciences (AREA)
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  • Life Sciences & Earth Sciences (AREA)
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  • Cosmetics (AREA)

Abstract

La présente invention porte sur des utilisations avantageuses des dérivés de 1,4-dihydropyridine et sur de nouvelles compositions cosmétiques ou dermatologiques renfermant un écran solaire et contenant des dérivés de 1,4-dihydropyridine.
PCT/EP2006/007691 2005-08-05 2006-08-03 Utilisation d'ecrans solaires ioniques contre les uv-a WO2007017179A1 (fr)

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007024347A1 (de) 2007-05-22 2008-11-27 Beiersdorf Ag Kosmetische Zubereitung mit ionischem UV-A-Filter und Bis-Ethylhexyloxyphenol Methoxyphenyl Triazin
DE102007024345A1 (de) 2007-05-22 2008-11-27 Beiersdorf Ag Kosmetische Zubereitung mit ionischem UV-A-Filter, 4-(tert.-Butyl)-4'-methoxy-di-ben-zoylmethan und 2-Ethylhexyl-2cyano-3,3-di-phenyl-acrylat
DE102007024346A1 (de) 2007-05-22 2008-11-27 Beiersdorf Ag Kosmetische Zubereitung mit ionischem UV-A-Filter und 2-(4'-Diethylamino-2'hydoxybenzoyl)-benzoesäurehexylester
DE102007024348A1 (de) 2007-05-22 2008-11-27 Beiersdorf Ag Kosmetische Zubereitung mit ionischem UV-A-Filter und 2,4,6-Tris-(biphenyl)-1,3,5-triazin
DE102008018787A1 (de) * 2008-04-11 2009-10-15 Beiersdorf Ag Zubereitung für die Tagespflege
DE102008028664A1 (de) * 2008-06-09 2009-12-10 Beiersdorf Ag Sonnenschutzmittel mit hohem UV-A-Schutz
KR20110073599A (ko) * 2008-10-22 2011-06-29 다우 글로벌 테크놀로지스 엘엘씨 Ｓｐｆ 부스터로서 메틸셀룰로즈를 혼입한 자외선차단제 조성물 및 방법
US20110268678A1 (en) * 2009-01-05 2011-11-03 Armstrong Ernest T Vitamin d forming sunscreen
US20120183480A1 (en) * 2009-09-29 2012-07-19 Shiseido Company, Ltd. Oil-In-Water Emulsified Composition
US20120237466A1 (en) * 2011-03-18 2012-09-20 James Graham Photo-filtering composition for hair and scalp
US20180243190A1 (en) * 2015-08-18 2018-08-30 The Arizona Board Of Regents On Behalf Of The University Of Arizona Activators of nrf2-dependent photoprotection and related uses thereof
CN109133330A (zh) * 2018-08-31 2019-01-04 江苏新亿源环保科技有限公司 一种聚丙烯基负载纳米光催化剂型生物填料的制备方法
CN110339146A (zh) * 2019-08-21 2019-10-18 广州臻颜化妆品有限公司 一种水包油包水粉底液及其制备方法
CN116019727A (zh) * 2022-08-16 2023-04-28 广州云也品牌管理有限公司 一种化妆品组合物及其在防晒中的应用

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WO2003068183A1 (fr) * 2002-02-12 2003-08-21 Dsm Ip Assets B.V. Nouvelles compositions antisolaires et nouveaux dihydropyridines et dihydropyranes
DE10348577A1 (de) * 2003-10-20 2005-05-12 Few Chemicals Gmbh UV-und blaues Licht absorbierende Verbindungen als Medium für die optische Datenspeicherung
WO2005080341A1 (fr) * 2004-02-13 2005-09-01 Dsm Ip Assets B.V. Ecrans solaires ioniques anti-uva et compositions contenant ceux-ci

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
WO2003068183A1 (fr) * 2002-02-12 2003-08-21 Dsm Ip Assets B.V. Nouvelles compositions antisolaires et nouveaux dihydropyridines et dihydropyranes
DE10348577A1 (de) * 2003-10-20 2005-05-12 Few Chemicals Gmbh UV-und blaues Licht absorbierende Verbindungen als Medium für die optische Datenspeicherung
WO2005080341A1 (fr) * 2004-02-13 2005-09-01 Dsm Ip Assets B.V. Ecrans solaires ioniques anti-uva et compositions contenant ceux-ci

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007024347A1 (de) 2007-05-22 2008-11-27 Beiersdorf Ag Kosmetische Zubereitung mit ionischem UV-A-Filter und Bis-Ethylhexyloxyphenol Methoxyphenyl Triazin
DE102007024345A1 (de) 2007-05-22 2008-11-27 Beiersdorf Ag Kosmetische Zubereitung mit ionischem UV-A-Filter, 4-(tert.-Butyl)-4'-methoxy-di-ben-zoylmethan und 2-Ethylhexyl-2cyano-3,3-di-phenyl-acrylat
DE102007024346A1 (de) 2007-05-22 2008-11-27 Beiersdorf Ag Kosmetische Zubereitung mit ionischem UV-A-Filter und 2-(4'-Diethylamino-2'hydoxybenzoyl)-benzoesäurehexylester
DE102007024348A1 (de) 2007-05-22 2008-11-27 Beiersdorf Ag Kosmetische Zubereitung mit ionischem UV-A-Filter und 2,4,6-Tris-(biphenyl)-1,3,5-triazin
DE102008018787A1 (de) * 2008-04-11 2009-10-15 Beiersdorf Ag Zubereitung für die Tagespflege
DE102008028664A1 (de) * 2008-06-09 2009-12-10 Beiersdorf Ag Sonnenschutzmittel mit hohem UV-A-Schutz
KR101637185B1 (ko) 2008-10-22 2016-07-07 다우 글로벌 테크놀로지스 엘엘씨 Ｓｐｆ 부스터로서 메틸셀룰로즈를 혼입한 자외선차단제 조성물 및 방법
US20110256076A1 (en) * 2008-10-22 2011-10-20 Fletcher Robert B Sunscreen compositions incorporating methycellulose as an spf booster and methods
KR20110073599A (ko) * 2008-10-22 2011-06-29 다우 글로벌 테크놀로지스 엘엘씨 Ｓｐｆ 부스터로서 메틸셀룰로즈를 혼입한 자외선차단제 조성물 및 방법
US20110268678A1 (en) * 2009-01-05 2011-11-03 Armstrong Ernest T Vitamin d forming sunscreen
US9724544B2 (en) * 2009-01-05 2017-08-08 Ernest T. Armstrong Vitamin D promoting sunscreen
US20120183480A1 (en) * 2009-09-29 2012-07-19 Shiseido Company, Ltd. Oil-In-Water Emulsified Composition
US9066860B2 (en) * 2009-09-29 2015-06-30 Shiseido Company, Ltd. Oil-in-water emulsified composition
US20120237466A1 (en) * 2011-03-18 2012-09-20 James Graham Photo-filtering composition for hair and scalp
US20180243190A1 (en) * 2015-08-18 2018-08-30 The Arizona Board Of Regents On Behalf Of The University Of Arizona Activators of nrf2-dependent photoprotection and related uses thereof
CN109133330A (zh) * 2018-08-31 2019-01-04 江苏新亿源环保科技有限公司 一种聚丙烯基负载纳米光催化剂型生物填料的制备方法
CN110339146A (zh) * 2019-08-21 2019-10-18 广州臻颜化妆品有限公司 一种水包油包水粉底液及其制备方法
CN116019727A (zh) * 2022-08-16 2023-04-28 广州云也品牌管理有限公司 一种化妆品组合物及其在防晒中的应用

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