WO2007017179A1

WO2007017179A1 - Use of ionic uv-a sunscreens

Info

Publication number: WO2007017179A1
Application number: PCT/EP2006/007691
Authority: WO
Inventors: Katja Berg-Schultz; Christine Mendrok-Edinger; Alexander Poschalko; Horst Westenfelder
Original assignee: Dsm Ip Assets B.V.
Priority date: 2005-08-05
Filing date: 2006-08-03
Publication date: 2007-02-15

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

— (M^s+) or M^s+(A )_{s 1}, wherein 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

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 — (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

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 o_rr ^ Ca„2+

The compounds

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

where X' is a precursor structure of XY.

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 a)

Process b)

analogously to

Process c)

Analogously for

Process d)

Analogously for

Process e)

ditto for Li

Process f) 1 Michael Na

2 πng opening 3 neutralisation

Process g)

see general scheme

Process h)

Process i)

Process j)

Similar to example 2:

Similar to example 1 :

K

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

d) X is a residue

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 R^s 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/C_1O 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 C_{12 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, C_{12 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 a^re 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 |_au^reth 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) 4-Dicyanomethylene-2,6-dιmethyl-1 ,4-dihydropyridine-N-(3-[N,N-dimethylamino]- propane)

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) 2-{1 -[2-(2-Chloro-ethoxy)-ethyl]-2,6-dιmethyl-1 H-pyπdιn-4-ylιdene}-malononιtrιle

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 C}M_N 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

Potassium Cetyl Phosphate ^~ _l ^"2 00 Cetyϊ Alcohol ^"P 3 OOJ

Glyceryl Myπstate ' ⁴J?⁰

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

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,

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

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

R² is hydrogen and the other of R¹ and R² is an electron-withdrawing group, R³, R⁴, R⁵ and R^b 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,

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

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,

Y is a counterion for stabilizing perfumes and fragrances.

9. Use of compounds of the general formula I

wherein

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,

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

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

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,

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⁺.