WO2007017179A1 - Use of ionic uv-a sunscreens - Google Patents
Use of ionic uv-a sunscreens Download PDFInfo
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- 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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- 0 CC(N(CCC*)C(C)=C1)=CC1=C(C#N)C#N Chemical compound CC(N(CCC*)C(C)=C1)=CC1=C(C#N)C#N 0.000 description 5
- JJLGUNORSYZKKS-UHFFFAOYSA-N CC(N(CCOCCO)C(C)=C1)=CC1=C(C#N)C#N Chemical compound CC(N(CCOCCO)C(C)=C1)=CC1=C(C#N)C#N JJLGUNORSYZKKS-UHFFFAOYSA-N 0.000 description 2
- XYBUCJYJVULPHW-UHFFFAOYSA-N CC(OC(C)=C1)=CC1=C(C#N)C#N Chemical compound CC(OC(C)=C1)=CC1=C(C#N)C#N XYBUCJYJVULPHW-UHFFFAOYSA-N 0.000 description 1
- YXHPYQFOOJCADR-UHFFFAOYSA-N CC1(CC1)[O](CCN)CCOC Chemical compound CC1(CC1)[O](CCN)CCOC YXHPYQFOOJCADR-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
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- 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
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- 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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Abstract
The present invention relates to advantageous uses of 1,4-dihydropyridine derivatives and to novel cosmetic or dermatological sunscreen compositions containing 1,4-dihydropyridine derivatives.
Description
Use of ionic UV-A sunscreens
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.
While there exists a large number of safe and effective UV-B absorbers, the number of UV- A absorbers suitable for the protection of human skin is rather restricted. A good 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. In particular for application to hair such as in hairsprays, shampoos, hair care products, etc., high requirements must be met, and the UV-absorber must adhere to the hair to provide sufficient protection.
Additionally 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.
While the number of available UV-A absorbers which meet at least some of the above requirements is already short, the number of UV-A absorbers which are hydrosoluble or which are suitable for application to the hair is even shorter. 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 However, 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 Furthermore, 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
Corresponding international patent application PCT/EP2005/001379 which is not pre- pubhshed discloses 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
A problem with many UV-sunscreens is that they tend to penetrate into the skin leading to an enhanced systemic exposure For solving this problem polymeric sunscreen agents were
developed as well as encapsulated sunscreen agents Particulated inorganic sunscreen agents also avoid this problem However, 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
Today only two true UV-A I filters are commercially available, Parsol 1789, a dibenzoylmethane derivative and Uvinul A plus, an amino substituted hydroxybenzophenone derivative of the structural formula
Thus it would be desirable to combine these filters in order to achieve a high protection in the UV-Arange
The 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 However, even though 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-methylbenzylιdene camphor, octocrylene or polyslιcone-15
It has surprisingly be found, that amino substituted hydroxybenzophenone derivatives such as Uvinul A plus (BASF AG), have a significant stability problem upon irradiation with UV- light when formulated together with a dibenzoylmethane derivative, such as Parsol 1789
Even the addition of a suitable triplet quencher for Parsol 1789 as described above does not prevent this degradation Thus, there is a significant need for UV-A I sunscreen agents which have a high compatibility with dibenzoylmethane derivatives in cosmetic and dermatological compositions in order to provide a high protection against UV-A radiation
The preparation of cosmetic and dermatological emulsions is particularly difficult in the presence of salts This problem is enhanced, if the salt is the sunscreen agent because in sunscreen compositions a rather high amount of sunscreen agent is necessary to provide a high SPF Therefore, while the UV-A sunscreen agents described in PCT/EP2005/001379 (and which will be described in more detail below) solve many problems which occur with prior art UV-A sunscreen agents, they are difficult to formulate into stable emulsions Therefore there is a need to provide stable emulsions containing these UV-A sunscreen agents
Furthermore, it would be advantageous to improve the water resistance of the ionic UV-A sunscreen agents of PCT/EP2005/001379
Finally, there is still need for compositions having better sunscreen activity
The present inventors found that the 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 Furthermore, 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
The disclosure of PCT/EP2005/001379 is included herein by reference
The UV-A sunscreens to which the present invention relates and which are disclosed in PCT/EP2005/001379 are compounds of the general formula (I)
wherein
R1 and R2 are identical or different electron-withdrawing groups or one of R1 and
R2 is hydrogen and the other of R1 and R2 is an electron-withdrawing group,
R3, R4, R5 and R6 are independently selected from hydrogen atoms, C1-C10 alkyl groups, C2-C10 alkenyl groups, C2-C10 alkynyl groups, C3-C10 cycloalkyl groups, C6-C10 aryl groups, the above groups being unsubstituted or optionally substituted by one to three substituents selected from C1-C6 alkyl groups, halogen, hydroxy and C1-C6 alkoxy groups, or R3 and R5 and/or R4 and R6 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 C1-C6 alkyl groups, C3-C6 cycloalkyl groups, C1-C6 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
Y is a counterion
As used herein, 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 -COOR8, -COR8 or -CONR8 2 group, wherein each R8 is independently hydrogen, C1-C21 alkyl (preferably C1-C6 alkyl), C2-C21 alkenyl (preferably C2-C6 alkenyl), C2-C21 alkynyl (preferably C2-C6 alkynyl), C3-C21 cycloalkyl (preferably C3-C8 cycloalkyl) or C6-C10 aryl (preferably phenyl), each of those groups or preferred groups being unsubstituted or optionally substituted by one to three substituents selected from C1-C6 alkyl groups, halogen, hydroxy and C1-C6 alkoxy groups Preferably at least one of residue R1 and residue R^ is a cyano group, a -COOR8, -COR8 or a -CONR8 2 group, more preferably at least one residue is a cyano group,
still more preferably both residue R1 and residue R2 are selected from a cyano group, a -COOR8, -COR8 or -CONR8 2 group, still more preferred residue R1 is a cyano group and residue R2 is selected from a -COOR8, -COR8 and -CONR8 2 group and most preferred both residue R1 and residue R2 each are a cyano group (CN group) It is also preferred that one residue is a cyano group and the other residue is a -COOR8 group
R3, R4, R5 and R6 are independently selected from hydrogen atoms Ci-C10 alkyl groups, C2-C10 alkenyl groups, C2-C10 alkinyl groups, C3-C10 cycloalkyl groups and C6-C10 aryl groups Each of these groups can be unsubstituted or substituted by one to three substituents selected from C1-C6 alkyl groups, halogen, hydroxy and C1-C6 alkoxy groups Alternatively, it is also possible that R3 and R5 and/or R4 and R6 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 C1-C6 alkyl groups, C3-C6 cycloalkyl groups, C1-C6 alkoxy groups, hydroxy or halogen Preferably R3, R4, R5 and R6 are independently selected from hydrogen atoms, Ci-C6 alkyl groups, C2-C6 alkenyl groups, C5-C8 cycloalkyl groups and a phenyl group, each of which is optionally substituted by one to three substituents, more preferably by one substituent as defined above It is also preferred that R3, R4, R5 and R6 are independently selected from hydrogen atoms and unsubstituted C1-C6 alkyl groups, C2-C6 alkenyl groups, C5-C8 cycloalkyl groups and phenyl groups If R3 and R5 and/or R4 and R6 are taken together with the carbon atom to which they are attached form a 5- or 6-membered ring, a 6-membered ring is preferred, and the rings are preferably unsubstituted or substituted with one substituent as defined above
Most preferably at least one of R3, R4, R5 and R6, more preferably two of R3, R4, R5 and R6, are hydrogen atoms and the other groups R3, R4, R5 and R6 are C1-C6 alkyl groups or C2-C6 alkenyl groups Most preferably R3 and R4 are hydrogen atoms and R5 and R6 are C1-C6 alkyl groups or C2-C6 alkenyl groups, more preferably C1-C3 alkyl groups
The alkyl groups can be branched or straight chain Preferred examples of C1-Ci0 alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, pentyl, neopentyl, hexyl, 2-ethylhexyl and octyl groups
Preferred examples of C3-C10 cycloalkyl groups are cyclopropyl, cyclobutyl cyclopentyl cyclohexyl, cycloheptyl and cyclooctyl groups
Preferred examples of C2-C6 alkenyl groups are ethenyl and n-propenyl groups.
Preferred examples of C6-C10 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. According to the present specification, 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. Preferably 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. The term "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. Preferably residue X contains 1 to 6 hetero atoms, and the hetero atoms are preferably selected from nitrogen, oxygen, sulfur and phosphor atoms. If 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.
It is also possible that 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. Of course, if a carbon atom in residue X is substituted by an amino group, there can also be an unsaturated bond, preferably a double bond between the carbon atom and the nitrogen atom. It is also possible that residue X and residue Y together form a zwitter ion structure.
if tne group which is positively or negatively charged in residue X is negatively charged, residue X carries preferably a single negative charge and is most preferably an acid residue such as a group -0-SO3 , -COO , -0-PO3H , -0-PO3 2 , -SO3 , -PO3H or -PO3 2 Most preferred is group -O-SO3 ' , -SO3 and a group -O-PO3H Typical examples of 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 group is interrupted by a nitrogen atom, the nitrogen atom bears a further group R8 as defined above
A preferred example of a residue X having a single negative charge is a residue
-(C(R9 2))n-(V)m-(C(R9 2))0-(U)p-(C(R9 2))q-W,
wherein each R9 is independently hydroxy or defined as residue R8 above and preferably is a hydrogen atom, hydroxy or a C1-C3 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 R8 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) and W is the residue bearing a negative charge, preferably an acid residue as defined above, most preferably a residue -0-PO3H , a residue -SO3 or a residue -O-SO3 , 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 atoms in residue X is 1 to 10, including the hetero atoms of functional group W, and with the proviso that index o is not O, if index m and index p are both 1 Preferably not more than four residues R9, more preferably not more than two residues R9 are different from hydrogen, most preferably all residues R9 are hydrogen
Another preferred example of a residue X having a single negative charge is a residue
-Ar -W,
wnerein Ar is an aromatic group, preferably a C6-C10 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
It is also preferred that the at least one group which is positively or negatively charged in residue X is a group which has one positive charge Most preferably this group which has one positive charge is a quaternary ammonium ion In this case, residue X is preferably a residue of the formula
wherein each R10 is independently hydrogen or R11 and each R11 is independently defined as residue R8 above, preferably is hydrogen, a C1-C10, preferably C1-C6 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-C6 alkyl, preferably C1-C3 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 In one embodiment of the invention, residue R11 may contain a negative charge and therefore encompass residue Y, e g one residue R11 can be an alkyl group which is substituted with a functional group bearing a negative charge such as an -SO3 group or a similar group
In a preferred embodiment, 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 Preferably, 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 If residue X is negatively charged, 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 If residue Y has more positive charges than residue X has negative charges, residue Y contains a further counterion which balances the additional charge or more than one residue X is balanced by one residue Y For example, residue Y can be
— (Ms+) or Ms+(A )s 1, wherein Ms+ 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
If residue X is positively charged, 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
one residue Y For example, residue Y can be — (Ms ) or Ms (A+)s 1, wherein Ms 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
If 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
It is also possible that X and Y are chemically bonded together, such as in moieties as -(CH2)rN+(R11)2-(CH2)rSθ3 , with r is as defined above and t is an integer of 1 to 10,
preferably 1 to 5, e.g. 2. In such embodiments, residues X and Y together form a zwitter ion structure.
Preferably residues R1 to R6, 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 R3 to R6 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, such as the quaternary ammonium ions of the formula -C(R10 2)r-N+(R11)3 as defined above, may have a lower water- solubility.
Preferred compounds of formula (I) are
and combinations or interchangements of the varied structure elements.
Particularly preferred compounds of formula I are the compounds of formula Il
wherein M+ is a counterion, which is preferably selected from Na+, K+, Li+, NH4 + and 0.5 equivalent of Mg2+ and Ca2+.
The most preferred compound of formula (I) is
which is referred to as 4-Dicyanomethylene-2,6-dimethyl-1 ,4-dihydropyridine-N- (ethyloxysulfate ester mono sodium salt) (see Example 2).
Preferred are also the compounds
wherein M+ is K+, Li+, NH4 + or 0.5 equivalent of Mg 22++ Λ orr ^ Ca„2+
may not have a high water-solubility, but they are particularly preferred for hair care applications.
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).
Knoevenagel reaction
Phosphate residues of the type -0-PO3 2' can for example be prepared from the corresponding alcohol function using e.g. POCI3 with a base as e.g. triethylamine [see e.g. M. -Z. Liu et al., Carbohydr. Res. 330 (3), 413-420 (2001)], with P2O5 and H3PO4 [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-SO3 ' can for example be prepared from the corresponding alcohol function using e.g. SO3 x pyridine [see e.g. W. J. Sanders et al., Tetrahedron 53
(48), 16391 -16422 (1997)], SO3 x NEt3 [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 H2SO4 [see e g S P Gaur et al , Indian J Chem Sect B 21 (1), 46-51 (1982)]
Additionally alternative synthetic routes can be followed using dehydracetic acid and derivatives thereof as starting material (see below), and a skilled person can easily adapt this synthetic route to prepare other compounds of formula (I)
Knoevenagel reaction
Some further preferred compounds of formula (I) and general methods for their production are shown below
Process b)
Process c)
Analogously for
Process d)
Process e)
Process f) 1 Michael Na
Process g)
see general scheme
Process h)
Process j)
Similar to example 2:
Similar to example 1 :
The following compounds of formula (I) are also particularly preferred:
Residues R1 and R2 are both cyano groups, residues R3, R4, R5 and R6 are independently selected from hydrogen atoms and C1-C6 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
a) X is a residue
-(C(R9 2))n-(V)m-(C(R9 2))0-(U)p-(C(R9 2))q-W,
wherein each R9 is independently hydrogen, hydroxy or Ci-C3 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-PO3H or a residue -0-SO3 , or
b) X is a residue
wherein residues R10 are independently selected from hydrogen atoms, hydroxyl groups and C1-C3 alkyl groups, and residues R11 are independently selected from hydrogen atoms and CrC6 alkyl groups which are optionally interrupted by 1 to 2 hetero atoms and which are optionally substituted by 1 to 3 hydroxyl groups, and r is an integer of 1 to 6, or
c) X is a residue
-(C(R9 2))n-(V)m-(C(R9 2))0-(U)p-(C(R9 2))q-W,
wherein each R9 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-PO3H or a residue -0-SO3 , or
wherein residues R10 are independently selected from hydrogen atoms, hydroxy! groups and CrC3 alkyl groups, and residues R11 are independently selected from hydrogen atoms and C1-C6 alkyl groups which are optionally interrupted by 1 to 2 oxygen atoms and which are optionally substituted by 1 to 3 hydroxyl groups, and r is an integer of 1 to 3, or
e) X is a residue
-(C(R9 2))n-(V)m-(C(R9 2))0-W,
wherein each R9 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, and W is a residue -0-PO3H" or a residue -0-SO3 ', or
f) X is a residue
wherein residues R10 are independently selected from hydrogen atoms and Ci-C3 alkyl groups, and residues R11 are independently selected from C1-C6 alkyl groups which are optionally interrupted by 1 to 2 hetero atoms and which are optionally substituted by 1 to 3 hydroxyl groups, and r is an integer of 1 to 3, or
g) X is a residue
-(C(R9 2))n-W,
wnerein each Rs is independently hydrogen, hydroxy or C1-C3 alkyl, and n is an integer of 1 to 6, and W is a residue -0-PO3H or a residue -0-SO3 , or
h) X is a residue
wherein residues R10 are independently selected from hydrogen atoms, hydroxyl groups and C1-C3 alkyl groups, and two residues R11 are C1-C3 alkyl groups, and one residue R11 is a C1-C6 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 R11 form together with the nitrogen atom a pyridinyl group which is unsubstituted or substituted with 1 to 5, preferably 1 to 3 substituent groups R8 as defined above
ι) One of the residues as defined in items a) to h) above, wherein one residue R9 or R10 is a saturated or unsaturated nitrogen containing hydrocarbon group containing up to 5 carbon atoms and one or two nitrogen atoms
Those compounds of formula (I) which comprise a residue
which is unsubstituted or substituted with 1 to 5, preferably 1 to 3 substituent groups R8 as defined above, have a particularly high water-solubility and those compounds of formula (I) are especially preferred
The compounds of formula (I) have adsorption maxima in the UV-A region The compounds of formula (I) are generally incorporated into compositions comprising a compound of formula (I) formulated into a suitable support or substrate Typically 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) In one preferred embodiment such compositions are suited for protecting the skin and/or hair against the deleterious effect of UV radiation In this case the compositions are cosmetic or pharmaceutical compositions which comprise a topically applicable, cosmetically or pharmaceutically acceptable vehicle and diluent as carrier
According to another embodiment 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
Product stability of perfume oils and fragrance substances is a problematic issue as the odorants are often very light sensitive This results in a reduced shelf life due to unpleasant off-odors or color changes The light induced photodegradation can be slowed down by storage of the perfume or fragrance in brown bottles However, due to aesthetic reason this is not always wanted Thus, sunscreen agents such as benzophenone-4 are used to improve the stability of perfume or fragrance compositions against light It has now surprisingly be found that compounds of formula (I) are especially suitable in the protection of perfumes or fragrances versus light induced photodegradation due to the excellent UV-A I absorbing properties
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
Most 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 Surprisingly, it has been found that 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% For the protection of photosensitive ingredients in hair dyes and cosmetics the same amounts and preferred amounts of the compounds of formula (I) can be used
For the preparation of light screening compositions, especially of preparations for dermatological and/or cosmetic use, such as skin protection and sunscreen formulations for everyday cosmetics a compound of formula (I) may be incorporated in auxiliary agents, e g a cosmetic base, which are conventionally used for such formulations Where convenient, 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
The term 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
The compositions contain the compound of formula (I) in an effective amount The term "effective amount" means generally at least 0 1 % by weight of the light screening composition Preferably 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 If 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 wt -% to 15 wt -%, based on the total weight of the compositions
For example, 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
If a combination of different sunscreen agents is used, 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 Preferably 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
The additional screening agents are advantageously selected from the compounds listed below without being limited thereto
Examples of 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-dιphenylacrylate (octocrylene, PARSOL® 340), ethyl 2-cyano-3,3-dιphenylacrylate and the like,
Camphor derivatives such as 4-methyl benzyhdene camphor (PARSOL® 5000), 3-benzylιdene camphor, camphor benzalkonium methosulfate, polyacrylamidomethyl benzyhdene camphor, sulfo benzyhdene camphor, sulfomethyl benzyhdene camphor, therephthalidene dicamphor sulfonic acid and the like,
3-(4'-Trιmethylammonιum)benzylιdene-bornan-2-on-methylsulfat (Mexoryl SK),
3-(4'-Sulfo)-benzylιdene-bornan-2-on and the salts (Mexoryl SL),
Polymer of N-[2(and 4)-(2-oxoborn-3-ylιden-methyl) benzyl] acrylamid (Mexoryl SW),
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-amιnobenzoate (PEG-25 PABA),
Benzophenones such as benzophenone-3, benzophenone-4, 2,2', 4, 4'- tetrahydroxy-benzophenone, 2,2'-dιhydroxy-4,4'-dιmethoxybenzophenone and the like,
Esters of Benzalmalonic acid such as dι-(2-ethylhexyl) 4- methoxybenzalmalonate,
Esters of 2-(4-ethoxy-anιlιnomethylene)propanedιoιc acid such as 2-(4- ethoxy anιlιnomethylene)propanedιoιc acid diethyl ester as described in the European Patent Publication EP 0895 776,
Organosiloxane compounds containing benzmalonate groups as described in the European Patent Publications EP 0358584 B1 , EP 0538431 B1 and EP 0709080 A1 ,
Drometπzole trisiloxane (Mexoryl XL),
Pigments such as microparticulated TiO2, and the like The term "microparticulated" refers to a particle size from about 5 nm to about 200 nm, particularly from about 15 nm to about 100 nm The TiO2 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 (PARSOLΘHS) 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
Tπazine derivatives such as octyl triazone (UVINUL T-150), dioctyl butamido tπazone (UVASORB HEB), bis ethoxyphenol methoxyphenyl tπazine (Tinosorb S) and the like
3,3'-(1 ,4-Phenylendιmethιn)-bιs (7,7-dιmethyl-2-oxobιcyclo-[2 2 1]heptan-1- methan sulfonic acid (Mexoryl SX),
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'-methoxydιbenzoyl- methane (PARSOL® 1789), dimethoxydibenzoylmethane, isopropyldibenzoylmethane and the like,
Benzotπazole derivatives such as 2,2'-methylene-bιs-(6-(2H-benzotrιazole-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)bιs-(1 H-benzιmιdazol-4,6-dιsulfonιc acid) (Neohehopan AP),
Amino substituted hydroxybenzophenones such as 2-(4-Dιethylamιno-2- hydroxy-benzoyl)-benzoιc acid hexylester (Uvmul A Plus) as described in the European Patent Publication EP 1046391 ,
2,4-Bιs[4-(2-ethylhexyl-oxy)-2-hydroxyphenyl]-6-(4-methoxyphenyl)-1 ,3,5- tπazin (Tinosorb S),
Pigments such as microparticulated ZnO or TiO2 and the like The term "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, tπmethoxycaprylylsilane, triethoxy caprylylsilane and silicium dioxide Such coatings are well known in the art Examples of such 'microparticulated' ZnO or TiO2 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 be doped by other metals such as manganese as e g described in WO 2004/058 209
Commercial examples which can be used according to the invention are published e g by ctfa (Cosmetic, Toiletry and Fragrance Association) and reference can be made to Uvmul® TiO2, Uvmul T hte SF, Uvmul T lite SFS by BASF, Eusolex® T-Avo by Merk, Optisol™ UV Absorber by Oxonica, Titanium dioxide AS by Cadre, Parsol TX by DSM without being limited hereto
The microparticulated ZnO or TiO2 and the like can be in the form of a powder or being pre- dispersed in oil and/ or water
As dibenzoylmethane derivatives have limited photostabihty it may be desirable to photostabilize these UV-A screening agents Thus, the term "conventional UV-A screening agent" also refers to dibenzoylmethane derivatives such as e g PARSOL® 1789 stabilized by, e g ,
3,3-Dιphenylacrylate derivatives as described in the European Patent Publications EP 0 514 491 B1 and EP 0 780 119 A1 ,
Benzylidene camphor derivatives as described in the US Patent No 5,605,680,
Organosiloxanes containing benzmalonate groups as described in the European Patent Publications EP 0358584 B1 , EP 0538431 B1 and EP 0709080 A1
Naphthalene carboxylic acid derivatives as described in WO 2002/087528 A1 such as Corapan TQ
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
Further preferred 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 TiO2 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 be doped by other metals such as manganese as e g described in WO 2004/058 209
Commercial examples which can be used according to the invention are published e g by the ctfa and reference can be made to Uvinul® TiO2, Uvinul T lite SF, Uvinul T lite SFS by BASF, Eusolex® T-Avo by Merk, Optisol™ UV Absorber by Oxonica, Titanium dioxide AS by
Cadre, Parsol TX by DSM without being limited hereto The microparticulated ZnO or TiO2 and the like can be in the form of a powder or being pre-dispersed in oil and/ or water
Thus, compositions containing a compound of formula (I) as defined above and titanium dioxide and/or zinc oxide are also preferred
Other preferred non-oenetrating UV screening agents are encapsulated UV screening agents such as the commercial products Eusolex UV pearls or other encapsulated agents The term "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 Such 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 00/72806 Particularly preferred are the encapsulated sunscreens as disclosed in US-A 6,303,149, WO 2005/009604 and WO 03/066209 which are included herein by reference
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 Most preferred are 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 μm to 8 μm, more preferably in the range from 3 to 5 μm and most preferably in the range from 3 to 4 μm
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-fιlters 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)
Preferred are also combinations containing a compound of formula (I) and additionally at least one other non-penetrating UV-sunscreen as described above Thus, 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
Particularly preferred are compositions containing a combination of a sunscreen agent according to formula (I) above and a micronized organic UV-fιlter which also has a relatively low skin penetration such as methylene bis-benzotriazolyl tetramethylbutylphenyl (Tinosorb M)
Particularly preferred are also 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 tπazone which sold under the trade name Uvasorb HEB or Ethylhexytπazone 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 preferably, the skin penetration rate of the additional sunscreen agent is even lower than the skin penetration rate of the sunscreen agent of formula (I)
Also preferred are compositions containing a combination of a sunscreen agent according to formula (I) and at least two additional sunscreen agents selected from the Triazine derivatives such as Uvinul T150, Uvasorb HEB, Tinosorb S, micronized organic UV-fιlters such as Methylene bis-benzotriazolyl tetramethylbutylphenol, and/ or polymeric UV-filter such as Parsol SLX, microparticulated titanium dioxide, zinc oxide and an encapsulated UV screening agent in order to provide sunscreen combinations with a very low skin penetration in order to minimize the systemic exposure
Surprisingly, the 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
Particularly preferred 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
Also it has surprisingly been found that 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-methylbenzylιdene 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 tπazone (Uvinul T 150). Optionally other UV sunscreen agents selected from the non-penetrating sunscreen agents as described above can be added
Particularly preferred are combinations of compounds of formula (I) with dibenzoylmethane derivatives such as Parsol 1789 or cinnamate derivatives such as Parsol MCX or combinations thereof
Surprisingly, the 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)
Particularly preferred are combinations of compounds of formula (I) with dibenzoylmethane derivatives such as Parsol 1789
Preferred are also combinations containing a compound of formula (I) and benzoic acid derivatives such as diethylamino hydroxybenzoyl hexyl benzoate (Uvinul A Plus) or triazine derivatives such as bis-ethylhexyloxyphenol methoxyphenyl triazine (Tinosorb S)
The 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
An additional amount of antioxidants/ preservatives is 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-carnosιne, D-carnosine, L-carnosine and derivatives (e g anserine), carotenoids, carotenes (e g α-carotene, β-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-acetyl-, methyl-, ethyl-, propyl-, amyl-, butyl- and lauryl-, palmitoyl-, oleyl-, y-ltnoleyl-, cholesteryl- and glycerylester) and the salts thereof, dilaurylthiodipropionate, distearylthiodipropionate, thiodipropionic acid and its derivatives (ester, ether, peptides, lipids, nucleotides, nucleosides and salts) as well as sulfoximine compounds (such as buthioninsulfoximine, homocysteinsulfoximine, buthioninsulfone, penta-, hexa-, heptathioninsulfoximine) in very low compatible doses (e g pmol bis μmol/kg), additionally (metal)-chelators (such as α-hydroxyfatty acids, palmic-, phytinic acid, lactoferrin), β-hydroxyacιds (such as citric acid, lactic acid, malic acid), huminic acid, gallic acid, gallic extracts, bilirubin, biliverdin, EDTA, EGTA and its derivatives, unsaturated fatty acids and their derivatives (such as γ-hnoleic acid, linolic acid, oleic acid), folic acid and its derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and derivatives (such as ascorbylpalmitate and ascorbyltetraisopalmitate, Mg-ascorbylphosphate, Na- ascorbylphosphate, ascorbylacetate), tocopherol and deπvates (such as vitamin-E-acetate), mixtures of nat vitamin E, vitamin A and derivatives (vitamin-A-palmitate and -acetate) as well as coniferylbenzoate, rutinic acid and derivatives, α-glycosylrutιn, ferulic acid, furfurylideneglucitol, camosine, butylhydroxytoluene, butylhydroxyanisole, tπhydroxybutyrophenone, urea and its derivatives, mannose and derivatives, zinc and derivatives (e g ZnO, ZnSO4), Selen and derivatives (e g selenomethionine stilbenes and derivatives (such as stilbenoxide, trans-stilbenoxide) and suitable derivatives (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of the named active ingredients One or more preservatives/antioxidants may be present in an amount about 0 01 wt % to about 10 wt % of the total weight of the composition of the present invention Preferably, one or more preservatives/antioxidants are present in an amount about 0 1 wt % to about 1 wt %
Typically 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-dιιsostearate, polyglycerol esters of oleic/isostearic acid, polyglyceryl-6 hexaπcinolate, polyglyceryl-4-oleate, polygylceryi-4 oleate/PEG-8 propylene glycol cocoate, oleamide DEA, TEA myπstate, TEA stearate, magnesium stearate, sodium stearate, potassium laurate, potassium ricinoleate, sodium
cocoate, sodium tallowate, potassium castorate, sodium oleate, and mixtures thereof Further suitable emulsifiers are phosphate esters and the salts thereof such as cetyl phosphate (Amphisol® A), diethanolamine cetyl phosphate (Amphisol®), potassium cetyl phosphate (Amphisol® K), sodium glyceryl oleate phosphate, hydrogenated vegetable glyceπdes phosphate and mixtures thereof Furthermore, one or more synthetic polymers may be used as an emulsifier For example, PVP eicosene copolymer, acrylates/C1O 3o alkyl acrylate crosspolymer, acryiates/steareth-20 methacrylate copolymer, PEG- 22/dodecyl glycol copolymer, PEG-45/dodecyl glycol copolymer, and mixtures thereof The preferred emulsifiers are cetyl phosphate (Amphisol® A), diethanoiamine cetyl phosphate (Amphisol®), potassium cetyl phosphate (Amphisol® K), PVP Eicosene copolymer, acrylates/C10-30-alkyl acrylate crosspolymer, PEG-20 sorbitan isostearate, sorbitan isostearate, and mixtures thereof The one or more emulsifiers are present in a total amount about 0 01 wt % to about 20 wt % of the total weight of the composition of the present invention Preferably, about 0 1 wt % to about 10 wt % of emulsifiers are used
The lipid phase can advantageously be chosen from
mineral oils and mineral waxes,
oils such as triglycerides of caprinic acid or caprylic acid, preferable castor oil,
oils or waxes and other natural or synthetic oils, in a preferred embodiment 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, octyldodecylmyπstate, cetearylisononanoate, isopropylmyristate, isopropylpalmitate isopropylstearate, isopropyloleate, n-butylstearate, n-hexyllaureate, n-decyloleate, isooctylstearate, isononylstearate, isononylisononanoate, 2- ethyl hexybalmitate 2-ethylhevyiiaurate, 2-hexy!decy!stearate, 2- octyldodecylpalmitate, stearylheptanoate, oleyloleate, oleylerucate, erucyloleate, erucylerucate, tridecylstearate, tridecyltrimellitate, as well as synthetic, half-synthetic or natural mixtures of such esters e g jojoba oil
Other 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 cocoglyceπde, 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 polyolefins are polydecenes, dialkyl ethers such as dicaprylylether, linear or cyclic silicone oils such as preferably cyclomethicone (octamethylcyclotetrasiloxane, cetyldimethicone, hexamethylcyclotrisiloxane, polydimethylsiloxane, poly(methylphenylsιloxane) and mixtures thereof
Other fatty components which can advantageously be incorporated in formulations of the present invention are isoeikosane, neopentylglycoldiheptanoate, propyleneglycoldicaprylate/dicaprate, caprylic/capπc/diglycerylsuccinate, butyleneglycol caprylat/caprat, Ci2-i3-alkyllactate, dι-C12-i3 alkyltartrate, tπisosteaπn, dipentaerythπtyl hexacaprylat/hexacaprate, propyleneglycolmonoisostearate, tricaprylin, dimethylisosorbid Especially beneficial is the use of mixtures C12 15-alkylbenzoate and 2- ethylhexyhsostearate, mixtures Ci2 15-alkylbenzoate and isotπdecylisononanoate as well as mixtures of C12 15-alkylbenzoate, 2-ethylhexylιsostearate and isotπdecylisononanoate
The oily phase of the formulation of the present invention can also contain natural vegetable or animal waxes such as bees wax, china wax, bumblebee wax and other waxes of insects as well as shea butter and cocoa butter
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 Additionally an emollient provides a softening or soothing effect on the skin surface and is generally considered safe for topical use Preferred emollients include mineral oils, lanolin, petrolatum, capπc/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
isononyl iso-nonanoate, ethers such as polyoxypropylene butyl ethers and polyoxypropylene cetyl ethers, and C-I2 15-alkyl benzoates, and mixtures thereof The most preferred emollients are hydroxybenzoate esters, aloe vera, C12 15-alkyl benzoates, and mixtures thereof An emollient is present in an amount of about 1 wt % to about 20 wt % of the total weight of the composition The preferred amount of emollient is about 2 wt % to about 15 wt %, and most preferably about 4 wt % to about 10 wt %
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 % in a composition of the present invention, preferably about 1 wt % to about 5 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 acrylate crosspolymers preferably a carbomer, such as carbopole® of type 980, 981 , 1382, 2984, 5984 alone or mixtures thereof Suitable neutralizing agents which may be included in the composition of the present invention to neutralize components such as e g an emulsifier or a foam builder/stabilizer include but are not limited to alkali hydroxides such as a sodium and potassium hydroxide, organic bases such as diethanolamine (DEA), tπethanolamine (TEA), aminomethyl propanol, and mixtures thereof, amino acids such as arginine and lysine and any combination of any foregoing The neutralizing agent can be present in an amount of about 0 01 wt % to about 8 wt % in the composition of the present invention, preferably, 1 wt % to about 5 wt %
The addition of electrolytes into the composition may be necessary to change the behavior of a hydrophobic emulsifier Thus, 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 Other suitable electrolytes can be on the basis of organic anions such as, but not limited to, lactate, acetate, benzoate, propionate, tartrate and citrate As 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
The cosmetic 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 When 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/OΛ/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 aerosol mousse The emulsions can also contain anionic, nonionic, cationic or amphoteric surfactants
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 Furthermore, 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 Surprisingly 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 an emulsion The compounds of formula (I) show a very low skin penetration and have excellent adhesiveness to skin and hair
It is desirable to have cosmetic or dermatological compositions having a high protection in the UV-A range, especially in the UV-A I range in order to avoid adverse effects such as premature skin aging, sunburn, immune suppression, and different types of skin cancer which are induced by UV-A irradiation However, it is very difficult to obtain a high UV-A and even more difficult achieve a high UV-A I protection in a cosmetic or dermatological formulation with only one single UV-A filter Thus, it is highly desirable to combine at least two UV-A filters to achieve a high protection level against UV-A I radiation However, there are not that many UV-A filters commercially available which effectively absorb in the UV-A I range Surprisingly it has been found that Parsol 1789, the most widely used commercially available UV-A filter is not compatible with Uvinul A Plus, a UV-A filter also having an absorption maxima in the UV-A I range (355nm) Both compounds are completely degraded upon irradiation with 10 MED
Unexpectedly sunscreen agents of formula (I) and in particular the sunscreen agents of formula (II) above are photostable over the whole UV-A and UV-B range, even under intensive UV radiation even if they are formulated with dibenzoylmethane derivatives such as Parsol 1789 Parsol 1789 itself is degraded upon UV irradiation and thus the addition of a suitable stabilizer into the cosmetic or dermatological compositions is preferred Thus, combinations of compounds of formula (I) (in particular of formula II) with Parsol 1789 and at least one known photostabihzer for Parsol 1789 is provided Preferred are combinations of compounds of formula (I) with Parsol 1789 and at least on photostabihzer selected from octocrylene (Parsol 340), polysιlιcone-15 (Parsol SLX), 4-methylbenzylιdene camphor (Parsol 5000), benzophenone-3, ethylhexyl methoxycinnamate (Parsol MCX) or diethylhexyl 2,6-naphthalate (Corapan TQ) Most preferred are combinations of compounds of formula (I) with Parsol 1789 and polysιlιcone-15 (Parsol SLX), combinations of compounds of formula (I) with Parsol 1789 and octocrylene (Parsol 340), combinations of compounds of formula (I) with Parsol 1789 and polysιlιcone-15 (Parsol SLX) and octocrylene (Parsol 340) in order to give photostable UV protection over the complete UV-range from 290-400nm Optionally other UV-screening agents can be added Since PCT/EP2005/001379 explicitly discloses compositions containing the compound of example 2, Parsol 5000 and Parsol MCX, a corresponding disclaimer has been added to some claims
The chemical name of Parsol 1789 is 4-tert -butyl-4'-methoxydιbenzoylmethane
Compounds according to formula (I) have a high photostabihty, but do not achieve the desired 100% level if used in concentration levels of < 3% Surprisingly it has been found, that the addition of at least one hydrosoluble UV-A or UV-B screening agent such as imidazole derivatives e g 2-phenyl benzimidazole sulfonic acid and its salts (PARSOL®HS) or Phenylene-1 ,4-bιs-benzιmιdazolsulfonιc acids or salts such as 2,2-(1 ,4-phenylene)bιs- (1 H-benzιmιdazol-4,6-dιsulfonιc acid) (Neohehopan AP) or combinations thereof lead to an enhanced photostabihty of compounds of formula (I) even when used in concentrations < 3% Thus, preferred are cosmetic or dermatological compositions containing compounds of formula (I) and at least one additional hydrosoluble UV-A, UV-B or broadband screening agent in a ratio of 5 1 to 1 10, preferably in ration of 2 1 to 1 5 Optionally other UV-A, UV-B or broadband screening agents can be present
In addition, it has surprisingly been found, that also the addition of 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% for stabilizing a sunscreen composition in the form of an emulsion, so that the emulsion is stable for at least three months at 43°C, preferably for at least six months at this temperature "Stability" of an emulsion means in the present specification that the emulsion does not separate into a water and an oil phase while stability of a compound means that the compound remains chemically unchanged, i e that the compound is not destroyed or decomposed or changed to another chemical compound
As discussed in the introductory part of the present application, 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 It is known that many ionic UV screening agents such as phenylbenzimidazolesulfonic acid or disodiumphenyldibenzimidazole tetrasulfonate cause problems regarding the stability of emulsions It was now unexpectedly found that 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 Thus, 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
Examples for thickening agents are as follows
a) Lipid thickeners:
Bees Wax AEC Beeswax (A&E Connock (Perfumery & Cosmetics) Ltd )
Glyceryl Hydroxystearate, Cetyl Palmitate, Microcrystalline Wax, Trihydroxystearin Unitina
BW (Universal Preserv-A-Chem, Inc)
Behenyl Alcohol Lanette 22 (Cognis Corporation, Care Chemicals)
Candelilla Wax AEC Candelilla Wax (A&E Connock (Perfumery & Cosmetics) Ltd )
Carnauba Wax AEC Camauba Wax (A&E Connock (Perfumery & Cosmetics) Ltd )
Ceresine Ceresine Wax (Megachem Pty Ltd )
Cetearyl Alcohol AEC Cetearyl Alcohol (A&E Connock (Perfumery & Cosmetics) Ltd )
Cetyl Alcohol AEC Cetyl Alcohol (A&E Connock (Perfumery & Cosmetics) Ltd )
Cetyl Palmitate Cutina CP (Cognis Corporation, Care Chemicals)
Glyceryl Stearate Tegin Pellets (Degussa Care Chemicals)
Glyceryl Mynstate Estol 3650 (Uniqema)
Hydrogenated Castor Oil Cutina HR Powder (Cognis Corporation, Care Chemicals)
Hydrogenated Palm Glycerides Lamesoft T 120 (Cognis Corporation, Care Chemicals)
Hydrogenated Peanut Oil Groundnut 36 (Karlshamns AB)
Hydrogenated Tallow Glycerides Almolan AE (Alma AB Chimica S R L)
Microcrystalline Wax AEC Microcrystalline Wax (A&E Connock (Perfumery & Cosmetics)
Ltd )
Myristyl Alcohol Lanette 14 (Cognis Corporation, Care Chemicals)
Myristyl Lactate Crodamol ML (Croda Chemicals Europe, Ltd )
Myristyl Mynstate Tegosoft MM (Degussa Care Specialties)
Ozokerite Ozokerite Wax (Megachem Pty Ltd )
Paraffin Calspa Wax (CaIa Products)
Petrolatum Merkur 1 15 - 831 (Merkur Vaseline GmbH & Co KG)
Polyethylene Hoechst Wax PE 130 (Clariant GmbH)
Stearic acid Stearic acid (Lipo Chemicals, Inc)
Stearyl Alcohol Lanette 18 (Cognis Corporation, Care Chemicals) b) Thickeners of vegetable and animal origin and their derivatives: b.1. Cellulose and cellulose derivatives:
Hydroxypropylcellulose Klucel Hydroxypropylcellulose (Hercules Incorporated)
Cellulose Arbocel A300 (J Rettenmaier & Sohne)
Cellulose Gum Akucell CMC (Robeco Inc)
Cetyl Hydroxyethylcellulose Unislim (Sederma, Inc/Croda Inc)
Ethyl Cellulose Brillance 515 (Gattefosse s a s)
Hydroxyethyl Ethylcellulose Elfacos CD 481 (Akzo Nobel Chemicals Inc )
Hydroxyethylcellulose Tylose H (Clariant Corporation)
Methylcellulose Methocel A (Amerchol Corporation)
Methyl Hydroxyethylcellulose Tylopur MH (Clariant Corporation)
Hydroxypropyl Methylcellulose Methocel E (Amerchol Corporation) b.2. Starch and starch derivatives:
Aluminum Starch Octenylsuccinate Dry-Flo PC (National Starch & Chemical Company)
Sodium Polyacrylate Starch Sanfresh ST-100C (Sanyo Chemical Industries Ltd) b.3. Guar Gum:
AEC Guar Gum (A&E Connock (Perfumery & Cosmetics) Ltd ) b.4. Locust Bean Gum:
Vidogum (Unipektin AG) b.5. Pectins:
Pectin Genu (Hercules Inc ) b.6. Agar:
Agar Powder (Megachem Pty Ltd ) b.7. Alginates:
Sodium Alginate Keltone LVCR (ISP International Specialty products)
Alginic Acid Kelacid (ISP International Specialty Products)
Propylene Glycol Alginate K3B426 (ISP International Specialty Products)
Sodium/calcium Alginate Kelset (ISP International Specialty Products) b.8. Carrageenan:
AEC Carrageenan Gel (A&E Connock (Perfumery & Cosmetics) Ltd )
b.9. Xanthan Gum:
Keltrol (in different qualities) (CP Kelco) Kelzan (in different qualities) (CP Kelco) Rhodicare (in different qualities) (Rhodia lnc ) b.10. Gelatin: AC Gelatin Powder 300 (Active Concepts LLC) c) Mineral and modified mineral thickeners: c.1. Silica:
Aerosil 130 (Degussa AG) c.2. Bentonite:
AEC Bentonite (A&E Connock (Perfumery & Cosmetics) Ltd ) c.3. Aluminium Stearate:
Hostacerin WO (Clariant Corporation) c.4. Zinc Stearate:
Radiastar 1170 (Oleon NV) c.5. Magnesium Aluminium Silicate:
Acti-Gel (Active Minerals) c.6. Aluminium-Magnesium- Hydroxystearate:
Giligel ALM (BK Giuhne Chemie GmbH & Co OHG) d) Synthetic Thickeners d.1. The carbomers and similar hydrocolloid thickeners.
Carbopol ETD 2001 Polymer (Noveon, lnc)
Carbopol ETD 2050 Polymer (Noveon, lnc)
Carbopol Ultrez 21 Polymer (Noveon, lnc)
Carbopol Ultrez 10 Polymer (Noveon, lnc)
Carbopol 934 Polymer (Noveon, lnc)
Carbopol 940 Polymer (Noveon, lnc)
Carbopol 941 Polymer (Noveon, lnc)
Carbopol 954 Polymer (Noveon, lnc)
Carbopol 980 Polymer (Noveon, lnc)
Carbopol 981 Polymer (Noveon, lnc)
Carbopol 2984 Polymer (Noveon, lnc)
Carbopol 5984 Polymer (Noveon, lnc)
Carbopol 934P Polymer (Noveon, lnc)
Pemulen TR-1 Polymer (Noveon, lnc)
Pemulen TR-2 Polymer (Noveon, Inc) d.2. PVM/MA Decadiene Crosspolymer or Sodium PVM/MA Decadiene Crosspolymer:
Stabileze 06 (International Specialty Products)
Stabileze QM (International Specialty Products)
Stabileze XL-80W (International Specialty Products) d.3. Acryiates/Steareth-20 Methacrylate Copolymer:
Aculyn 22 (Rohm and Haas Company, Inc) d.4. Polyethylene Glycols, Ethoxylated Carboxylic Acids and Ethoxylated Fatty
Alcohols:
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
Polyacrylamides, C13-14 Isoparaffin, Laneth-7 Flocare FL 920 3% (SNF S A ) Sodium Acrylates Copolymer, Mineral Oil, PPG-1 Trιdeceth-6 Salcare SC 91 (Ciba Specialty Chemicals)
Polyquatemιum-37, Propylene Glycol Dicaprylate/Dicaprate, PPG-1 Trιdeceth-6 Salcare SC 96 (Ciba Specialty Chemicals)
Particularly preferred 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
Particularly preferred are also 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 myπstate, glyceryl stearate, etc , fatty acids such as steaπc acid, etc , hydrogenated fats such as hydrogenated castor oil, hydrogenated palm glyceπdes, 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 the sunscreen agents of formula (I) as defined above, which were stable for at least six months at 43°C and which did not separate into a water and oil phase
Most preferred are compositions containing a sunscreen agent of formula (I) and cellulose or cellulose derivatives (such as hydroxyethylceNulose) or xanthan gums (such as Keltroi in different qualities) or carbomers( such as Carbopols) and mixtures thereof
According to the present invention it was also found that 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
Examples of emulsifiers are as follows
a) Amphoteric Surfactants
Cocamidopropyl Betaine lncronam 30 (Croda Chemicals Europe Ltd ) b) Anionic Surfactants: b.1. Carboxylic acids and salts thereof:
Stearic Acid Emersol 120 (Cognis Corporation)
Laurie Acid Prifrac 2920 (Uniquema)
Oleic Acid Emersol 210 (Cognis Corporation)
Sodium Tallowate Norfox XXX Granules (Norman, Fox & Co )
Sodium Cocoate Norfox Coco Powder (Norman, Fox &Co )
Sodium Stearate AEC Sodium Stearate (A&E Connock (Perfumery & Cosmetics) Ltd )
Magnesium Stearate Radiastar 1100 (Oleon NV)
TEA-myπstate AEC TEA-Mynstate (A&E Connock (Perfumery & Cosmetics) Ltd )
TEA-stearate AEC TEA-Stearate (A&E Connock (Perfumery & Cosmetics) Ltd )
Potassium Laurate
Potassium Ricinoleate
Potassium Castorate
b.2. Alkylsulfates, Alkylethersulfates and Alkylsulfonates:
Alkyl Sulfates (fatty alcohol sulfates) Sodium Lauryl Sulfate Texapon K 12 P (Cognis
Deutschland GmbH & Co KG)
Alkyl Benzene Sulfonates Sodium Dodecyl Benzene Sulfonate Bio Soft (Stepan Company)
Alkane sulfonates or secondary alkyl sulfates and fatty acid methyl ester sulfonates
Sodium C13-17 Alkane Sulfonate Marlon PS 30 (Sasol Germany GmbH)
Alkyl ether sulfates Sodium |_aureth Sulfate Texapon NSO (Cognis Care Chemicals GmbH
& Co KG) and Phenol Ether Sulfates
Sulfosuccinates Sodium Dioctyl Sulfosuccinate Triton GR-5M Surfactant (Dow Chemicals
USA)
Acyl isethionates Sodium Cocoyl lsethionate Hostapon SCI-65 (Claπant Corporation)
Alkanolamine sulfates, Taurines, Methyltaurines Sodium Methyl Stearoyl Taurate Sofcare
ST (Kao Corporation), Imidazole Sulfates b.3. Alkyl Phosphates:
Cetyl Phosphate Amphisol A (DSM Nutritional Products)
Potassium Cetyl Phosphate Amphisol K (DSM Nutritional Products) c) Cationic Surfactants:
Quaternaries Stearalkonium Chloride Incroquat SDQ-25 (Croda Chemicals Europe Ltd ) d) Nonionic Surfactants: d.1. Fatty alcohols:
Cetearyl Alcohol Lanette O (Cognis Corporation, Care Chemicals)
Cetyl Alcohol Lanette 16 (Cognis Corporation, Care Chemicals)
Stearyl Alcohol Lanette 18 (Cognis Corporation, Care Chemicals)
Cetearyl Alcohol Lanette O (Cognis Corporation, Care Chemicals)
Laneth Laneth-5 Polychol 5 (Croda Chemicals Europe, Ltd )
Laureth Laureth-7 Genapol LA 070 (Clariant Corporation)
Octoxynol Octoxynol-16 Triton X-165 Surfactant (Dow Chemical USA)
Nonoxynol Nonoxynol-30 Arkopal N-300 (Clariant Corporation) d.2. Sorbitan and Sorbitol derivatives like:
Sorbitan Oleate Dehymuls SMO (Cognis France)
Sorbitan Sesquioleate Arlacel C (Uniquema Americas)
Sorbitan lsostearate Arlacel 987 (Uniquema Americas)
Sorbitan Trioleate Arlacel 85 (Uniquema Americas)
Polysorbate 60 Tween 60 (Uniquema Americas)
PEG-10 Sorbitan Laurate Liposorb L-10 (Lipo Chemicals, lnc )
Sorbitan Laurate Span 20 (Uniquema Americas)
Sorbitan Sesquusostearate AEC Sorbitan Sesqunsostearate (A&E Connock (Perfumery &
Cosmetics) Ltd )
PEG-6 lsostearate Olepal Isosteaπque (Gattefosse s a s )
PPG-17 Dioleate
Sorbitan Stearate Arlacel 60 (Uniquema Americas) d.3. Sucrose and Glucose derivatives like:
Sucrose Distearate Crodesta F-10 (Croda Chemicals Europe, Ltd)
Sucrose Cocoate Crodesta SL-40 (Croda Chemicals Europe, Ltd )
Methyl Glucose Sesqunsostearate no trade name
Methyl Glucose lsostearate lsolan IS (Degussa Care Specialties)
Cetearyl Glucoside Tego care CG 90 (Degussa Care Specialties) d.4. Alkanolamides like:
Stearamide DEA Colamid 286 (Colonial chemical lnc )
PEG-4 Stearamide Nikkol TAMDS-4 (Nikko Chemicals Co , Ltd ) d.5. Amine oxides:
Cocamidopropylamine Oxide Colalux CAO-35 (Colonial Chemical lnc ) d.6. Ethoxyiated carboxylic Acids or Polyethyleneglycol esters and
Polyethyleneglycol ethers:
Steareth-2 Bπj 72 (Uniquema Americas)
Steareth-21 Brij 721 (Uiniquema Americas)
PEG-9 Laurate AEC PEG-9 Laurate (A&E Connock (Perfumery & Cosmetics) Ltd )
PEG-40 Hydrogenated Castor Oil Cremophor RH-40 (BASF Corporation)
Ceteareth-25 Cremophor A25 (BASF Corporation)
PEG-7 Hydrogenated Castor Oil Cremophor WO-7 (BASF Corporation)
PEG-30 Dipolyhydroxystearate Arlacel P 135 (Uniquema Americas) d.7. Monoglycerides:
Monoglycerides Succinate
Sodium Cocomonoglyceride Sulfate Nikkol SGC-80N (Nikkol Chemicals Co Ltd ) d.8. Glyceryl Esters and Polyglyceryl Esters:
Polyglyceryl-10 lsostearate Nikkol Decaglyn 1-IS (Nikko Chemicals Co , Ltd)
Polyglyceryl-6 Oleate Sunsoft Q-17F (Taiyo Kagaku Company, Ltd )
Polyglyceryl-3-Dιιsostearate Hostacerin TGI (Claπant Corporation)
Polyglyceryl-4-Oleate AEC Polyglyceryl-4-oleate (A&E Connock (Perfumery & Cosmetics)
Ltd )
PEG-20 Almond Glycerides Crovol A-40 (Croda, lnc )
Polyglyceryl-2 Dipolyhydroxystearate Dehymuls PGPH (Cognis Corporation, Care
Chemicals)
Polyglyceryl-3 Methylglucose Distearate Tego Care 450 (Degussa Care Specialties) d.9. Dimethicone Copolyols:
PEG/PPG-18/18 Dimethicone Dow Corning 190 Surfactant (Dow Corning Corporation) d.10. Meroxapols:
Meroxapol 174 Pluronic 17 R4 (BASF Corporation) d.11. Poloxamers:
Poloxamer 124 Pluronic L-44 (BASF Corporation) d.12. Mixtures
Sorbitan Oleate (and) Hydrogenated Castor Oil (and) Beeswax (and) Stearic Acid Arlacel
481 (Uniquema Americas)
Sorbitan Stearate (and) Sucrose Cocoate Arlatone 2121 (Uniquema Americas)
Polyglyceryl-4-oleate (&) PEG-8 Propylene Glycol Cocoate (A&E Connock (Perfumery &
Cosmetics) Ltd )
Particularly preferred for the preparation of emulsions containing the sunscreen agents of formula (I) as defined above, independent of whether these emulsions are O/W emulsions or W/O emulsions, are ionic emulsifiers and the salts thereof such as e g cetylphosphate, potassium cetylphosphate, tπlaureth-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
With these emulsifiers it became possible to formulate emulsions containing the sunscreen agents of formula (I) as defined above, which were stable for at least three months at 43°C
As discussed above, water-soluble UV-screening agents (such as UV-screening agents which are ionic or in the form of pigments) sometimes have the problem that they are removed from the skin and hair with water even if they are applied in the form of an emulsion Therefore, the UV protection of an sun protecting composition is reduced e g after swimming or water sports To reduce this problem it is preferred to combine the compounds of formula (I) in cosmetic and dermatological sunscreen compositions with film forming agents for increasing the water resistance of the compositions Furthermore, it was
unexpectedly found that some film forming agents even increase 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 Witco Organo Silicones Group), polyvinylpyrrolidone/ vinylacetate copolymers (e g Luvisco! VA 64 powder of BASF AG) etc
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 tπcontanyl polyvinylpyrrolidone (e g Antaron WP-660) which are available from GAF Chemicals Cooperation or ISP Furthermore, vinyl pyrrolidone/eicosane copolymers such as the compound Ganex V-220 of the company ISP and Stearoxy Dimethicone (Abil Wax 2434), Behenoxy Dimethicone (Abil Wax 2440), Stearyl Dimethicone (Abil Wax 9800), Cetyl Dimethicone (Abil Wax 9801 , Abil Wax 9814, Abil Wax 9840), C24-28 Alkyi Methicone (Abil Wax 9810 P), Aery lates/C 12-22 Alkyl Methacrylate Copolymer (Allianz OPT available from ISP or Aculyn PE Polymer from Rohm and Haas Company, lnc ) are preferred
Particularly preferred are also cosmetic or dermatological compositions containing a compound of formula (I) in addition with so-called "boosters" which enhance the activity of UV sunscreen agents Such boosters 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
The 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
The following examples are provided to further illustrate the processes and compositions of the present invention These examples are illustrative only and are not intended to limit the scope of the invention in any way
Example 1
4-Dicyanomethylene-2,6-dimethyl-1 ,4-dihydropyridine-N-(ethyloxy-ethyloxyphosphate ester mono sodium salt):
a) 4-Dicyanomethylene-2,6-dimethyl-1 ,4-dihydropyridine-N-(ethyloxy-ethanol)
A 350 ml three necked reaction flask, equipped with a thermometer, a reflux condenser and an oil bath with a magnetic stirrer was charged with 30.1g (175mmol) of 4- Dicyanomethylene-4H-pyran (prepared according HeIv. Chim. Acta 1962, 1908-1917) and 20.2g (192 mmol) of 2-(2-Aminoethoxy)-ethanol (Fluka) in 150 ml of n-Butanol and heated for 90 Min. under Ar atmosphere. After cooling the bulky suspension was filtered the filter residue was washed consecutively with Ethylacetate, Diisopropylether and Pentane, to yield after drying 20.3 g of slightly fawn crystals. M. p. 157-1580C. UV(THF) 360 and 372 nm (32'332)
b) 4-Dicyanomethylene-2,6-dimethyl-1 ,4-dihydropyridine-N-(ethyloxyethyloxyphosphate ester mono sodium salt)
A 750 ml four necked reaction flask, equipped with a thermometer, dropping funnel, a reflux condenser, pH electrode and a cooling bath with a magnetic stirrer was charged under Argon with 19.5 g (75mmol) of the above prepared 4-Dicyanomethylene-2,6-dimethyl-1 ,4- dihydropyridine-N-(ethyloxy-ethanol) and 13.6 ml (97.5 mmol) of Triethylamine (Fluka) in
250 ml of THF and cooled to 100C Then a solution of 13 8g (90 mmol) of POCI3 in 50 ml of THF is added by means of the dropping funnel within 15 Mm This mixture is stirred for 16 hours at room temperature, the reaction is traced by HPLC and the precipitate is filtered off to remove the NEt3 x HCI formed The filtrate is again cooled to 10°C and 1 mg of 18-crown- 6 is added followed by 97 5 ml of 2 0-n aqueous NaOH while checking the pH The reaction was stirred for further 90 Mm and additional 2 0-n aqueous NaOH was added at 2O0C until pH = 4 was reached At this point the aqueous phase was separated and washed with 100 ml of Ethylacetate By addition of 50 ml of saturated aqueous NaCI solution the product precipitate and could be filtered off and washed with 200 ml of Acetone After drying 18 2 g of colorless crystals were obtained , Solubility 168 g/l in Water This salt was recrystallized from DMF M p 158-1590C, UV (Water) 350 nm (E = 979) The photostability of this product was measured according to Berset et al , lnternat J Cosmetic Science 18 167-177 (1996) using a solution of a mixture of water/glycerol = 7 3 as liquid phase The product was found to be photostable
Example 2
4-Dιcyanomethylene-2,6-dιmethyl-1 ,4-dιhydropyrιdιne-N-(ethyloxysulfate ester mono sodium salt)
a) 4-Dιcyanomethylene-2,6-dιmethyl-1 ,4-dιhydropyrιdιne-N-ethaπe-2-ol
A 350 ml three necked reaction flask, equipped with a thermometer, a reflux condenser and an oil bath with a magnetic stirrer was charged with 25 8g (150mmol) of A- dιcyanomethylene-4H-pyran (prepared according HeIv Chim Acta 1962, 1908-1917) in 100 ml of ethanolamine (Fluka) and heated to 800C for 30 Mm under Ar atmosphere Shortly after the start, an exothermic reaction is observed After cooling, the mixture is diluted with
100 ml of n-Butanol and filtered off The filter residue was washed consecutively with 2x 10 ml of cold water, and 2x 100 ml of Acetone After drying 17 5 g of slightly yellowish crystals were obtained M p 267-2680C UV(THF) 360 and 372 nm (26'305)
b) 4-Dιcyanomethylene-2,6-dιmethyl-1 ,4-dιhydropyπdιne-N-(ethyloxysulfate ester mono sodium salt)
A 100 ml reaction flask equipped with a stirrer, reflux condenser, thermometer, oil bath and Ar atmosphere is charged with 2 15 g (10 mmol) of the above 4-dιcyanomethylene-2,6- dιmethyl-1 ,4-dιhydropyrιdιne-N-ethane-2-ol and 1 91 g (12 mmol) of sulfurtrioxyde-pyridine complex (Fluka) in a mixture of 30 ml of acetonitrile/pyridine = 9 1 This mixture is heated with strong stirring to 600C for 30 Mm Already after 10 Mm practically no starting material could be detected by HPLC At room temperature the mixture was diluted with 30 ml of acetone and filtered The residue was washed with acetone, dnsopropyl ether and pentane and dried to yield 3 1 g of colorless crystal m p 209 - 2100C This material was dissolved in 30 ml of water One equivalent of aq 1-n NaOH was added and the mixture was stirred for 15 Mm and concentrated at the rotavap using high vacuum 50 ml of water were added again to the residue and it was concentrated as above This process was repeated again two times, until no smell of pyridine could be traced The dry substance was again dissolved in five times its weight of water, precipitated by the addition of 200 ml of THF, filtered and the residue was washed with THF and acetone to yield 2 9 g of colorless crystals M p 198°C decomposition, UV(water) 352 nm (E= 1261 ) Solubility >= 25 g/l in Water The photostabihty of this product was measured according to Berset et al , lnternat J Cosmetic Science 18 167-177 (1996) using a solution of a mixture of water/glycerol = 7 3 as liquid phase The product was found to be photostable
Example 3
4-Dιcyanomethylene-2,6-dιmethyl-1 ,4-dιhydropyrιdιne-N-[3-(N,N-dιmethyl-N-(ethoxy-ethoxy ethanol-yl)-propyl-ammonιum iodide]
A 250 ml three necked reaction flask, equipped with a thermometer, a reflux condenser and an oil bath with a magnetic stirrer was charged with 14.5g (82.2mmol) of A- dicyanomethylene-4H-pyran (prepared according HeIv. Chim. Acta 1962, 1908-1917) and 10.1g (99 mmol) of 3-(N,N-dimethylamino)-propylamine (Fluka) in 145 ml of n-butanol and heated for two hours under Ar atmosphere. After cooling the suspension was filtered the filter residue was washed with cold n-butanol, to yield after drying 10.4 g of slightly yellowish crystals. M. p. 187-188 0C. UV(ethanol) 360nm (37'287).
b) 2-[2-(2-lodoethoxy)-ethoxy]-ethanol
A 25 ml reaction flask, equipped with a reflux condenser, an oil bath and a magnetic stirrer was charged with 2g (11.9mmol) of 2-[2-(2-chloroethoxy)-ethoxy]-ethanol (Fluka), 4 g of sodium iodide and 3 g of sodium hydrogencarbonate in 20 ml of Acetone. The reaction mixture is refluxed over night and when cold, filtered. The filtrate is concentrated at the rotavap, dissolved in 5 ml of CH2CI2 and filtered again. Then the filtrate is concentrated again at the rotavap to yield 2.5g of a yellow oil. The NMR shows a pure substance (CDCI3) 2.58 s broad (1 H/OH); 3.22 t (2H/CH2-J); 3.53-3.77 m (101-1/CH2-O).
c) 4-Dicyanomethylene-2,6-dimethyl-1 ,4-dihydropyridine-N-[3-(N,N-dimethyl-N-(ethoxy- ethoxy ethanol-yl)-propyl-ammonium iodide]
A 50 ml reaction flask, equipped with a reflux condenser, an oil bath and a magnetic stirrer was charged with 1.28g (5 mmol) of the above prepared 4-dicyanomethylene-2,6-dimethyl- 1 ,4-dihydropyridine-N-(3-[N,N-dimethylamino]-propane), 1.34 g (5.5 mmol) of the above described 2-[2-(2-iodoethoxy)-ethoxy]-ethanol in 15 ml of DMF. The reaction mixture is refluxed over night and shows no starting material by TLC. The reaction mixture was concentrated at the rotavap, followed by HV drying. The residue is washed with cyclohexane and then with ethylacetate followed by recrystallization from ethanol. Yield 2.09 g of brown crystals. M. p. 130-1800C decomp ; UV(ethanol) 362 nm (37'946).
Example 4
1 -{2-[2-(4-Dιcyanomethylene-2,6-dιmethyl-4H-pyrιdιn-1 -yl)-ethoxy]-ethyl}-pyπdιnιum chloride
A 750 ml four necked reaction flask, equipped with a thermometer, dropping funnel, a reflux condenser, a cooling and a heating bath with a magnetic stirrer was charged under Argon with 19 5 g (75 mmol) of the above prepared 4-Dιcyanomethylene-2,6-dιmethyl-1 ,4- dιhydropyrιdιne-N-(etholoxy-ethanol) (Example 6 1 a) and a trace of triethylamine (Fluka) in 250 ml of THF and cooled to 100C Then a solution of 10 7 g (90 mmol) of SOCI2 in 50 ml of THF is added by means of the dropping funnel within 15 mm This mixture is stirred for 1 hour at room temperature and then heated to reflux for four hours The reaction is traced by HPLC The mixture is poured onto ice, and the product is filtered off and recrystallized from ethylacetate White crystals were obtained, m p 148-149°C
b) 1 -{2-[2-(4-Dιcyanomethylene-2,6-dιmethyl-4H-pyπdιn-1 -yl)-ethoxy]-ethyl}-pyrιdιnιum chloride
A 50 ml reaction flask, equipped with a reflux condenser, a heating bath and a magnetic stirrer was charged under Argon with 1 4 g (5 mmol) of the above 2-{1 -[2-(2-chloro-ethoxy)- ethyl]-2,6-dιmethyl-1 H-pyrιdιn-4-ylιdene}-rnalononιtπle in 25 ml of pyridine and heated to reflux for 5 hours A heavy suspension was formed, which was filtered off and washed with a small amount of cold pyridine followed by THF After drying 1 69 g of fine crystals were obtained, m p 248-251 °C/decomp UV (water) 352 nm (E = 1149) Solubility in water » 200 g/l
Example 5
3-[3-(4-Dιcyanomethylene-2,6-dιmethyl-4H-pyπdιn-1 -yl)-phenoxy]propane-1 -sulfonic acid
a) 2-[1 -(3-Hydroxy-phenyl)-2,6-dimethyl-1 H-pyπdιn~4-ylιdene]-malononιtπle
A 10 ml reaction flask, equipped with a reflux condenser, a magnetic stirrer and an oil bath was charged with 0 86 g (5 mmol) of 4-dιcyanomethylene-4H-pyran (prepared according to HeIv Chim Acta 1962, 1908-1917) and 2 8 g (25 mmol) of 3-amιnophenol (Fluka) under Ar atmosphere and heated to 1400C for 5 hours Still hot, the mixture was poured onto 100 ml of 2n HCI and extracted twice with 100 ml of ethylacetate The combined organic phases were backwashed with 2n HCI, concentrated at the rotavap and dried The crystals were washed with warm ethylacetate and MeOH and dried again to yield 460 mg of white crystals M p > 3000C, TLC (EtOAc hexane = 1 1 on silica gel) Rf = 0 15
b) 3-[3-(4-Dιcyanomethylene-2,6-dιmethyl-4H-pyrιdιn-1 -yl)-phenoxy]-propane-1 -sulfonic acid
A 50 ml three necked reaction flask, equipped with a thermometer, a reflux condenser, a magnetic stirrer and a heating bath was charged under Argon with 263 mg ( 1 mmol) of the above 2-[1-(3-hydroxy-phenyl)-2,6-dιmethyl-1 H-pyrιdιn-4-ylιdene]-malononιtrιle and 26 5 mg (1 05 mmol) of dry NaH (95%) suspended in a mixture of 20 ml of dry THF and 0 1 ml of dry DMF Hydrogen formation was observed After 45 mm 134 mg (1 1 mmol) of 1 ,3- propansultone was added to the suspension, and the reaction mixture was heated to 70°C for 5 hours and followed by HPLC When cold, the mixture was filtered, and the residue
Cl CMN 58
washed with little THF to yield 260 mg of a white powder This was recrystallized from MeOH/CH2CI2, washed with CH2CI2 and dried to yield 190 mg of colorless crystals m.p. 200°C/decomp. UV (water) 352 nm (E = 1 150) solubility in water > 50 g/l.
Example 6
Preparation of a O/W sunscreen lotion UV-B and UV-A:
Broad-spectrum sunscreen lotion containing 2% of the compound of Example 2
%w/w Compound Chemical Name
Part A
4 PARSOL MCX Ethylhexyl methoxycinnamate
12 Cetiol LC Cocoyl-caprylate caprate
4 Dermol 185 lsostearyl neopentanoate
0.25 PEG-2-stearate Diethyleneglycol monostearate
1 Cetylalcohol Cetylalcohol
0.25 MPOB/PPOB Methyl-propylparabene
0.1 EDTA BD EDTA-sodium salt
1 Amphisol DEA Diethanolamine cetylphosphate
Part B
2 Product of Example 1
0.2 Permulene TR-1 Acrylate C10-C30 alkylacrylate
67.4 Water deionized Water deionized
5 Propylene glycol 1 ,2-Propanediol
2 Product of example 2
0.8 KOH (10%) Potassium hydroxide
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.
Example 7
Sun milk waterproofed
%w/w Ingredient Chemical Name
Part A
4 PARSOL 5000 4-Methylbenzylidene camphor
8 Parsol MCX Ethylhexyl methoxicinnamate
Uvinul T 150 Ethylhexyltriazone
1 Silicone DC 200/350 cs Dimethicone
Lanette O Cetylstearyl alcohol
3 Softisan 100 Hydrogenated coco-glycerides
6 Tegosoft TN C12-15 Alkyl benzoate
7 Cetiol B Dibutyl adipate
2 VITAMIN E ACETATE Tocopheryl acetate
1 Berkemyol (Grape Seed) Palmitoyl Grape seed Extract
0 05 BHT Butylhydroxytoluol
0 10 Edeta BD Disodium EDTA
0 60 Phenonip Phenoxyethanol & Methylparaben
& Ethylparaben & Propylparaben
& Butylparaben
2 AMPHISOL Cetyl phosphate DEA
Example 8
Sprayable Sunscreen lotion
Ingredients INCI Nomenclature % W / W
A) PARSOL MCX Ethylhexyl Methoxycinnamate 6 00
PARSOL 5000 4-Methylbenzylιdene Camphor 2 00
Emulgade SE-PF Glyceryl Stearate (and) Ceteareth- 7 00
20 (and) Ceteareth-12 (and)
Cetearyl Alcohol (and) Cetyl
Palmitate
Eumulgin B-2 Ceteareth-20 6 00
Myπtot 318 Caprylic/Capric Triglyceride 3 00
Cetiol A Hexyl Laurate 6 00
Silicone DC 345 fluid Cyclomethicone 7 00
Antaron V-220 PVP/Eicosene Copolymer 2 00
Edeta BD Disodium EDTA 0 10
Butylated BHT 0 05
Hydroxytoluene
Phenonip Phenoxyethanol & Methylparaben & 0 60
Ethylparaben & Propylparaben &
Butylparaben
B) Water deionized Aqua q s 100
Glycerin Glycerin 5 00
Product of example 2 2 00
KOH 10% sol Potassium Hydroxide 2 40
Procedure:
Heat part A) to 85°C while stirring When homogeneous, add part B) (80°C) under stirring Then add part C) (4O0C) while stιrnng(be sure that Parsol HS has been completely dissolved, if traces remain, add a small quantity of the neutralizing base until the solution is clear pH>7) Finally adjust the pH to a minimum of 7 0, and cool to RT
Example 9
O/W VITAMINIZED BROAD SPECTRUM SUNSCREEN LOTION
Ingredients INCI Nomenclature % W / W
A) PARSOL MCX Ethylhexyl Methoxycinnamate 4 00
PARSOL 1789 Butyl Methoxydibenzoylmethane 1 00
PARSOL 5000 4-Methylbenzιlιdene Camphor 3 50
Estol GMM 3650 Glyceryl Myπstate 4 00
Cetyl Alcohol Cetyl Alcohol 2 00
Ganex V-220 PVP/Eicosene Copolymer 2 00
Tegosoft TN C12-15 Alkyl Benzoate 10 00
Myπtol 318 Caprylic/Capric Triglyceride 6 00
Butylated Hydroxytoluene BHT 0 05
Edeta BD Disodium EDTA 0 10
Phenonip Phenoxyethanol & Methylparaben & 0 60
Ethylparaben & Propylparaben &
Butylparaben
AMPHISOL K Potassium Cetyl Phosphate 2 00
VITAMIN E ACETATE Tocopheryl Acetate 2 00
B) Water deionized Aqua ad 100
Propylene Glycol Propylene Glycol 5 00
Carbopol 981 ( 1 % sol ) Carbomer 10 00
D-PANTHENOL 75L Panthenol 2 70
C) KOH ( 10% sol ) Potassium Hydroxide 0 70
D) Water deionized Aqua 20 00
Product of Example 2 2 00
PARSOL HS Phenylbenzimidazole Sulfonic Acid 2 00
KOH ( 10% sol ) Potassium Hydroxide 4 00
Procedure:
Heat part A) to 85°C while stirring When homogeneous, add part B) and C) pre-heated to 75°C under agitation Add part D) pre-heated to 75°C (be sure that PARSOL HS has completely dissolved, if traces remain, add a small quantity of the neutralizing base until the solution is clear) Homogenize at 11000 rpm for 30 sec Cool to room temperature
Physical Data: pH 7 20
Viscosity (Brookfield RVT, 25°C, spindle 6, 10 rpm) approx 12350 cP
Example 10
Protective Styling Hair Mousse
Ingredients INCI Nomenclature % W / W
A) Water Aqua 83 40
Celquat L-200 Polyquaternιum-4 2 00
Aminoxid WS 35 Cocamidopropylamine Oxide 0 40
Silicone DC 193 PEG-12 Dimethicone 0 20
Germaben Il Propylene Glycol & Diazolidinyl Urea 1 00
& Methylparaben & Propylparaben
Product of Example 2 3 00
B) Propane / Butane 10 00
100 00
Procedure:
Part A Add the ingredients in the order shown under agitation Charge in adequate containers with part B
Example 11
Lip Balm
Ingredients INCI Nomenclature % W / W
A) Parsol SLX Polysιlιcone-15 5 00
Parsol 1789 Butyl Methoxydibenzoylmethane 2 00
Eutanol G Octyldodecanol 22 40
Ricinus Oil Ricinus Communis (Castor) Seed Oil 22 00
Myπtol 318 Caprylic/Capπc Triglyceride 18 00
Softisan 649 Bis-Diglyceryl Polyacyladιpate-2 7 00
Syncrowax HR-C Tπbehenin 2 00
Camauba Wax 2442 Copernicia Cerifera (Carnauba) Wax 8 00
Beeswax White 100% Beeswax 10 00
VITAMIN E ACETATE Tocopheryl Acetate 2 00
Jojoba Oil Simmondsia Chinensis (Jojoba) 1 00
Seed Oil
Bisabolol Bisabolol 0 20
D-PANTHENOL 75 L Panthenol 0 20
B) Product of Example 2 0 20
C) Perfume Perfume Qs
Procedure:
Cool while mixing
Example12
Make up / Foundation / Day Cream
Ingredients INCI Nomenclature % w / w
A) PARSOL SLX Polysilicone 15 4 00
Eutanol G Octyldodecanol 4 00
Teg in Glyceryl Stearate SE 4 50
Talcum Talc 1 00
Titanium Dioxide 1 171 Titanium Dioxide 6 00
Sicovit Brown 75 E 172 Iron Oxides 0 80
Ricinus Oil Ricinus Communis (Castor) Seed Oil 8 00
Arlacel 83 Sorbitan Sesquioleate 0 50
Brij 72 Steareth-2 0 50
VITAMIN E ACETATE Tocopheryl Acetate 2 00
Edeta BD Disodium EDTA 0 10
Butylated Hydroxytoluene BHT 0 05
Phenonip Phenoxyethanol & Methylparaben & 0 60
Ethylparaben & Butylparaben &
Propylparaben & lsobutylparaben
Amphisol K Potassium Cetyl Phosphate 2 00
B) Water deionized Aqua ad 100
Propylene Glycol Propylene Glycol 5 00
Carbopol 980 Carbomer 1 00
Product of Example 2 2 00
C) Dow Corning 344 Fluid Cyclomethicone 4 00
Dow Comma 200/350 cs Dimethicone 1 00
Procedure:
Heat part A) to 85°C while stirring When homogeneous, add part B) pre-heated to 750C While mixing, cool to ambient temperature, be sure that the Temperature not over 25°C and add part C) under stirring Pass trough a 3-Rollmιll
PhvsicalData: pH 5 24
Viscosity (Brookfield RVT1 25°C, spindle 7, 10 rpm) approx 175000 cP
Example 13
Sunscreen Gel Lotion
Ingredients INCI Nomenclature % W / W
A) Pemulen TR-2 Aery lates/C 10-30 Alky Acrylate 0 60
Crosspolymer
Carbopoi »80 Carbomer 0 20
Phenonip Phenoxyethanol & Methylparaben & 0 60
Ethylparaben & Propylparaben &
Butylparaben
Edeta BD Disodium EDTA 0 1
Product of example 2 1 00
Aqua Aqua ad 100
PARSOL 1789 Butyl Methoxydibenzoylmethane 2 00
PARSOL 340 Octocryleπe 1 80
Myπtol 318 Capryhc/Capπc Triglyceride 13 70
Antaron V-216 VP/Hexadecene Copolymer 1 00
VITAMIN E ACETATE Tocopheryl Acetate 0 50
Uvιnul TIO2 Titanium Dioxide 5 00
Butylated Hydroxytoluene BHT 0 05
C) Tris Amino Tromethamine 1 04
D) Perfume Perfume q s
Procedure:
Disperse Pemulen TR-2 and Carbopoi 980 in phase A) at room temperature Heat part B) to 85°C while stirring When homogeneous, add part B) to A) under strong agitation (turbine) and vacuum Then, add part C) Finally add part D) around 400C Cool to ambient temperature while stirring
PhysicalData: pH 7 00
Viscosity (Brookfield RVT, 25°C, spindle 6, 10 rpm) approx 24100 cP
Example 14
Sunscreen Gel
Ingredients INCI Nomenclature % W / W
A) Deiomzeα water Aqua ad 100
Pemulen TR-1 Acrylate/C10-30Alkyl Acrylate 1 00
Crospolymer
Propylene Glycol Propylene Glycol 6 00
Edeta BD Disodium EDTA 0 10
Phenonip Phenoxyethanol & Methylparaben & 0 60
Ethylparaben & Propylparaben &
Butylparaben
B) KOH (10% sol ) Potassium Hydroxide 4 50
C) Deionized water Aqua 20 00
Product of Example 2 4 00
KOH (10% sol ) Potassium Hydroxide 7 20
D) D-PANTHENOL 75 L Panthenol 1 30
Procedure:
Heat part A) to 500C while stirring When homogeneous, add part B) under agitation Then, add part C) pre-heated to 50°C, while stirring (be sure that PARSOL HS has completely dissolved, if traces remain, add a small quantity of the neutralizing base until the solution is clear) Cool to 400C and add part D), homogenize at 11000 rpm for 30 sec Cool to room temperature while stirring
PhysicalData: pH 7 2
Viscosity (Brookfield RVT, 25°C, spindle 5, 10 rpm) approx 13700 cP
Example 15
Hair Relaxer
Ingredients INCI Nomenclature % W / W
A) Emulium Delta Cetyl Alcohol & Glyceryl Stearate & 8 00
PEG-75 Stearate & Ceteth-20 &
Steareth-20
Lorol C 16 Cetyl Alcohol 2 00
Petrolatum white Petrolatum 5 00
Silkflo 364 Hydrogenated Polydecene 15 00
Phenonip Phenoxyethanol & Methylparaben & 0 50
Ethylparaben & Propylparaben &
Butylparaben & lsopropylparaben
Parsol SLX Polysιlιcone-15 1 00
B) Buffer Solution pH 11 Aqua, 0 1 M NaOH, 0 05M NaHCO3 60 90
1 ,2-Propanedιol Propylene Glycol 5 00
Product of example 2 1 00
EDETA BD Disodium EDTA 0 10
C) Sodiumhydroxid (30%) Sodium Hydroxide 1 50
100 00
Procedure:
Heat part A and part B separately to 75°C under moderate agitation When homogeneous, add part A to B under agitation Let cool to 400C and add part C Homogenize
Physical Data: pH 12 7
Viscosity (Brookfield RVT, 25°C, spindle 7, 10rpm) approx 5240OcP
Example 16
Protective Hairdressing Cream
Ingredients INCI Nomenclature % W / W
A) Lipovol J Simmondsia Chinensis (Jojoba) Seed 3 00
On
Apricot Kernel Oil Prunius Armeniaca (Apricot) Kernel 3 00
Oil
Silicone DC 556 Fluid Phenyl Trimethicone 2 00
Finsolv TN C12-15 Alkyl Benzoate 2 00
Teg in Glyceryl Stearate SE 2 00
Parsol SLX Dimethico-diethyl benzalmalonate 4 00
Vitamin E Acetate Tocopheryl Acetate 0 50
Lanette O Cetearyl Alcohol 1 6
B) Water Aqua 78 6
Product of example 1 00
C) Genamin KDM-F Behentπmonium Chloride 1 00
Hydrotriticum QM Aqua (and) Cocodimonium 0 3
Hydroxypropyl Hydrolyzed Wheat
Protein
Germaben Il Propylene Glycol & Diazolidinyl Urea 1 00
& Methylparaben
100 00
Procedure:
Heat part A and part B separately to 65°C under moderate agitation When homogeneous, add part A to B under agitation Let cool to 400C and add part C Homogenize
Physical Data: pH 4 2
Viscosity (Brookfield RVT, 25°C, spindle 5, 10rpm) approx 17000 cP
Example 17
Cosmetic compositions with a particularly low penetration of UV-sunscreen agents
Inqredfents INQ Nomenclature %Ww %vώM %Ww %Ww %w/w %w/w %yrfw %wSw
A) Amphisd K Potassium Catyl Phosphate 2,∞ 2,00 2,00 2,00 2,00 2,00 200 2,00 Lord C 16 Cetyl Alcohd 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 Estd QVM 3650 Glyceryl Myπstate 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 Myπtd 318 Caprylic/Capnc Triglyceride 13,00 13,00 12,00 12,00 12,00 13,00 13,00 13,00 Tegosoft TN C12-15AJkyl Benzoate 7,00 7,00 6,00 6,00 6,00 7,00 7,00 7,00 Phenonip Phenoxyethand, Parabens 1 ,00 1,00 1,00 1,00 1 00 1 00 i,oo 1,00
BHT BhT 0,05 0,05 0,05 0,05 0,05 0,05 0,05 0,05
Uvιnul TiO2 Titanium Dioxide 3,00 3,00 3,00 2,00 Pared SLX Pdysilicone-15 5,00 3,00 4,00 3,00 2,00
B) Water Aqua 59,15 56,15 58,65 49,65 58,15 54,15 52,15 48,15
Product of example 2 2,00 3,00 1,50 1,50 2,00 1,00 2,00 2,00
Encapsulated Ethyhexyl 15,00 10,00
EEHMc Methoxyαnnamate
Propylene Glycd Propylene dyed 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00
Edeta BD EDTA 0,10 010 0,10 0,10 0,10 0,10 0,10 0,10
Keltrd T Xanthan Gum 0,40 0,40 0,40 0,40 0,40 0,40 0,40 0,40
NaOH 10% Sodium Hydroxide 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30
Benzotnazdyl
C) Tinosorb M 6,00 5,00 4,00
Tetramethylbutylphend
D) NaOH 10% Sodium Hydroxide qs qs qs qs qs qs qs qs
Sun 100.00 100.00 100.00 K ».00 1C ».00 1C ».00 1C ».00 100.00
Procedure
Heat part A to 800C Part B Combne water and Propylene Qykd and add Parsd A 1200 under stirring until it is sdved Add the rest of part B and heat to 80°C Add F
^ BtopartAuncler stιmng areJ rκyrogenize 30 secorιds 9500 rpm Let cod down under stirring, add part C under stirring and homogenize agan 30 seconds with 6500 rpm Adjust the PH to 65 with part D
Example 18
The high photostabihty of the UV-suπscreen agents of formula (I) above in the presence of Parsol 1789 in a sunscreen composition was shown in the following composition
jNCjJNtom e net ature __ J %w/w
Myπtol_31_8 Caprylic/Capric Tπglyceπde 1 3"θO
TegosofTTN CΪ2-15 Alky I Benzoate 7 £θ|
Phenonip Phenoxyethanol, Parabens 1 00'
BHT 0 05]
Parsol 1789 Butyl Methoxydibenzoyl Methane 2 00
1
B) Water Aqua i ,r60 35
1 PrOdUCt of example 2 2 00] 1_2_Propyle^ne GJycql p op]
TDTAT ™ 0 10
J<eltrorr Xanthan Gum 0 20
NaOH J0%_ sol Sodium Hydroxyde 0 30
C) JMaOH ^OΥo sdt^ Sodium Hydroxyde Sum r100.00
i Procedure __
Heat part A and B to 8O0C Add Part A to part B under stirring and 1 let cool down to 6O0C Homogenize 45 seconds with 9500 rpm Let cool down under stirring Adjust the pH with part C
After irradiation with 10 MED a recovery of 4-Dιcyanomethylene-2,6-dιmethyl-1 ,4- dιhydropyrιdιne-N-(ethyloxysulfate ester mono sodium salt) (Example 2) of 90% could be found
Example 19
The following sunscreen compositions were prepared and evaluated according to the Australian Standard
Formula No. 100101- 023 024 025
% % %
A) Amphisol Cetyϊ Phosphate 1 ~50 1 50 " 1 50
Lorol C 16 , Cetyl Alcohol j 1 20 1 20 1 20
Tegin Glyceryl Stearafe SE 2 00 "2 00 2 00
My7itor3T8 ^aprylic/Capπc triglyceride 5 00 5 00 5 00
Tegosoft TN ~ '~C12vi5 Alkyl Benzoate 8 00 8 00 8 00
Dow Corning 200/100cs Simethicone " 0 30* 0 30 "^O 30
Phenonip Phenoxyethanol, Parabens 0 80 0 80 0 80
"BHT " BHT 0 05" 0 05 0 05
"Parsol "MCX , Ethylhexyl Methoxycinnamate, 5 00
Parsol 5000 Methylbenzyhdene Camphor ' 4 00
Water Aqua 47 65 46 65 \ 38 65
Parsol A 1200 2 00~ 3 00 "2 00
1 3-Butyleneglycol Butylene Glycol 5 00^ 5 00 5 00
Edeta BD~ " ", EDTA " " " 0 1 θ" 0 10 0 10 bomer ( ~—
Carbopol ETD 2050 Car 0 20~ ~ 0 20
Keϊtrol f Xanϊhan Gum , "" 0 20 0 20 0 20
Trizmabase 25% sol Tromethamine 4 00 4 00 4 00
I
' WateF Aqua 2b 00 20 00 20 00
>arsol A 1200 " 2 00 2 00 2 00
Tnzmabase 25% sol Tromethamine ] qs qs qs
Sum 100.00 100.00 100.00
Procedlure _^ L -
Heat part A and B to 8O0C Add Part A to part B under stirring and let cool down to 60°C Dissolve part C and add C to part AB at 6O0C under stimng Homogenize 45 seconds with 9500 rpm Let cool down under stirπng Adjust the pH with part D
The transmission through a film of the sun care formulations with a film thickness of 8 μm has been measured The definition of the Australian Standard is Between 320 nm and 360 nm the transmission should be below 10%
The results are shown in Fig 1
Example 20
The in vitro SPF of a standard O/W emulsion containing the UV sunscreen agent of example 2 and in combination with other UV sunscreen agents in the indicated concentration have been measured using an Optometries SPF Analyzer system The results are shown in the following table
It can be seen that the compound of example 2 shows a synergistic effect with Parsol MCX and Parsot 1789
Example 21
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-fιlters, lnt J Cosmet Sci 18, 167-188 (1996)
'measured by UV absorption of irradiated sample vs non-irradiated sample
It can be seen that unexpectedly glycerin stabilizes the compounds of example 2 in an emulsion
Example 22
The UVA balances of a standard O/W emulsion containing the UV sunscreen agent of example 2 and in combination with other UV sunscreen agents in the indicated concentrations have been measured using the German norm DIN 67502 The results are shown in the following table
It can be seen that the compound of example 2 shows a synergistic effect with Parsol 1789
Claims
Claims:
1 Use of a compound of the general formula I
wherein
R1 and R2 are identical or different electron-withdrawing groups or one of R1 and
R2 is hydrogen and the other of R1 and R2 is an electron-withdrawing group,
R3, R4, R5 and R6 are independently selected from hydrogen atoms, C1-C10 alkyl groups, C2-Ci0 alkenyl groups, C2-Ci0 alkynyl groups, C3-C10 cycloalkyl groups or C6-C10 aryl groups, the above groups being unsubstituted or optionally substituted by one to three substituents selected from C1-C6 alkyl groups, halogen, hydroxy and C1-C6 alkoxy groups, or R3 and R5 and/or R4 and R6 taken together with the carbon atom to which they are attached form a 5- or 6-membered ring which is optionally substituted with one to four substituents selected from C1-C6 alky! groups, C3-C6 cycloalkyl groups, C1-C6 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
Y is a counteπon
in a cosmetic or dermatologica! sunscreen composition for reducing systemic exposure caused by skin penetration of sunscreen agents
2 Use according to claim 1 , wherein the sunscreen composition contains at least one additional UV-sunscreen agent which is non-penetrating or has a reduced skin penetration rate selected from polymeric sunscreen agents, encapsulated sunscreen agents and microparticulated inorganic sunscreen agents and micronized organic sunscreen agents and triazine derivatives
3 Use according to claim 2, wherein the sunscreen composition contains additionally at least one sunscreen agent selected from Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine, Ethylhexytπazone, Diethylbutamido tπazone, Methylene bis-benzotπazolyl tetramethylbutylphenyl, Polysιlιcone-15, microparticulated TιO2 or ZnO or combinations thereof
4 Use of a compound of the general formula I
wherein
R1 and R2 are identical or different electron-withdrawing groups or one of R1 and
R2 is hydrogen and the other of R1 and R2 is an electron-withdrawing group,
R3, R4, R5 and R6 are independently selected from hydrogen atoms, Ci-C10 alkyl groups, C2-C10 alkenyl groups, C2-C10 alkynyl groups, C3-C10 cycloalkyl groups or C6-C10 aryl groups, the above groups being unsubstituted or optionally substituted by one to three substituents selected from C1-C6 alkyl groups, halogen, hydroxy and C1-C6 alkoxy groups, or R3 and R5 and/or R4 and R6 taken together with the carbon atom to which they are attached form a 5- or 6-membered ring which is optionally substituted with one to four substituents selected from C1-C6 alkyl groups, C3-C6 cycloalkyl groups, C1-C6 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
Y is a counterion
in combination with a stabilizer and/or an emulsifier to increase the stability of a UV- sunscreen composition in the form of an emulsion, so that the emulsion is stable for ai ieast three month at 43°C, wherein the stabilizer is selected from cellulose and cellulose derivatives, carbomers, 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, polyethylene glycols of different chain length, natural and synthetic waxes, fatty alcohols, fatty acid esters, esters of glycerol with fatty acids, fatty acids, hydrogenated fats, mineral oil and further fractions of the oil distillation and mixtures thereof and the emulsifier is selected from ionic emulsifiers and the salts thereof and polymeric emulsifiers and mixtures thereof
5 Use according to claim 4 wherein the emulsifier is selected from cetylphosphate, potassium cetylphosphate, tπlaureth-4-phosphate, fatty acids and their salts, preferably stearic acid, polymeric emulsifiers, preferably steareth-2, steareth-21 , ceteareth-20, PEG-7 hydrogenated castor oil and PEG-45/dodecyl glycol copolymer and mixtures thereof
6 Use of a compound of the general formula I
wherein
R1 and R2 are identical or different electron-withdrawing groups or one of R1 and
R2 is hydrogen and the other of R1 and R2 is an electron-withdrawing group, R3, R4, R5 and Rb are independently selected from hydrogen atoms, Ci-C10 alkyl groups, C2-Ci0 alkenyl groups, C2-Ci0 alkynyl groups, C3-C10 cycloalkyl groups or C6-Ci0 aryl groups, the above groups being unsubstituted or optionally substituted by one to three substituents selected from C1-C6 alkyl groups, halogen, hydroxy and C1-C6 alkoxy groups, or R3 and R5 and/or R4 and R6 taken together with the carbon atom to which they are attached form a 5- or 6-membered ring which is optionally substituted with one to four substituents selected from C1-C6 alkyl groups, C3-C6 cycloalkyl groups, Ci-C6 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
Y is a counterion
in combination with a film forming agent to increase the water resistance of a sunscreen composition in the form of an emulsion or gel
7 Use according to claim 6, wherein the film forming agent is selected from polyurethanes, dimethicone, copolyol, polyacrylates, polyvinylpyrrolidone/vinylacetate copolymers and polymers on the basis of polyvinylpyrrolidone
8 Use of compounds of the general formula I
wherein
R1 and R2 are identical or different electron-withdrawing groups or one of R1 and
R2 is hydrogen and the other of R1 and R2 is an electron-withdrawing group, R3, R4, R5 and R6 are independently selected from hydrogen atoms, C1-Ci0 alkyl groups, C2-C10 alkenyl groups, C2-C10 alkynyl groups, C3-C10 cycloalkyl groups or C6-C10 aryl groups, the above groups being unsubstituted or optionally substituted by one to three substituents selected from C1-C6 alkyl groups, halogen, hydroxy and C1-C6 alkoxy groups, or R3 and R5 and/or R4 and R6 taken together with the carbon atom to which they are attached form a 5- or 6-rnembered ring which is optionally substituted with one to four substituents selected from C1-C6 alkyl groups, C3-C6 cycloalkyl groups, C1-C6 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
Y is a counterion for stabilizing perfumes and fragrances.
9. Use of compounds of the general formula I
wherein
R1 and R2 are identical or different electron-withdrawing groups or one of R1 and
R2 is hydrogen and the other of R1 and R2 is an electron-withdrawing group,
R3, R4, R5 and R6 are independently selected from hydrogen atoms, C1-C10 alkyl groups, C2-C10 alkenyl groups, C2-C10 alkynyl groups, C3-C10 cycloalkyl groups or C6-C10 aryl groups, the above groups being unsubstituted or optionally substituted by one to three substituents selected from C1-C6 alkyl groups, halogen, hydroxy and C1-C6 alkoxy groups, or R3 and R5 and/or R4 and R6 taken together with the carbon atom to which they are attached form a 5- or 6-membered ring which is optionally substituted with one to four substituents selected from C1-C6 alkyl groups, C3-C6 cycloalkyl groups, C1-C6 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
Y is a counterion for stabilizing dyes and/or pigments in inks, cosmetics and hair dyes
10 Use of compounds of the general formula I
wherein
R1 and R2 are identical or different electron-withdrawing groups or one of R1 and
R2 is hydrogen and the other of R1 and R2 is an electron-withdrawing group,
R3, R4, R5 and R6 are independently selected from hydrogen atoms, C1-C10 alkyl groups, C2-C10 alkenyl groups, C2-C10 alkynyl groups, C3-C10 cycloalkyl groups or C6-C10 aryl groups, the above groups being unsubstituted or optionally substituted by one to three substituents selected from C1-C6 alkyl groups, halogen, hydroxy and C1-C6 alkoxy groups, or R3 and R5 and/or R4 and R6 taken together with the carbon atom to which they are attached form a 5- or 6-membered ring which is optionally substituted with one to four substituents selected from C1-C6 alkyl groups, C3-C6 cycloalkyl groups, C1-C6 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
Y is a counterion as co-emulsifier for sunscreen compositions
11 Use of compounds of the general formula I
wherein
R1 and R2 are identical or different electron-withdrawing groups or one of R1 and
R2 is hydrogen and the other of R1 and R2 is an electron-withdrawing group,
R3, R4, R5 and R6 are independently selected from hydrogen atoms, Ci-C10 alkyl groups, C2-Ci0 alkenyl groups, C2-Ci0 alkynyl groups, C3-Ci0 cycloalkyl groups or C6-Ci0 aryl groups, the above groups being unsubstituted or optionally substituted by one to three substituents selected from Ci-C6 alkyl groups, halogen, hydroxy and Ci-C6 alkoxy groups, or R3 and R5 and/or R4 and R6 taken together with the carbon atom to which they are attached form a 5- or 6-membered ring which is optionally substituted with one to four substituents selected from Ci-C6 alkyl groups, C3-C6 cycloalkyl groups, Ci-C6 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
Y is a counterion for increasing the UV-A balance of other UV-A filters
12 Use according to claim 1 1 , wherein the other UV-A filter is Parsol 1789 or Uvmul A Plus
13 Use according to any of claims 1 to 12, wherein X is an alkyl, alkyl aryl or alkyl cycloalkyl 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
14 Use according to claim 13, wherein X is a C1-Ci0 alkylene group containing optionally 1 to 10 hetero atoms and comprising at least one group which is positively or negatively charged
15 Use according to any of claims 1 to 14, wherein X contains 1 to 6 hetero atoms
16 Use according to claim 15, wherein the hetero atoms are selected from nitrogen, oxygen, sulfur and phosphor atoms
17 Use according to any of claims 1 to 16, wherein the group which is positively or negatively charged has one positive charge
18 Use according to claim 17, wherein the group which has one positive charge is a quaternary ammonium group
19 Use according to claim 18, wherein Y is a halogen atom
20 Use according to any of claims 1 to 19, wherein the group which is positively or negatively charged has one negative charge
21 Use according to claim 20, wherein the group which has one negative charge is selected from a group consisting of -COO , -0-SO3 and -0-PO3H
22 Use according to claim 21 , wherein Y is an alkaline metal atom, an earth alkaline metal atom, a triethanol ammonium ion, an aminomethylpropanol ion or a tristromethamine ion
23 Use according to any of claims 1 to 22, wherein residue R3 and R4 are each hydrogen atoms
24 Use according to any of claims 1 to 23, wherein residues R5 and R6 are independently selected from hydrogen atoms and CrC6 alkyl groups
25 Use according to any of claims 1 to 24, wherein residues R1 and R2 are Doth cyano groups
26 Use according to any of claims 1 to 12, wherein the compound of formula (I) is a compound of the formula (II)
wherein M+ is a counteπon
27 Use according to claim 26, wherein M+ is selected from Na+, K+, Li+, NH4 + and 0 5 equivalent of Mg2+ and Ca2+
28 Use according to any of claims 1 to 12 wherein the compound of formula (I) is
29 Sunscreen composition comprising a compound of formula (II)
wherein M+ is a countenon, in combination with a dibenzoylmethane derivative, an additional photostabihzer or a combination of a dibenzoylmethane derivative and an additional photostabihzer, with the proviso that M+ is not Na+, if the additional photostabihzer is ethylhexyl methoxycinnamate in combination with butyl methoxy dibenzoylmethane
30 Sunscreen composition according to claim 29, wherein the dibeπzoylmethane derivative is 4-tert butyl-4'-methoxydιbenzoylmethane
31 Sunscreen composition according to claim 29 or 30, wherein the photostabihzer is selected from octocrylene, 4-methylbenzylιdene camphor, diethylhexyl 2,6-naphthalate, polysιlιcone-15, benzophenone-3, ethylhexyl methoxy cinnamate or combinations thereof
32 Sunscreen composition comprising a compound of formula (II)
wherein M+ is a counteπon, in combination with one or more additional UV-screening agents selected from Parsol HS, Neohehopen AP, Uvinul A+ and mixtures thereof, with the proviso that M+ is not Na+ if the additional UV-screening agent is Parsol HS
33 Ink composition comprising a compound of formula (II)
wherein M+ is a counterion
34 Sunscreen composition containing a compound formula (I), as defined in any of claims 10 and 13 to 28 and a film forming agent
35 Sunscreen composition according to claim 34, wherein the film forming agent is selected from polyurethanes, dimethicone, copolyol, polyacrylates, polyvinylpyrrolidone/vinylacetate copolymers and polymers on the basis of polyvinylpyrrolidone
36. Sunscreen composition containing a compound of formula (I) as defined in any of claims 10 and 13 to 28 and a booster.
37. Compound of the formula
wherein M+ is a counterion which is different from Na+ and K+.
38. Compound according to claim 35, wherein M+ is selected from Li+, NH4 + and 0.5 equivalent of Mg2+ and Ca2+.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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EP05017041 | 2005-08-05 | ||
EP05017041.4 | 2005-08-05 |
Publications (1)
Publication Number | Publication Date |
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WO2007017179A1 true WO2007017179A1 (en) | 2007-02-15 |
Family
ID=37027624
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2006/007691 WO2007017179A1 (en) | 2005-08-05 | 2006-08-03 | Use of ionic uv-a sunscreens |
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WO (1) | WO2007017179A1 (en) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102007024348A1 (en) | 2007-05-22 | 2008-11-27 | Beiersdorf Ag | Cosmetic formulation for use in cosmetic sprays, particularly in sun protective agents, comprises dicyanomethylene-dimethyl-dihydropyridine-(ethyloxysulfate ester mono sodium salt), tris (biphenyl)-triazine, UV filters and diols |
DE102007024345A1 (en) | 2007-05-22 | 2008-11-27 | Beiersdorf Ag | Cosmetic preparation, useful e.g. as a sunscreen, comprises 4-dicyanomethylene-2,6-dimethyl-1,4-dihydropyridin-N-(ethyloxysulfate ester salt), 4-(tert.-butyl)-4'-methoxydibenzoylmethane and 2-ethylhexyl-2-cyano-3,3-diphenylacrylate |
DE102007024346A1 (en) | 2007-05-22 | 2008-11-27 | Beiersdorf Ag | Cosmetic formulation for protecting skin aging, particularly UV-induced skin aging, and for use in cosmetic sprays as sun protective agents, comprises dihydropyridine ethyloxysulfate ester salt and hydoxybenzoyl benzoic acid hexyl ester |
DE102007024347A1 (en) | 2007-05-22 | 2008-11-27 | Beiersdorf Ag | Cosmetic formulation for protecting skin aging, particularly UV-induced skin aging, and for use as sun protective agents, comprises dihydropyridine ethyloxysulfate ester salt and ethylhexyloxyphenol methoxyphenyl triazine |
DE102008018787A1 (en) * | 2008-04-11 | 2009-10-15 | Beiersdorf Ag | Preparation for the day care |
DE102008028664A1 (en) * | 2008-06-09 | 2009-12-10 | Beiersdorf Ag | Cosmetic preparations, especially sun-screen preparations, containing titanium dioxide and zinc oxide particles, hexyl diethylamino-hydroxybenzoyl-benzoate and panthenol |
KR20110073599A (en) * | 2008-10-22 | 2011-06-29 | 다우 글로벌 테크놀로지스 엘엘씨 | Sunscreen compositions incorporating methylcellulose as an spf booster and methods |
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 |
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Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102007024348A1 (en) | 2007-05-22 | 2008-11-27 | Beiersdorf Ag | Cosmetic formulation for use in cosmetic sprays, particularly in sun protective agents, comprises dicyanomethylene-dimethyl-dihydropyridine-(ethyloxysulfate ester mono sodium salt), tris (biphenyl)-triazine, UV filters and diols |
DE102007024345A1 (en) | 2007-05-22 | 2008-11-27 | Beiersdorf Ag | Cosmetic preparation, useful e.g. as a sunscreen, comprises 4-dicyanomethylene-2,6-dimethyl-1,4-dihydropyridin-N-(ethyloxysulfate ester salt), 4-(tert.-butyl)-4'-methoxydibenzoylmethane and 2-ethylhexyl-2-cyano-3,3-diphenylacrylate |
DE102007024346A1 (en) | 2007-05-22 | 2008-11-27 | Beiersdorf Ag | Cosmetic formulation for protecting skin aging, particularly UV-induced skin aging, and for use in cosmetic sprays as sun protective agents, comprises dihydropyridine ethyloxysulfate ester salt and hydoxybenzoyl benzoic acid hexyl ester |
DE102007024347A1 (en) | 2007-05-22 | 2008-11-27 | Beiersdorf Ag | Cosmetic formulation for protecting skin aging, particularly UV-induced skin aging, and for use as sun protective agents, comprises dihydropyridine ethyloxysulfate ester salt and ethylhexyloxyphenol methoxyphenyl triazine |
DE102008018787A1 (en) * | 2008-04-11 | 2009-10-15 | Beiersdorf Ag | Preparation for the day care |
DE102008028664A1 (en) * | 2008-06-09 | 2009-12-10 | Beiersdorf Ag | Cosmetic preparations, especially sun-screen preparations, containing titanium dioxide and zinc oxide particles, hexyl diethylamino-hydroxybenzoyl-benzoate and panthenol |
KR101637185B1 (en) | 2008-10-22 | 2016-07-07 | 다우 글로벌 테크놀로지스 엘엘씨 | Sunscreen compositions incorporating methylcellulose as an SPF booster and methods |
US20110256076A1 (en) * | 2008-10-22 | 2011-10-20 | Fletcher Robert B | Sunscreen compositions incorporating methycellulose as an spf booster and methods |
KR20110073599A (en) * | 2008-10-22 | 2011-06-29 | 다우 글로벌 테크놀로지스 엘엘씨 | Sunscreen compositions incorporating methylcellulose as an spf booster and methods |
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 (en) * | 2018-08-31 | 2019-01-04 | 江苏新亿源环保科技有限公司 | A kind of preparation method of polypropylene-base load nano-photo catalytic dosage form biologic packing material |
CN110339146A (en) * | 2019-08-21 | 2019-10-18 | 广州臻颜化妆品有限公司 | A kind of W/O/W foundation emulsion and preparation method thereof |
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