WO2016012586A1

WO2016012586A1 - Sunscreen formulations optimized for the formation of vitamin d

Info

Publication number: WO2016012586A1
Application number: PCT/EP2015/066985
Authority: WO
Inventors: Bernd Herzog; Dieter Kockott; Heike Floesser-Mueller
Original assignee: Basf Se
Priority date: 2014-07-25
Filing date: 2015-07-24
Publication date: 2016-01-28
Also published as: KR102483132B1; CN106659653B; JP7204715B2; KR20170034891A; JP2022180512A; CN115227593A; US11419804B2; BR112017001490A2; JP2017521463A; JP2021001211A; EP3171945A1; CN106659653A; US20180200170A1; BR112017001490B1

Abstract

The present invention relates to a sunscreen formulation comprising at least one of the UV filters (A) selected from (a) triazine derivatives; (b) cinnamic acid derivatives; (c) bis-resorcinyl triazines; (f) benzimidazole derivatives; (i₅) 4-Methylbenzylidene Camphor; (h) benzoyl piperazine derivatives; (j) benzoxazole derivatives; (k) diarylbutadiene derivatives; (I) phenyl benzotriazole derivatives; (n) benzylidene malonates; (o₃) TEA-Salicylate; (r) imidazoline derivatives; (u) inorganic UV filters selected from metal oxides; (v) naphthalates; and (w) merocyanine derivatives; and optionally comprising at least one of the UV filters (B) selected from (d) aminobenzophenone derivatives; (e) dibenzoylmethane derivatives; (g) β,β-Diphenylacrylate derivatives; (i₅) camphor derivatives different from; (o₃) salicylate derivatives different from; (p) anthranilate derivatives; and (s) benzalmalonate derivatives; wherein the ratio R of the effective irradiance for previtamin D₃ formation E_pvd to the effective irradiance for erythema formation E_eron the skin is at least 1.8, for increasing the transmittance of UV radiation on human skin for the production of cholecalciferol (previtamin D₃) and simultaneously for the use in a method for protecting the human skin against UV radiation when exposed to the sun, which method comprises applying said sunscreen formulation to the skin.

Description

Sunscreen formulations optimized for the formation of Vitamin D Description The present invention relates to a method for increasing the transmittance of UV radiation for the production of cholecalciferol (vitamin D₃) on the human skin and simultaneously protecting the human skin against said UV radiation when exposed to the sun.

It is well known that chronic exposure to sunlight may have damaging effects to human skin. Depending on the wavelength UV radiation causes different types of skin damage. UV-B radiation (about 290 to about 320 nm) is responsible for sunburn and can cause skin cancer. UV-A radiation (about 320 to about 400 nm) while producing tanning of the skin contributes also to sunburn and the induction of skin cancers. Nowadays it is well acknowledged that adequate sun protection should include broadband protection, that means, i.e. sunscreen should protect against both UVA and UVB radiation. Since 2006 the European Recommendation, requires a minimum UVA protection related to the level of UVB protection which implies that the UVA-PF (UVA protection factor) is at least 1/3 of the SPF (sun protection factor).

Apart from the known damaging effects of UV radiation a certain amount of UVB radiation is necessary for the formation of vitamin D₃ and its precursors in the skin.

By reducing the erythemally effective irradiance (=E_r) with sunscreens in order to prevent sun- burn the effective irradiance responsible for vitamin D₃ formation (=E_pvD) is reduced as well.

Thus, sunscreens can reduce or even prevent the vitamin D₃ production in skin. This is not surprising, because the radiation which is responsible for causing sunburn (erythema) and skin damage is in the same of radiation range which is also responsible for epidermal vitamin D₃ synthesis. It has been shown that topical application of a sunscreen with a sun protection factor of 8 prevented any increase in circulating concentrations of vitamin D₃ after a whole-body exposure to simulated sunlight that would have caused mild sunburn. Hence, the use of sunscreen can diminish the body's own production of vitamin D₃ and chronic sunscreen use can lead to unwanted lower vitamin D₃ levels in blood. The problem underlying the present invention is to find sunscreens which counteract the inhibition of vitamin Deformation during sun exposure. Surprisingly it was found that sunscreens comprising at least one specific UV filter will comply with these requirements.

Therefore, the present invention refers to a sunscreen formulation comprising at least one of the UV filters (A) selected from

(a) triazine derivatives;

(b) cinnamic acid derivatives;

(c) bis-resorcinyl triazines;

(f) benzimidazole derivatives;

(i₅) 4-Methylbenzylidene Camphor;

(h) benzoyl piperazine derivatives;

(j) benzoxazole derivatives;

(k) diarylbutadiene derivatives;

(I) phenyl benzotriazole derivatives;

(n) benzylidene malonates;

(o₃) TEA-Salicylate;

(r) imidazoline derivatives;

(u) inorganic UV filters selected from metal oxides;

(v) naphthalates; and

(w) merocyanine derivatives; and

optionally comprising at least one of the UV filters (B) selected from

(d) aminobenzophenone derivatives;

(e) dibenzoylmethane derivatives;

(g) β,β-Diphenylacrylate derivatives;

(i) camphor derivatives different from (i₅);

(o) salicylate derivatives different from (o₃);

(p) anthranilate derivatives; and

(s) benzalmalonate derivatives; wherein

the ratio R of the effective irradiance for vitamin D₃ formation E_pvd to the effective irradiance for erythema formation E_er on the skin is at least 1.8,

for increasing the transmittance of UV radiation on human skin for the production of vitamin D₃ and simultaneously for the use in a method for protecting the human skin against UV radiation when exposed to the sun, which method comprises applying said sunscreen formulation to the skin. Effective Irradiance

The effective irradiance E_er can be calculated by multiplying the irradiance of the light source (= standard sun irradiance S( )) with the respective action spectrum s_er(k) for erythema formation and SpvD^) for vitamin D3 production, respectively at any wavelength in a spectral range according to the following formulas:

(Eler): Effective irradiance E_er for erythema formation E_er = iS(X) s_erM d

(EI_PVD): Effective irradiance E_PVD for vitamin D3 formation: E_PVD = ίβ(λ) svoQ ) dλ The ratio of the effective irradiance for vitamin D₃ formation and the effective irradiance for erythema formation R = E_pVD/E_er under conditions of natural sunlight is approximately

_ _ _ 1 « 2

Rsun ^— F

This can be illustrated by Fig 1 :

The UV filter classes as defined in claim 1 comprise different kinds of UV filters, i.e. UV-B filters (290 - 320 nm), UV-AII filters (320 - 340 nm), and broad spectrum and UV-AI filters (340 - 400 nm).

In the following representatives of common UV filter classes are listed.

Suitable triazine derivatives (a) are selected from

(a-i) Ethylhexyl Triazone;

(a₂) Tris-Biphenyl Triazine;

(a₃) Diethylhexyl Butamido Triazone,

(a₄) Phenylene Bis-Diphenyltriazine;

(a₅) 5,6,5',6'-tetraphenyl-3,3'-(1 ,4-Phenylene)bis(1 ,2,4-Triazine) corresponding to the formula

(a₆) Benzoic acid, 4,4'-[[6-[[3-[1 ,3,3,3-tetramethyl-1 -[(trimethylsilyl)oxy]-1 -disiloxanyl]propyl]- amino]-1 ,3,5-triazine-2,4-diyl]diimino]bis-, dibutyl ester of formula

Suitable cinnamic acid derivatives (b) are selected from

(bi) Ethylhexyl Methoxy Cinnamate;

(b₂) Isopropyl Methoxy Cinnamate;

(b₃) Isoamyl Methoxy Cinnamate;

(b₄) Diisopropyl Methyl Cinnamate,

(b₅) Cinnoxate;

(b₆) Glyceryl Ethylhexanoate,

(b₇) 2-Propenoic acid, 3-(4-ethoxyphenyl)-, 2-methylphenyl ester of formula

(b₈) 2-Propenoic acid, 3-(4-methoxyphenyl)-, 2-methylphenyl ester of formula

Propanedioic acid, 2-[(4-methoxyphenyl)methylene]-, 1 ,3-bis(2-methylbutyl) ester of formula

Me 0

(bio) Propanedioic acid, 2-[(4-methoxyphenyl)methylene]-, 1 ,3-bis(2-ethylhexyl) ester of formula

E t o

Suitable Bis-resorcinyl triazines (c) are selected from

(Ci ) Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine; and

(c₂) Aqueous dispersion of Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine / Polymethyl Methacrylate.

Suitable aminobenzophenone derivatives (d) are selected from (di) Diethylamino Hydroxybenzoyl Hexyl Benzoate.

Suitable dibenzoylmethane derivatives (e) are selected from

(e-i) Butyl Methoxy Dibenzoyl Methane; and

(e₂) Isopropyl Dibenzoylmethane.

Suitable benzimidazole derivatives (f) are selected from

(f-i) Phenyl Benzimidazole Sulfonic Acid; and

(f₂) Disodium Phenyl Dibenzimidazole Tetrasulfonate.

Suitable β,β-Diphenylacrylate derivatives (g) are selected from

(gi) Octocrylene; and

(g₂) Etocrylene. Suitable benzoyl-piperazine derivatives (h) are selected from

(h-i) 1 ,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)piperazine.

Suitable camphor derivatives (i) are selected from

(i-i) Terephthalylidene Dicamphor Sulfonic Acid;

(1₂) Benzylidene Camphor Sulfonic Acid;

(1₃) Camphor Benzalkonium Methosulfate;

(1₄) 3-Benzylidene Camphor;

(1₅) Methylbenzylidene Camphor; and

(1₆) Polyacrylamidomethyl Benzylidene Camphor.

Suitable benzoxazole derivatives (j) are selected from

(ji) Ethylhexyl Bis-lsopentylbenzoxazolylphenyl Melamine.

Suitable diarylbutadiene derivatives (k) are selected from

(k^ 1 ,1 -dicarboxy(2,2^'-dimethyl-propyl)-4,4-diphenylbutadiene.

Suitable phenyl benzotriazole derivatives (I) are selected from

(l-i) Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol;

(l₂) Drometrizole trisiloxane;

(l₃) Phenol, 2-(2H-benzotriazol-2-yl)-6-[[(2-ethylhexyl)oxy]methyl]-4-methyl- of formula

(1₄) Benzotriazolyl Dodecyl p-Cresol;

(1₅) polymeric benzotriazole type UV filter as described in US 201 10195036 ,

WO 201 1097555; e.g. a polymer prepd. from a dimer diol (C₃₆H₇2O), ditrimethylolpropane, di-methyl adipate, methyl adipate, and methyl 3-(2H-benzotriazol-2-yl)-5-(1 , 1 - dimethylethyl)-4-hydroxybenzenepropanoate; and

(1₆) 2-(2H-Benzotriazol-2-yl)-6-(2-ethylhexyloxymethyl)-4-methyl-phenol corresponding to formula

Suitable malonic acid derivatives (n) are selected from

-i) benzylidene malonates of formula , wherein

Ri is methyl; ethyl; propyl; or n-butyl;

if R-i is meth l, then

R₂ and R₃, independently from each other are hydrogen; or methyl;

R₄ is methyl; ethyl; or n-propyl; R₅ and R₆ independently from each other are hydrogen; or CrC₃alkyl; if R-_\ is ethyl; propyl; or n-butyl, then

R is isopropyl. Preferabl , in formula (BM)

R-i is methyl. Most preferred is the compound of formula

Exam les of compounds of formula (BM) are listed in the Table 1 below:

Table 1 : Examples of monomeric benzylidene malonates according to the present invention

(BM6) methyl

(BM7) methyl

(BM8) methyl

(BM9) methyl or-

(BM10) ethyl ^■A

(BM1 1 ) propyl ^■A

(BM12) n-butyl

(BM13) methyl

Further suitable malonates (n) refer to

(n₂) Diethylhexyl Syringylidenemalonate corresponding to formula

Suitable salicylate derivatives are selected from

(0₁) Ethylhexyl Salicylate;

(0₂) Dipropyleneglycol Salicylate;

(0₃) TEA Salicylate; and

(0₄) Homosalate Suitable anthranilate derivatives (p) refer to

(Pi) Menthyl Anthranilate.

Suitable imidazoline derivatives (r) are selected from

(r-ι) Ethylhexyl Dimethoxybenzylidene; and

(r₂) Dioxoimidazoline Propionate.

Suitable benzamalonate derivatives are selected from

(Si ) Polysilicone-15.

Suitable inorganic UV filters (u) are selected from

(ui) Zinc Oxide;

(u₂) Fe₂0₃; and

(u₃) Titanium Dioxide.

Suitable naphthalates (v) are selected from

(v-i) Diethylhexyl 2,6-Naphthalate.

Preferably the sunscreen formulation according to the present invention has an SPF of at least 2.

More preferably the sunscreen formulation according to the present invention has an SPF of at least 6. The sunscreen formulation according to the present invention comprises 1 , or more than 1 UV filter.

For example, the sunscreen formulation according to the present invention may comprise 1 , 2, 3, 4, 5 or 6 UV filters selected from the UV filter classes as defined in claim 1 .

Preferably the sun screen formulation according to the present invention comprises the UV filters selected from

(a-i) Ethylhexyl Triazone.

(a₂) Tris-Bephenyl Triazine;

(a₃) Diethylhexyl Butamido Triazone;

(Ci ) Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine; (c₂) Aqueous dispersion of Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine / Polymethyl

Methacrylate;

(di) Diethylamino Hydroxybenzoyl Hexyl Benzoate;

(e-i) Butyl Methoxy Dibenzoyl Methane;

(f-i) Phenyl Benzimidazole Sulfonic Acid;

(f₂) Disodium Phenyl Dibenzimidazole Tetrasulfonate;

(gi) Octocrylene;

(h-i) 1 ,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)piperazine;

( ) Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol;

(l₂) Drometrizole trisiloxane ;

(l₆) 2-(2H-Benzotriazol-2-yl)-6-(2-ethylhexyloxymethyl)-4-methyl-phenol;

(i-i) Terephthalylidene Dicamphor Sulfonic Acid;

(rii) Compound of formula (BM9);

(oi) Ethylhexyl Salicylate;

(o₄) Homosalate;

(Pi) Menthyl Anthranilate;

(si) Polysilicone-15;

(ui) Zinc Oxide; and

(u₃) Titanium Dioxide;

More preferably the sun screen formulation according to the present invention comprises the UV filters selected from

(a-i) Ethylhexyl Triazone;

(bi) Ethylhexyl Methoxy Cinnamate;

(Ci ) Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine;

(di) Diethylamino Hydroxybenzoyl Hexyl Benzoate;

(l-i) Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol;

(e-i) Butyl Methoxy Dibenzoyl Methane;

(f-i) Phenyl Benzimidazole Sulfonic Acid;

(gi) Octocrylene; and

(u₃) Titanium Dioxide.

Preferably this sun screen formulation has an SPF of at least 6.

Even more preferably the sun screen formulation according to the present comprises the UV filters selected from

(bi) Ethylhexyl Methoxy Cinnamate; (Ci ) Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine;

(di) Diethylamino Hydroxybenzoyl Hexyl Benzoate;

(l-i ) Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol;

(ei ) Butyl Methoxy Dibenzoyl Methane;

(f-i ) Phenyl Benzimidazole Sulfonic Acid; and

(gi) Octocrylene.

Preferably this sun screen formulation has an SPF of at least 6.

Furthermore, the sun screen formulation according to the present preferably comprises the UV filters selected from

(Ci ) Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine;

(di) Diethylamino Hydroxybenzoyl Hexyl Benzoate;

(l-i ) Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol; and

(e-i ) Butyl Methoxy Dibenzoyl Methane.

Preferably this sun screen formulation has an SPF of at least 6.

Preferably, the sun screen formulation according to the present comprises the UV filter concentrations selected from

(a) 0.1 -40 % b.w. triazine derivatives;

(b) 0.1 - 30 % b.w. cinnamic acid derivatives;

(c) 0.1 - 10 % b.w. bis-resorcinyl triazines;

(f) 0.1 - 10 % b.w. benzimidazole derivatives;

(is) 0.1 - 10 % b.w. 4-Methylbenzylidene Camphor;

(h) 0.1 - 10 % b.w. benzoyl piperazine derivatives;

(j) 0.1 - 10 % b.w. benzoxazole derivatives;

(k) 0.1 - 20 % b.w. diarylbutadiene derivatives;

(I) 0.1 - 30 % b.w. phenyl benzotriazole derivatives;

(n) 0.1 - 20 % b.w. benzylidene malonates;

(o₃) 0.1 - 15 % b.w. TEA-Salicylate;

(r) 0.1 - 10 % b.w. imidazoline derivatives;

(u) 0.1 - 50 % b.w. inorganic UV filters selected from metal oxides;

(v) 0.1 - 20 % b.w. naphthalates; and

(w) 0.1 - 20 % b.w. merocyanine derivatives; and

optionally comprising at least one of the UV filters (B) selected from

(d) 0.1 - 20 % b.w. aminobenzophenone derivatives; (e) 0.1 - 5 % b.w. dibenzoylmethane derivatives;

(g) 0.1 - 1 % b.w. β,β-Diphenylacrylate derivatives;

(i) 0.1 - 10 % b.w. camphor derivatives different from (i₅);

(o) 0.1 - 35 % b.w. salicylate derivatives different from (o₃);

(P) 0.1 - 10 % b.w. anthranilate derivatives; and

(s) 0.1 - 10 % b.w. benzalmalonate derivatives.

More preferably, the sun screen formulation according to the present comprises the UV filter concentrations selected from

(ai) 1 - 3 % b.w. Ethylhexyl Triazone;

(bi) 1 - 3.5 % b.w. Ethylhexyl Methoxycinnamate;

(Ci ) 0.6 - 10 % b.w. Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine;

(di) 0.8 - 10 % b.w. Diethylamino Hydroxybenzoyl Hexyl Benzoate;

(e-i) 2 - 3 % b.w. Butyl Methoxydibenzoylmethane;

(f-i) 2 - 3 % b.w. Phenyl Benzimidazole Sulfonic Acid;

(gi) 2.0 - 2.5 % b.w. Octocrylene;

( ) 2 - 7.5 % b.w. Methylene Bis-Benzotriazolyl Tetramethylbutylphenol; and

(u₃) 3.0 - 3.5 % b.w. Titanium Dioxide. The sunscreen formulations according to the present invention achieve an SPF of > 15 by the use of the UV filter combinations of

(di) Diethylamino Hydroxybenzoyl Hexyl Benzoate;

(l-i) Methylene Bis-benzotriazolyl Tetramethyl Butylphenol; and

(e-i) Butyl Methoxy Dibenzoyl Methane; most preferably

(di) 9.0 - 1 1.0 % b.w. of Diethylamino Hydroxybenzoyl Hexyl Benzoate;

( ) 2.5 - 3.5 % b.w. of Methylene Bis-Benzotriazolyl Tetramethylbutylphenol; and

(e-i) 2.5 - 3.5 % b.w Butyl Methoxydibenzoylmethane.

The sunscreen formulations according to the present invention achieve an SPF of > 30 by the use of the UV filter combinations of

(Ci ) Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine;

(di) Diethylamino Hydroxybenzoyl Hexyl Benzoate;

(l-i) Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol; and

(e-i) Butyl Methoxy Dibenzoyl Methane;

most preferably

(Ci ) 1 .5 - 2.5 % b.w. of Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine;

(di) 9.5 - 10.5 % b.w. of Diethylamino Hydroxybenzoyl Hexyl Benzoate; ( ) 7 - 8 % b.w. of Methylene Bis-Benzotriazolyl Tetramethylbutylphenol; and

(e-i) 2.5 - 3.5 % b.w. of Butyl Methoxydibenzoylmethane.

Preferably sunscreen formulation according to the present invention are used, wherein the UV filters are selected from the broadband (spectrum of 340 to 400 nm) UV filters

(Ci ) Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine;

(c₂) Aqueous dispersion of Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine / Polymethyl Methacrylate;

(f₂) Disodium Phenyl Dibenzimidazole Tetrasulfonate;

( ) Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol;

(l₂) Drometrizole trisiloxane;

(ui) Zinc Oxide; and optionally

(e-i) Butyl Methoxy Dibenzoyl Methane;

(di) Diethylamino Hydroxybenzoyl Hexyl Benzoate;

(i-i) Terephthalylidene Dicamphor Sulfonic Acid; and

(Pi) Menthyl Anthranilate.

Furthermore, the present invention refers to sunscreen formulations comprising a UV filter se- lected from

(a) triazine derivatives

(b) cinnamic acid derivatives;

(c) bis-resorcinyl triazines;

(f) benzimidazole derivatives;

(h) benzoyl-piperazine derivatives;

(is) 4-Methylbenzylidene Camphor;

(I) phenyl benzotriazole derivatives;

(n) benzylidene malonates;

(03) TEA-Salicylate;

(r) imidazoline derivatives;

(u) inorganic UV filters selected from metal oxides;

(v) naphthalates; and

(w) merocyanine derivatives;

wherein the sunscreen formulation contains only one of the selected UV filters.

Preferably sunscreen formulations are used, wherein the UV filters are selected from broadband

(spectrum of 340 to 400 nm) UV filters

(Ci ) Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine; (c₂) Aqueous dispersion of Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine / Polymethyl Methacrylate;

(f₂) Disodium Phenyl Dibenzimidazole Tetrasulfonate;

(l-i) Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol;

(i-i) Terephthalylidene Dicamphor Sulfonic Acid; and

(ui) Zinc Oxide;

wherein the sunscreen formulation contains only one of the selected UV filters.

Furthermore, sunscreen formulations are preferred, which comprise particulate UV filters selected from

(a₂) Tris-Bephenyl Triazine;

(h-i) 1 ,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)piperazine;

(l-i) Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol;

(ui) Zinc Oxide; and

(u₃) Titanium Dioxide.

Furthermore, sunscreen formulations are preferred, which comprise non-particulate UV filters selected from

(a-i) Ethylhexyl Triazone.

(a₃) Diethylhexyl Butamido Triazone;

(Ci ) Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine;

(di) Diethylamino Hydroxybenzoyl Hexyl Benzoate;

(e-i) Butyl Methoxy Dibenzoyl Methane;

(f-i) Phenyl Benzimidazole Sulfonic Acid;

(f₂) Disodium Phenyl Dibenzimidazole Tetrasulfonate;

(gi) Octocrylene;

(h-i) 1 ,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)piperazine;

(l-i) Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol;

(l₂) Drometrizole trisiloxane ;

(l₆) 2-(2H-Benzotriazol-2-yl)-6-(2-ethylhexyloxymethyl)-4-methyl-phenol;

(ii) Terephthalylidene Dicamphor Sulfonic Acid;

(rii) Compound of formula (BM9);

(oi) Ethylhexyl Salicylate;

(o₄) Homosalate;

(Pi) Menthyl Anthranilate; and ) Polysilicone-1

The preferred ratio of the effective irradiance for vitamin D₃ formation E_pvd to the effective irradi- ance for erythema formation E_er on the skin of the sunscreen formulations according to the pre- sent invention wherein is at least 1 .8, preferably at least 1 ,85, more preferably at least 1 ,90 even more preferably > 1 ,95, most preferably at least 2,0 and upmost preferably at least 2,1 .

Further sunscreen formulations according to the present invention wherein the ratio of the effective irradiance for vitamin D₃ formation E_pvd to the effective irradiance for erythema formation E_er on the skin is at least 1.8; and which contain the UV filter combinations CSF 1 - CSF 32 of Table 1 are preferred.

According to the present invention sunscreen compositions with optimized transparency for improved vitamin D₃ production in a huge range of SPFs up to > SPF60 can be provided, which include but are not limited to the sun protection factors (abbreviated as SPF) proposed by the European Commission Recommendation: SPF 6, 15, 30, 50 and 50+ (>60). According to the EC Recommendation an SPF of 6 belongs to the class of "low protection", an SPF 15 to the "medium protection", an SPF 30 and 50 to the "high protection", and SPF 50 + (requiring SPF min 60) to the "very high protection" category.

Regarding broadband protection the EC recommendation says that the ratio of UVA-PF/SPF should at least be 1/3, and the critical wavelength (CW) at least 370 nm. For low UVA protection the UVA-PF/SPF ratio is significantly lower, for high UVA-protection, it is far higher than 1/3. Sunscreens necessarily reduce both E_er and E_pvd on the skin. The ratio R = E_pvd/E_er can be optimized by choosing an adequate UV filter combination. The higher the said ratio R , the better the sunscreen will perform concerning the vitamin D₃ production for a given protection against

The sun screen formulation according to the present invention is especially useful for the protection of organic materials that are sensitive to ultraviolet light, especially human and animal skin and hair, against the action of UV radiation and simultaneously for increasing the transmit- tance of UV radiation for the production of vitamin D₃ on the human ski. Such UV filter combinations are therefore suitable as light-protective agents in cosmetic and pharmaceutical prepa- rations. The sun screen formulations according to the present invention contain from 1 to 50 % by weight, preferably 1 - 20 % by weight, preferably from 3 to 15 % by weight, based on the total weight of the formulation, the combination of UV filters as defined in claim 1 and a cosmetically tolerable adjuvant

The sun screen formulations according to the present invention can be prepared by physically mixing the UV filters as defined in claim 1 with the adjuvant using customary methods, for example by simply stirring together the individual components, especially by making use of the dissolution properties of already known cosmetic UV absorbers, for example Ethylhexyl Meth- oxycinnamate (UV filter component (bi)). The UV filters as defined in claim 1 can be used in the sunscreen formulation, for example, without further treatment.

Some of the UV filters used in the sunscreen of the present invention, for example ( ) Methylene Bis-Benzotriazolyl Tetramethylbutylphenol, (a₂) Tris-Biphenyl Triazine or (h-ι) 1 ,4-(2-(4- diethylamino-2-hydroxybenzoyl)benzoyl)piperazine cane used in their micronized state (na- noscalar organic filters, particulate organic filters, UV-absorber pigments).

Any known process suitable for the preparation of microparticles can be used for the preparation of the micronised UV filters, for example wet-milling (low viscous micronization process for pumpable dispersions), with a hard grinding medium, for example zirconium silicate balls in a ball mill and a protective surfactant or a protective polymer in water or in a suitable organic solvent, wet-kneading (high viscous micronization process non pump-able pastes) using a continuous or discontinuous (batch) kneader, spray-drying from a suitable solvent, by the expansion according to the RESS process (Rapid Expansion of Supercritical Solutions) of supercritical fluids (e.g. C0₂), or by precipitation from suitable solvents, including supercritical fluids.

Suitable milling apparatus for the preparation of the micronized organic UV filters are for example, a jet mill, ball mill, vibratory mill or hammer mill, preferably a high-speed mixing mill or ball mills. The grinding is preferably carried out with a grinding aid.

The micronized UV filters so obtained usually have an average particle size from 0.02 to 2 micrometer, preferably from 0.05 to 1.5 micrometer and more especially from 0.1 to 1 .0 micrometer. The micronized UV filters used in the present invention are preferably present as aqueous dispersions. The grinding of the sparingly soluble organic compounds used in the present invention is preferably carried out with a grinding aid. The dispersing agent is used as a low molecular weight grinding aid for all the above micronisation processes. Preferred useful grinding aids for an aqueous dispersion are anionic surfactants with a HLB value higher than 8, more preferably higher than 10. Any conventionally usable anionic, non-ionic or amphoteric surfactants can be used as

dispersing agents (component (b)). Such surfactant systems may comprise for example: car- boxylic acids and their salts: alkaline soap of sodium, potassium and ammonium, metallic soap of calcium or magnesium, organic basis soap such as Laurie, myristic, palmitic, stearic and oleic acid etc ... Alkyl phosphates or phosphoric acid esters, acid phosphate, diethanolamine phosphate, potassium cetyl phosphate. Ethoxylated carboxylic acids or polyethyleneglycol esters, PEG-n acylates. Fatty alcohol polyglycolether such as laureth-n, myreth-n, ceteareth-n, stea- reth-n, oleth-n. Fatty acid polyglycolether such as PEG-n-stearate, PEG-n oleate, PEG-n co- coate. Monoglycerides and polyol esters. C12-C22 fatty acid mono- and di-esters of addition products of from 1 to 100 mol of ethylene oxide with polyols. Fatty acid and polyglycerol ester such as monostearate glycerol, diisostearoyl polyglyceryl-3-diisostearates, polyglyceryl-3- diisostearates, triglyceryl diisostearates, polyglyceryl-2-sesquiisostearates or polyglyceryl di- merates. Mixtures of compounds from a plurality of those substance classes are also suitable. Fatty acid polyglycolesters such as monostearate diethylene glycol, fatty acid and polyethylene glycol esters, fatty acid and saccharose esters such as sucre esters, glycerol and saccharose esters such as sucre glycerides. Sorbitol and sorbitan, sorbitan mono- and di-esters of saturat- ed and unsaturated fatty acids having from 6 to 22 carbon atoms and ethylene oxide addition products. Polysorbate-n series, sorbitan esters such as sesquiisostearate, sorbitan, PEG- (6)isostearate sorbitan, PEG-(10)-sorbitan laurate, PEG-17- dioleate sorbitan. Glucose derivatives, C8-C22 alkyl-mono and oligo-glycosides and ethoxylated analogues with glucose being preferred as the sugar component. 0/W emulsifiers such as methyl gluceth-sesquistearate, sor- bitan stearate/sucrose cocoate, methyl glucose sesquistearate, cetearyl alcohol/cetearyl gluco- side. W/0 emulsifiers such as methyl glucose dioleate/ methyl glucose isostearate. Sulfates and sulfonated derivatives, dialkylsulfosuccinat.es, dioctyl succinate, alkyllauryl sulfonate, linear sulfonated parafins, sulfonated tetraproplyne sulfonate, sodium lauryl sulfates, amonium and etha- nolamine lauryl sulfates, lauyl ether sulfates, sodium laureth sulfates or sodium myreth sulfates, sulfosuccinates, aceyl isothionates, alkanolamide sulfates, taurines, methyl taurines, imidazole sulfates. Zwitterionic or amphoteric surfactants that carry at least one quaternary ammonium group and at least one carboxylate and/or sulfonate group in the molecule. Zwitterionic surfactants that are especially suitable are betaines, such as N-alkyi-N,N-dimethylammonium glyci- nates, cocoalkyldimethylammonium glycinate, N-acylaminopropyi-N,N-dimethylammonium glycinates, cocoacylaminopropyldimethylammonium glycinate and 2-alkyl-3-carboxymethyl-3- hydroxyethylimidazolines each having from 8 to 18 carbon atoms in the alkyl or acyl group and also cocoacylaminoethylhydroxyethylcarboxymethylglycinate, N-alkylbetaine, Nalkylaminobeta- ines. Examples of suitable mild surfactants as dispersing agents, that is to say surfactants especially well tolerated by the skin, include fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and/or di-alkyl sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, a. -olefin sulfonates, ethercarboxylic acids, alkyl oli- goglucosides, fatty acid glucamides, alkylamidobetaines and/or protein fatty acid condensation products, the latter preferably being based on wheat proteins. Non ionic surfactants such as PEG-6 beeswax (and) PEG-6 stearate (and) polyglyceryl-2-isostearate [Apifac], glyceryl stearate (and) PEG-1 00 stearate. [Arlacel 165], PEG-5 glyceryl stearate (arlatone 983 S], sorbitan oleate (and) polyglyceryl-3 ricinoleate. [Arlacel 1689), sorbitan stearate and sucrose cocoate [arlatone 2121], glyceryl stearate and laureth-23 [Cerasynth 945], cetearyl alcohol and ceteth-20 [Cetomacrogol Wax], cetearyl alcohol and colysorbate 60 and PEG-150 and stearate- 20[Polawax GP 200, Polawax NF], cetearyl alcohol and cetearyl polyglucoside [Emulgade PL 1618], cetearyl alcohol and ceteareth-20 [Emulgade 1 OOONI, Cosmowax]. cetearyl alcohol and PEG-40 castor oil [Emulgade F Special], cetearyl alcohol and PEG-40 castor oil and sodi- urn cetearyl sulfate [Emulgade F], stearyl alcohol and steareth-7 and steareth-10 [Emulgator E 2155], cetearyl alcohol and szeareth-7 and steareth-10 [Emulsifying wax U.S.N.F], glyceryl stearate and PEG-75 stearate [Gelot 64], propylene glycol ceteth-3 acetate .[Hetester PCS), propylene glycol - 8- isoceth-3 acetate [Hetester PHA], cetearyl alcohol and ceteth-12 and oleth- 12 [Lanbritol Wax N 21 ], PEG -6 stearate and PEG-32 stearate [Tefose 1500], PEG-6 stearate and ceteth-20 and steareth-20 [Tefose 2000], PEG-6 stearate and ceteth-20 and glyceryl stearate and steareth-20 [Tefose 2561], glyceryl stearate and ceteareth-20 [Teginacid H, C, X]. Anionic emulsifiers such as PEG-2 stearate SE, glyceryl stearate SE [Monelgine, Cutina KD], propylene glycol stearate [Tegin P], cetearyl Alcohol and Sodium cetearyl sulfate [Lanette N, Cutina LE, Crodacol GP], cetearyl alcohol and sodium lauryl sulfate [Lanette W], trilaneth-4 phopshate and glycol stearate and PEG-2 stearate [Sedefos 75], glyceryl stearate and sodium lauryl Sulfate [Teginacid Special]. Cationic acid bases such as cetearyl alcohol and cetrimonium bromide. Most preferred dispersing agents (b) are sodium alkyl sulfates or sodium alkyl ether sulfates, such as sodium laureth sulfate [Texapon N70 from Cognis] or sodium myreth sulfate [Texapon K14 S from Cognis]. The specific dispersing agents may be used in an amount of, for example, from 1 to 30 % by weight, especially from 2 to 20 % by weight and preferably from 3 to 10 % by weight, based on the total weight of the composition. Useful solvents are water, brine, (polyethylene glycol, glycerol or cosmetically acceptable oils. Other useful solvents are disclosed below in the sections entitled "Esters of fatty acids", "Natural and synthetic triglycerides, including glyceryl esters and derivatives", "Pearlescent waxes", "Hydrocarbon oils" and "Silicones or siloxanes". If the formulations according to the present invention represent water- and oil-containing emulsions (e.g. W/O, O/W, 0/W/O and W/O/W emulsions or microemulsions) they contain, for example, from 0.1 to 30 % by weight, preferably from 0.1 to 15 % by weight and especially from 0.5 to 10 % by weight, based on the total weight of the composition, of the UV filters selected from (a) - (x), from 1 to 60 % by weight, especially from 5 to 50 % by weight and preferably from 10 to 35 % by weight, based on the total weight of the composition, of at least one oil component, from 0 to 30 % by weight, especially from 1 to 30 % by weight and preferably from 4 to 20 % by weight, based on the total weight of the composition, of at least one emulsifier, from 10 to 90 % by weight, especially from 30 to 90 % by weight, based on the total weight of the composi- tion, of water, and from 0 to 88.9 % by weight, especially from 1 to 50 % by weight, of further cosmetically tolerable adjuvants.

Suitable oil components of oil-containing compositions (e.g. oils, W/O, O/W, 0/W/O and W/O/W emulsions or microemulsions) are for example Guerbet alcohols based on fatty alcohols having from 6 to 18, preferably from 8 to 10, carbon atoms, esters of linear C₆-C₂4 fatty acids with linear C3-C24 alcohols, esters of branched C₆-Ci₃carboxylic acids with linear C₆-C₂4 fatty alcohols, esters of linear C₆-C₂4 fatty acids with branched alcohols, especially 2-ethylhexanol, esters of hy- droxycarboxylic acids with linear or branched C₆-C₂2 fatty alcohols, especially dioctyl malates, esters of linear and/or branched fatty acids with polyhydric alcohols (for example propylene gly- col, dimer diol or trimer triol) and/or Guerbet alcohols, triglycerides based on C₆-Ci₀ fatty acids, liquid mono-/di-/tri-glyceride mixtures based on C₆-Ci₈ fatty acids, esters of C₆-C₂4 fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, especially benzoic acid, esters of C₂- Ci₂dicarboxylic acids with linear or branched alcohols having from 1 to 22 carbon atoms or pol- yols having from 2 to 10 carbon atoms and from 2 to 6 hydroxy groups, vegetable oils (such as sunflower oil, olive oil, soybean oil, rapeseed oil, almond oil, jojoba oil, orange oil, wheat germ oil, peach kernel oil and the liquid components of coconut oil), branched primary alcohols, substituted cyclohexanes, linear and branched C₆-C₂₂ fatty alcohol carbonates, Guerbet carbonates, esters of benzoic acid with linear and/or branched C₆-C₂₂alcohols (e.g. Finsolv^® TN), linear or branched, symmetric or asymmetric dialkyl ethers having a total of from 12 to

36 carbon atoms, especially from 12 to 24 carbon atoms, for example di-n-octyl ether, di-n-decyl ether, di-n-nonyl ether, di-n-undecyl ether, di-n-dodecyl ether, n-hexyl n-octyl ether, n-octyl n- decyl ether, n-decyl n-undecyl ether, n-undecyl n-dodecyl ether, n-hexyl n-undecyl ether, di-tert- butyl ether, diisopentyl ether, di-3-ethyldecyl ether, tert-butyl n-octyl ether, isopentyl n-octyl ether and 2-methyl pentyl-n-octyl ether; ring-opening products of epoxidized fatty acid esters with polyols, silicone oils and/or aliphatic or naphthenic hydrocarbons. Also of importance are monoesters of fatty acids with alcohols having from 3 to 24 carbon atoms. That group of substances comprises the esterification products of fatty acids having from 8 to 24 carbon atoms, for example caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotride- canoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and technical-grade mixtures thereof (obtained, for example, in the pressure removal of natural fats and oils, in the reduction of aldehydes from Roelen's oxosynthesis or in the dimerisation of unsaturated fatty acids) with alcohols, for example isopropyl alcohol, caproic alcohol, capryl alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linoyl alcohol, linolenyl al- cohol, elaeostearyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and technical-grade mixtures thereof (obtained, for example, in the high- pressure hydrogenation of technical-grade methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as monomer fractions in the dimerisation of unsaturated fatty alcohols). Of special importance are isopropyl myristate, isononanoic acid Ci₆-Ci₈alkyl esters, stearic acid 2-ethylhexyl ester, cetyl oleate, glycerol tricaprylate, coconut fatty alcohol capri- nate/caprylate and n-butyl stearate. Further oil components that can be used are dicarboxylic acid esters, such as di-n-butyl adipate, di(2-ethylhexyl) adipate, di(2-ethylhexyl) succinate and diisotridecyl acetate, and also diol esters, such as ethylene glycol dioleate, ethylene glycol diisotridecanoate, propylene glycol di(2-ethylhexanoate), propylene glycol diisostearate, propyl- ene glycol dipelargonate, butanediol diisostearate and neopentyl glycol dicaprylate. Preferred mono- or poly-ols are ethanol, isopropanol, propylene glycol, hexylene glycol, glycerol and sorbitol. It is also possible to use di- and/or trivalent metal salts (alkaline earth metal, Al³⁺ inter alia) of one or more alkyl carboxylic acids. The oil components can be used in an amount of, for example, from 1 to 60 % by weight, especially from 5 to 50 % by weight and preferably from 10 to 35 % by weight, based on the total weight of the composition

Any conventionally usable emulsifier can be used for the cosmetic compositions according to the present invention.

Suitable emulsifiers are for example, non-ionic surfactants from the following groups:

addition products of from 2 to 30 mol of ethylene oxide and/or from 0 to 5 mol of propylene oxide with linear fatty alcohols having from 8 to 22 carbon atoms, with fatty acids having from 12 to 22 carbon atoms and with alkylphenols having from 8 to 15 carbon atoms in the alkyl group, for example ceteareth-20 or ceteareth-12;

C12-C22 fatty acid mono- and di-esters of addition products of from 1 to 30 mol of ethylene oxide with polyols having from 3 to 6 carbon atoms, especially with glycerol; glycerol mono- and di-esters and sorbitan mono- and di-esters of saturated and unsaturated fatty acids having from 6 to 22 carbon atoms and ethylene oxide addition products thereof, for example glyceryl stearates, glyceryl isostearates, glyceryl oleates, sorbitan ole- ates or sorbitan sesquioleates;

- C₈-C₂2alkyl-mono- and -oligo-glycosides and ethoxylated analogues thereof, degrees of oligomerisation of from 1 .1 to 5, especially from 1.2 to 1 .4, being preferred, and glucose being preferred as the sugar component;

addition products of from 2 to 60 mol, especially from 15 to 60 mol, of ethylene oxide with castor oil and/or hydrogenated castor oil;

- polyol esters and especially polyglycerol esters, for example diisostearoyl polyglyceryl-3- diisostearates, polyglyceryl-3-diisostearates, triglyceryl diisostearates, polyglyceryl-2- sesquiisostearates or polyglyceryl dimerates. Mixtures of compounds from a plurality of those substance classes are also suitable;

partial esters based on linear, branched, unsaturated or saturated C₆-C₂2 fatty acids, ricino- leic acid and also 12-hydroxystearic acid and on glycerol, polyglycerol, pentaerythritol, di- pentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. methyl glucoside, butyl glucoside, lauryl glucoside) and also polyglucosides (e.g. cellulose), for example polyglyc- eryl-2-dihydroxystearates or polyglyceryl-2-diricinoleates;

mono-, di- and tri-alkylphosphates and also mono-, di- and/or tri-PEG-alkylphosphates and salts thereof;

wool wax alcohols;

one or more ethoxylated esters of natural derivatives, for example polyethoxylated esters of hydrogenated castor oil;

silicone oil emulsifiers, for example silicone polyol;

- polysiloxane/polyalkyl/polyether copolymers and corresponding derivatives, for example cetyl dimethicone copolyol;

mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol (see DE-A-1 165 574) and/or mixed esters of fatty acids having from 6 to 22 carbon atoms, methylglucose and polyols, preferably glycerol or polyglycerol, for example polyglyceryl-3-glucose dis- tearates, polyglyceryl-3-glucose dioleates, methyl glucose dioleates or dicocoyl pentae- rythryl distearyl citrates; and also

polyalkylene glycols.

The addition products of ethylene oxide and/or of propylene oxide with fatty alcohols, fatty ac- ids, alkylphenols, glycerol mono- and di-esters and also sorbitan mono- and di-esters of fatty acids, or with castor oil, are known, commercially available products. They are usually homo- logue mixtures, the average degree of alkoxylation of which corresponds to the ratio of the amounts of ethylene oxide and/or propylene oxide and substrate with which the addition reaction is carried out. Ci₂-Ci₈ fatty acid mono- and di-esters of addition products of ethylene oxide with glycerol are known, for example, from DE-A-2 024 051 as fat-restoring substances for cosmetic preparations.

Cs-C-isAlkyl-mono- and -oligo-glycosides, their preparation and their use are known from the prior art. They are prepared especially by reacting glucose or oligosaccharides with primary alcohols having from 8 to 18 carbon atoms. Suitable glycoside radicals include monoglycosides in which a cyclic sugar radical is glycosidically bonded to the fatty alcohol and also oligomeric glycosides having a degree of oligomerisation of up to preferably about 8. The degree of oligo- merisation is a statistical average value based on a homologue distribution customary for such technical-grade products.

It is also possible to use zwitterionic surfactants as emulsifiers. The term "zwitterionic surfactants" denotes especially surface-active compounds that carry at least one quaternary ammonium group and at least one carboxylate and/or sulfonate group in the molecule. Zwitterionic surfactants that are especially suitable are the so-called betaines, such as N-alkyl-N,N-dimethyl- ammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylamino- propyl-N,N-dimethylammonium glycinates, for example cocoacylaminopropyldimethyl- ammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines each having from 8 to 18 carbon atoms in the alkyl or acyl group and also cocoacylaminoethylhydroxyethylcar- boxymethylglycinate. Special preference is given to the fatty acid amide derivative known by the CTFA name cocamidopropyl betaine. Likewise suitable as emulsifiers are ampholytic surfactants. Ampholytic surfactants are to be understood as meaning especially those which, in addition to containing a C₈-Ci₈-alkyl or -acyl group, contain at least one free amino group and at least one -COOH or -S0₃H group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants include N-alkylglycines, N-alkylpropionic acids, N-al- kylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropyl- glycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids, each having approximately from 8 to 18 carbon atoms in the alkyl group.

Ampholytic surfactants to which special preference is given are N-cocoalkylamino-propionate, cocoacylaminoethylaminopropionate and Ci₂-Ci₈acylsarcosine. In addition to the ampholytic emulsifiers there also come into consideration quaternary emulsifiers, special preference is giv- en to those of the esterquat type, preferably methyl-quaternised di-fatty acid triethanolamine ester salts. Non-ionic emulsifiers are preferred, preferably ethoxylated fatty alcohols having from 8 to 22 carbon atoms and from 4 to 30 EO units.

The emulsifiers may be used in an amount of, for example, from 1 to 30 % by weight, especially from 4 to 20 % by weight and preferably from 5 to 10 % by weight, based on the total weight of the composition. It is, however, also possible in principle to dispense with the use of emulsifiers.

The compositions according to the invention, for example creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick preparations, powders or ointments, may in addition contain, as further adjuvants and additives, mild surfactants, super- fatting agents, pearlescent waxes, consistency regulators, thickeners, polymers, silicone compounds, fats, waxes, stabilisers, biogenic active ingredients, deodorising active ingredients, anti- dandruff agents, film formers, swelling agents, antioxidants, hydrotropic agents, preservatives, insect repellents, self-tanning agents, solubilizers, perfume oils, colorants, bacteria-inhibiting agents and the like.

Substances suitable for use as super-fatting agents are, for example, lanolin and lecithin and also polyethoxylated or acrylated lanolin and lecithin derivatives, polyol fatty acid esters, mono- glycerides and fatty acid alkanolamides, the latter simultaneously acting as foam stabilisers.

Examples of suitable mild surfactants, that is to say surfactants especially well tolerated by the skin, include fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and/or di- alkyl sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, α-olefin sulfonates, ether carboxylic acids, alkyl oligoglucosides, fatty acid glu- camides, alkylamidobetaines and/or protein fatty acid condensation products, the latter preferably being based on wheat proteins.

Suitable pearlescent are for example: alkylene glycol esters, especially ethylene glycol dis- tearate; fatty acid alkanolamides, especially coco fatty acid diethanolamide; partial glycerides, especially stearic acid monoglyceride; esters of polyvalent, unsubstituted or hydroxy-substituted carboxylic acids with fatty alcohols having from 6 to 22 carbon atoms, especially long-chained esters of tartaric acid; fatty substances, for example fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which in total have at least 24 carbon atoms, especially laurone and distearyl ether; fatty acids, such as stearic acid, hydroxystearic acid or behenic ac- id, ring-opening products of olefin epoxides having from 12 to 22 carbon atoms with fatty alcohols having from 12 to 22 carbon atoms and/or polyols having from 2 to 15 carbon atoms and from 2 to 10 hydroxy groups, and mixtures thereof. Suitable consistency regulators are especially fatty alcohols or hydroxy fatty alcohols having from 12 to 22 carbon atoms and preferably from 16 to 18 carbon atoms, and in addition partial glycerides, fatty acids and hydroxy fatty acids. Preference is given to a combination of such substances with alkyl-oligoglucosides and/or fatty acid N-methylglucamides of identical chain length and/or polyglycerol poly-12-hydroxystearates. Suitable thickeners include, for example, Aerosil types (hydrophilic silicic acids), polysaccharides, especially xanthan gum, guar-guar, agar-agar, alginates and Tyloses, carboxymethyl cellulose and hydroxymethyl cellulose, also relatively high molecular weight polyethylene glycol mono- and di-esters of fatty acids, polyacry- lates (e.g. Carbopol^® from Goodrich or Synthalen^® from Sigma), polyacrylamides, polyvinyl alcohol and polyvinylpyrrolidone, surfactants, for example ethoxylated fatty acid glycerides, esters of fatty acids with polyols, for example pentaerythritol or trimethylolpropane, fatty alcohol ethox- ylates with restricted homologue distribution and alkyl-oligoglucosides as well as electrolytes, such as sodium chloride or ammonium chloride.

Suitable cationic polymers are, for example, cationic cellulose derivatives, for example a quar- ternised hydroxymethyl cellulose obtainable under the name Polymer JR 400^® from Amerchol, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternised vinylpyrroli- done/vinyl imidazole polymers, for example Luviquat^® (BASF), condensation products of poly- glycols and amines, quaternised collagen polypeptides, for example lauryldimonium hydroxy- propyl hydrolyzed collagen (Lamequat^®L/Grijnau), quaternised wheat polypeptides, polyeth- yleneimine, cationic silicone polymers, for example amidomethicones, copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetriamine (Cartaretin^®/Sandoz), copolymers of acrylic acid with dimethyldiallylammonium chloride (Merquat^® 550/Chemviron), polyaminopolyamides, as described, for example, in FR-A-2 252 840, and the crosslinked water-soluble polymers thereof, cationic chitin derivatives, for example quaternised chitosan, optionally distributed as microcrystals; condensation products of dihaloalkyls, for example dibromobutane, with bisdi- alkylamines, for example bisdimethylamino-1 ,3-propane, cationic guar gum, for example Jaguar^® C-17, Jaguar^® C-16 from Celanese, quaternised ammonium salt polymers, for example Mirapol^® A-15, Mirapol^® AD-1 , Mirapol^® AZ-1 from Miranol.

Suitable anionic, zwitterionic, amphoteric and non-ionic polymers are for example, vinyl ace- tate/crotonic acid copolymers, vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl maleate/isobornyl acrylate copolymers, methyl vinyl ether/maleic anhydride copolymers and esters thereof, uncrosslinked polyacrylic acids and polyacrylic acids crosslinked with polyols, acrylamidopropyltrimethylammonium chloride/acrylate copolymers, octyl acrylamide/methyl methacrylate/tert-butylaminoethyl methacrylate/2-hydroxypropyl methacrylate copolymers, poly- vinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers, vinylpyrrolidone/dimethylaminoethyl methacrylate/vinyl caprolactam terpolymers and also optionally derivatised cellulose ethers and silicones. Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpoly- siloxanes, cyclic silicones, and also amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine-, glycoside- and/or alkyl-modified silicone compounds, which at room temperature may be in either liquid or resinous form. Also suitable are simethicones, which are mixtures of dimethicones having an average chain length of from 200 to 300 dimethylsiloxane units with hydrogenated silicates. A detailed survey by Todd et al. of suitable volatile silicones may in addition be found in Cosm. Toil. 91 , 27 (1976).

Typical examples of fats are glycerides, and as waxes there come into consideration, inter alia, beeswax, carnauba wax, candelilla wax, montan wax, paraffin wax, hydrogenated castor oils and fatty acid esters or microwaxes solid at room temperature optionally in combination with hydrophilic waxes, e.g. cetyl stearyl alcohol or partial glycerides. Metal salts of fatty acids, for example magnesium, aluminum and/or zinc stearate or ricinoleate, may be used as stabilizers.

Biogenic active ingredients are to be understood as meaning, for example, tocopherol, tocoph- erol acetate, tocopherol palmitate, ascorbic acid, deoxyribonucleic acid, retinol, bisabolol, allan- toin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes.

Suitable deodorizing active ingredients are for example, antiperspirants like aluminum chloro- hydrates (see J. Soc. Cosm. Chem. 24, 281 (1973)). Aluminum chlorohydrate corresponding to formula AI₂(OH)₅CI x 2.5 H₂0, known and commercially available under the trade mark Locron^® of Hoechst AG, Frankfurt (FRG), is especially preferred (see J. Pharm. Pharmacol. 26, 531 (1975)). Beside the chlorohydrates, it is also possible to use aluminium hydroxy-acetates and acidic aluminium/zirconium salts. Esterase inhibitors may be added as further deodorising ac- tive ingredients. Such inhibitors are preferably trialkyi citrates, such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and especially triethyl citrate (Hydagen^® CAT, Henkel KGaA, Dijsseldorf/FRG), which inhibit enzyme activity and hence reduce odor formation. Further suitable esterase inhibitors are sterol sulfates or phosphates, for example lanosterol, cholesterol, campesterol, stigmasterol and sitosterol sulfate or phosphate, dicarboxylic acids and esters thereof, for example glutaric acid, glutaric acid monoethyl ester, glutaric acid diethyl ester, adipic acid, adipic acid monoethyl ester, adipic acid diethyl ester, malonic acid and malonic acid diethyl ester and hydroxycarboxylic acids and esters thereof, for example citric acid, malic acid, tartaric acid or tartaric acid diethyl ester. Antibacterial active ingredients that influence the microbial flora and kill, or inhibit the growth of, sweat-decomposing bacteria can likewise be present in the preparations (especially in stick preparations). Examples include chitosan, phe- noxyethanol and chlorhexidine gluconate. 5-Chloro-2-(2,4-dichlorophenoxy)-phenol (Irgasan^®, BASF has also proved especially effective.

Customary film formers include, for example, chitosan, microcrystalline chitosan, quaternised chitosan, polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers, polymers of quaternary cellulose derivatives containing a high proportion of acrylic acid, collagen, hyaluronic acid and salts thereof and similar compounds. Suitable swelling agents for aqueous phases are montmorillonites, clay mineral substances, Pemulen and also alkyl-modified types of Carbopol (Goodrich). Further suitable polymers and swelling agents can be found in the review by R. Lochhead in Cosm. Toil. 108, 95 (1993).

For improvement of the flow behavior it is also possible to employ hydrotropic agents, for exam- pie ethanol, isopropyl alcohol or polyols. Suitable polyols for that purpose comprise preferably from 2 to 15 carbon atoms and at least two hydroxy groups.

The polyols may also contain further functional groups, especially amino groups, and/or may be modified with nitrogen. Typical examples are as follows:

- glycerol;

alkylene glycols, for example ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and also polyethylene glycols having an average molecular weight of from 100 to 1000 Dalton;

technical oligoglycerol mixtures having an intrinsic degree of condensation of from 1 .5 to 10, for example technical diglycerol mixtures having a diglycerol content of from 40 to 50 % by weight;

methylol compounds, such as, especially, trimethylolethane, trimethylolpropane, tri- methylolbutane, pentaerythritol and dipentaerythritol;

lower alkyl-glucosides, especially those having from 1 to 8 carbon atoms in the alkyl radical, for example methyl and butyl glucoside;

sugar alcohols having from 5 to 12 carbon atoms, for example sorbitol or mannitol;

sugars having from 5 to 12 carbon atoms, for example glucose or saccharose;

amino sugars, for example glucamine;

dialcohol amines, such as diethanolamine or 2-amino-1 ,3-propanediol. Suitable preservatives include, for example, phenoxyethanol, formaldehyde solution, Parabens, pentanediol or sorbic acid and the further substance classes listed in Schedule 6, Parts A and B of the Cosmetics Regulations. Suitable perfume oils are mixtures of natural and/or synthetic aromatic substances. Representatives of natural aromatic substances are, for example, extracts from blossom (lilies, lavender, roses, jasmine, neroli, ylang-ylang), from stems and leaves (geranium, patchouli, petitgrain), from fruit (aniseed, coriander, carraway, juniper), from fruit peel (bergamot, lemons, oranges), from roots (mace, angelica, celery, cardamom, costus, iris, calmus), from wood (pinewood, san- dalwood, guaiacum wood, cedarwood, rosewood), from herbs and grasses (tarragon, lemon grass, sage, thyme), from needles and twigs (spruce, pine, Scots pine, mountain pine), from resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials also come into consideration, for example civet and castoreum. Typical synthetic aromatic substances are, for example, products of the ester, ether, aldehyde, ketone, alcohol or hydro- carbon type.

Aromatic substance compounds of the ester type are, for example, benzyl acetate, phenoxy- ethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethyl-benzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allyl- cyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether; the aldehydes include, for example, the linear alkanals having from 8 to 18 hydrocarbon atoms, citral, citronellal, citronellyl oxyacetaldehyde, cyclamen aldehyde, hy- droxycitronellal, lilial and bourgeonal; the ketones include, for example, the ionones, a- isomethylionone and methyl cedryl ketone; the alcohols include, for example, anethol, citronel- lol, eugenol, isoeugenol, geraniol, linalool, phenyl ethyl alcohol and terpinol; and the hydrocarbons include mainly the terpenes and balsams. It is preferable, however, to use mixtures of various aromatic substances that together produce an attractive scent. Ethereal oils of relatively low volatility, which are chiefly used as aroma components, are also suitable as perfume oils, e.g. sage oil, camomile oil, clove oil, melissa oil, oil of cinnamon leaves, lime blossom oil, juni- per berry oil, vetiver oil, olibanum oil, galbanum oil, labolanum oil and lavandin oil. Preference is given to the use of bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenyl ethyl alcohol, a- hexyl cinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde, linalool, boisambrene forte, ambroxan, indole, hedione, sandelice, lemon oil, tangerine oil, orange oil, allyl amyl glyco- late, cyclovertal, lavandin oil, muscatel sage oil, β-damascone, bourbon geranium oil, cyclohexyl salicylate, vertofix coeur, iso-E-Super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romillat, irotyl and floramat alone or in admixture with one another.

Suitable colorants that are permitted for cosmetic purposes are for example published in "Kosmetische Farbemittel" of the Farbstoffkommission der Deutschen Forschungsgemeinschaft, Verlag Chemie, Weinheim, 1984, pages 81 to 106 may be used. The colorants are generally used in concentrations of from 0.001 to 0.1 % by weight, based on the total mixture.

Typical examples of bacteria-inhibiting agents are preservatives that have a specific action against gram-positive bacteria, such as 2,4,4'-trichloro-2'-hydroxydiphenyl ether, chlorhexidine (1 ,6-di(4-chlorophenyl-biguanido)hexane) or TCC (3,4,4'-trichlorocarbanilide).

A large number of aromatic substances and ethereal oils also have antimicrobial properties. Typical examples are the active ingredients eugenol, menthol and thymol in clove oil, mint oil and thyme oil. A natural deodorizing agent of interest is the terpene alcohol farnesol (3,7,1 1 -trime- thyl-2,6,10-dodecatrien-1 -ol), which is present in lime blossom oil. Glycerol monolaurate has also proved to be a bacteriostatic agent. The amount of the additional bacteria-inhibiting agents present is usually from 0.1 to 2 % by weight, based on the solids content of the cosmetic composition according to the present invention. The cosmetic compositions according to the present invention may furthermore contain as adjuvants anti-foams, such as silicones, structurants, such as maleic acid, solubilizers, such as ethylene glycol, propylene glycol, glycerol or diethylene glycol, opacifiers, such as latex, sty- rene/PVP or styrene/acrylamide copolymers, complexing agents, such as EDTA, NTA, β-ala- ninediacetic acid or phosphonic acids, propellants, such as propane/butane mixtures, N₂0, di- methyl ether, C0₂, N₂ or air, so-called coupler and developer components as oxidation dye precursors, thioglycolic acid and derivatives thereof , thiolactic acid, cysteamine, thiomalic acid or a-mercaptoethanesulfonic acid as reducing agents or hydrogen peroxide, potassium bromate or sodium bromate as oxidizing agents. Insect repellents are for example, N,N-diethyl-m-toluamide, 1 ,2-pentanediol or insect repellent 3535.

Suitable self-tanning agents are dihydroxyacetone, erythrulose or mixtures of dihydroxyacetone and erythrulose. Cosmetic formulations according to the invention are contained in a wide variety of cosmetic preparations, especially the following preparations:

skin-care preparations, e.g. skin emulsions, multi-emulsions or skin oils;

cosmetic personal care preparations, e.g. facial make-up in the form of day creams or pow- der creams, face powder (loose or pressed), rouge or cream make-up, eye-care preparations, e.g. eye shadow preparations, mascara, eyeliner, eye creams or eye-fix creams; lip- care preparations, e.g. lipsticks, lip gloss, lip contour pencils, nail-care preparations, such as nail varnish, nail varnish removers, nail hardeners or cuticle removers;

light-protective preparations, such as sun milks, lotions, creams or oils, sunblocks or tropi- cals, pre-tanning preparations or after-sun preparations;

skin-tanning preparations, e.g. self-tanning creams;

depigmenting preparations, e.g. preparations for bleaching the skin or skin-lightening preparations;

insect-repellents, e.g. insect-repellent oils, lotions, sprays or sticks;

The final formulations may exist in a wide variety of presentation forms, for example:

in the form of liquid preparations as a W/O, O/W, 0/W/O, W/O/W or PIT emulsion and all kinds of microemulsions,

in the form of a gel,

- in the form of an oil, a cream, milk or lotion,

in the form of a powder, a lacquer, a tablet or make-up,

in the form of a stick,

in the form of a spray (spray with propellant gas or pump-action spray) or an aerosol, in the form of a foam, or

- in the form of a paste.

Important cosmetic compositions for the skin are light-protective preparations, such as sun milks, lotions, creams, oils, sunblocks or tropicals, pretanning preparations or after-sun preparations, also skin-tanning preparations, for example self-tanning creams. Of particular interest are sun protection creams, sun protection lotions, sun protection oils, sun protection milks and sun protection preparations in the form of a spray.

A. Examples for UV filters and UV filter combinations according to the present invention Methods

Calculation of spectral transmittance Τ(λ) of sunscreens

For calculation of the spectral transmittance Τ(λ) of sunscreens with given filter compositions, a simulation tool is used. The tool is based on the following elements: a database with UV spectra of the relevant UV filters (given as decade molar extinction coefficients), a mathematical description of the irregularity profile of the sunscreen film on the skin, consideration of changes in UV filter concentration due to photo-instabilities, and consideration of formulation influences like the distribution of the UV filters in the oil and water phase of an emulsion.

Determination of SPF (erythema attenuation) and attenuation factor of pre-vitamin D formation

It's known from scientific literature that whole body exposure to 1 MED erythemal radiation exposure (Minimum Erythema Dose, this is the minimum amount of UV-B radiation after 24h ex- posure) = 250 J/m² erythemal radiant exposure is equivalent to an oral intake of about 10,000 IU vitamin D₃. For maximum solar input (according to COLIPA, sun in zenith, cloudless sky) it takes about 20 minutes to receive 1 MED. The recommended intake of vitamin D₃ ranges from 1 ,000 up to 4,000 lU/day. A daily supply of 2000 lU/day are recommended by the DGE

(Deutsche Gesellschaft fur Ernahrung 201 1 ). This recommendation relates to a lack of endoge- neous/epidermal vitamin D₃ production, e.g. due to no exposure to UV radiation. This amount of Vitamin D3 can be produced in skin after f 20/5 = 4 minutes under the conditions that the unprotected skin is exposed to the above mentioned maximum solar input. Sunscreens attenuate the erythema irradiation and vitamin D₃-effective radiation. MED = Minimum Erythema Dose = the minimum amount of UVB radiation [J/m²] that produces a first redness on skin 24 hours after exposure = 250 J/m² erythemal radiation (standardized value) 1 IU = 25 ng Vit D₃ .

The SPF is calculated according to the following formula

By analogy to the SPF the attenuation factor for vitamin D₃-effective radiation AF_PVD is defined as

Ε_λ(λ) spectral solar irradiance,

Τ(λ) spectral transmittance of a given sunscreen and both, the

Ser^) action spectrum of erythema

Spv_d^) action spectrum of vitamin D₃ formation in the skin,.

Calculation of E_ER, E_VD, E_VD/E_er, SPF, AF_VD using the BASF Sunscreen Simulator:

(www.basf.com/sunscreensimulator; Herzog, B.; Osterwalder, U. In Silico Determination of Topical Sun Protection. Cosm Sci Tech. 2011 ; 62: 1-8.

The exposure time t_PVD for producing the equivalent amount of the recommended vitamin D₃ intake of 2,000 IU with or without a sunscreen is

tpyp = 4 x AFpyp minutes

when the protected skin is exposed to the above mentioned maximum solar input.

The attenuation factors AF_PVD and the exposure times t_PVD for the some examples of sunscreens are given in table 4.

Examples of filter compositions are chosen to achieve sun protection factors (abbreviated as SPF) of 6, 15, and 30.

Results

Example A1 : SPF 6 sunscreens

Table 1 shows the compositions as well as the calculated values of SPF, E_pVd/E_er ratio, UVA-PF, UVA-PF/SPF-ratio and critical wavelength CW for four SPF 6 sunscreens as explained above.

Figure 3 shows the spectral transmittances of sunscreen films referring to the four different types of UV filter compositions leading to SPF 6.

Example A2: SPF 15 sunscreens

Table 2 shows the compositions as well as the calculated values of SPF, E_PVd/E_er ratio, UVA-PF, UVA-PF/SPF-ratio and critical wavelength CW for four SPF 15 sunscreens.

Table 2: UV filter compositions for SPF 15 with different levels of E_Pvd/E_er ratio and UVA protection

In Figure 4 the simulated spectral transmittances of sunscreen films referring to the four different types of UV filter compositions leading to SPF 15 are depicted.

Example A3: SPF 30 sunscreens

Table 3 shows the compositions and the calculated values of SPF, E_pvci/Eer ratio, UVA-PF, UVA- PF/SPF-ratio and critical wavelength CW for four SPF 30 sunscreens

Figure 5 shows the simulated spectral transmittances of sunscreen films referring to the four different types of UV filter compositions leading to SPF 30.

The examples A3.3 and A3.4 demonstrate that the transmittance of sunscreens for vitamin D₃- effective radiation can be optimized even if the SPF is the same.

Example A4: Determination of recommended amount of Vitamin D/day

The exposure time t_PVD for getting the recommended Vitamin D intake of 2000 lU/day is tpvD = 4 x AFPVD minutes when the protected skin is exposed to the above mentioned maximum solar input. The attenuation factors AF_PVD and the exposure times t_PVD for the 4 examples of sunscreens are given in table 4.

The exposure times t_PVD for sun exposure with sunscreens e.g. with SPF = 30 are with about 2 hours within the usual time frame of sun bathers. Thus it makes really sense to optimize sunscreens in terms of low attenuation factors AF_PVD-

Weiqht

Type UV Filter Composition SPF EvitD _E_er

[%]

4 Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol

2 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine

1 ,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)-

A2.4 8 15.7 2.00 piperazine

Aqueous dispersion of Bis-Ethylhexyloxyphenol Methox¬

5

yphenyl Triazine / Polymethyl Methacrylate

1 ,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)-

20

piperazine

2 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine

A3.3 3 Diethylamino Hydroxybenzoyl Hexyl Benzoate 32.9 1 .96

2 Ethylhexyl Triazone

Aqueous dispersion of Bis-Ethylhexyloxyphenol Methox¬

7.5

yphenyl Triazine / Polymethyl Methacrylate

1 Phenyl Benzimidazole Sulfonic Acid

A5.3 61.2 1 .94

3 Ethylhexyl Triazone Weiqht

Type UV Filter Composition SPF EyitD _E_er

[%]

2 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine

6 Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol

8 Diethylamino Hydroxybenzoyl Hexyl Benzoate

1 ,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)pi-

20

perazine

Aqueous dispersion of Bis-Ethylhexyloxyphenol Methox¬

10

yphenyl Triazine / Polymethyl Methacrylate

12 Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol

A3.3 30.1 1 .82

12 Tris-Biphenyl Triazine

14 Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol

A2.4 1 ,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)pi- 15.0 2.04

20

perazine

12 Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol

A3.3 30.0 1 .83

5 Titanium Dioxide

16 Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol

3 Titanium Dioxide

A3.4 4 Diethylamino Hydroxybenzoyl Hexyl Benzoate 30.7 2.03

1 ,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)pi-

20

perazine

14 Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol

A3.3 30.9 1 .84

5 Drometrizole trisiloxane

2 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine

5 Compound of formula (PBT2)

A2.3 15.6 1 .86

1 ,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)-

2

piperazine

2 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine

3 Compound of formula (PBT2)

A2.4 16.3 2.02

1 ,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)-

16

piperazine

16 Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol

3.5 Titanium Dioxide

A4.3 50.5 1 .81

6% Compound of formula (PBT2)

6 Drometrizole trisiloxane

14 Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol

A2.4 3 Titanium Dioxide 30.7 1 .85

4 Compound of formula (PBT2)

16 Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol

3.5 Titanium Dioxide

6 BTEM

A5.3 60.2 1 .89

6 Drometrizole trisiloxane

1 ,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)pipera-

10

zine

A1.4 9 Diethylamino Hydroxybenzoyl Hexyl Benzoate 6.3 2.18

A1.3 3 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 7.3 1 .87

3 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine

A2.4 1 ,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)- 15.6 2.05

20

piperazine

2 Octocrylene

A3.3 30.6 1 .94

2 Butyl Methoxy Dibenzoyl Methane Weiqht

Type UV Filter Composition SPF EyitD _E_er

[%]

2.5 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine

8 Terephthalylidene Dicamphor Sulfonic Acid

1 ,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)-

12

piperazine

3 Polisilicone-15

A2.3 2 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 16.3 1 .87

4 Disodium Phenyl Dibenzimidazole Tetrasulfonate

1 Diethylhexyl Butamido Triazone

A2.3 2 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 15.5 1 .81

3 Disodium Phenyl Dibenzimidazole Tetrasulfonate

25 Zinc Oxide

A2.3 15.7 1 .92

1 .2 Titanium Dioxide

9 Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol

1 .5 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine

A3.4 25 Zinc Oxide 31.2 2.01

1 ,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)-

20

piperazine

A1.3 15 Zinc Oxide 6.6 1 .97

4 Ethylhexyl Salicylate

2 Butyl Methoxy Dibenzoyl Methane

1 .5 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine

1 .5 Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol

A3.3 30.9 1 .89

3 Benzophenone-3

3 Titanium Dioxide

1 ,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)-

16

piperazine

4 Ethylhexyl Salicyate

2 Butyl Methoxy Dibenzoyl Methane

1 .5 Tinosorb^®S

1 .5 Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol

A3.3 31.4 1 .89

3 Benzophenone-4

3 Titanium Dioxide

1 ,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)-

16

piperazine

4 Homomenthyl Salicyate

2 Butyl Methoxy Dibenzoyl Methane

1 .5 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine

1 .5 Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol

A3.3 30.8 1 .90

3 Benzophenone-4

3 Titanium Dioxide

1 ,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)-

16

piperazine

A1.4 5 Terephthalylidene Dicamphor Sulfonic Acid 6.06 2.03

2 Octocrylene

1 Butyl Methoxy Dibenzoyl Methane

A2.3 4 Terephthalylidene Dicamphor Sulfonic Acid 15.2 1 .91

1 Benzophenone-3

5 Menthyl Anthranilate

A3.3 3 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 30.0 1 .96 Weiqht

Type UV Filter Composition SPF EyitD _E_er

[%]

5 Diethylamino Hydroxybenzoyl Hexyl Benzoate

5 Compound of formula (BM9)

1 ,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)pipera-

12

zine

3 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine

6 Diethylamino Hydroxybenzoyl Hexyl Benzoate

A3.4 4 Compound of formula (BM9) 30.1 2.01

1 ,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)pipera-

16

zine

3 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine

A3.3 10 Diethylamino Hydroxybenzoyl Hexyl Benzoate 30.1 1 .87

3 Ethylhexyl Triazone

A0.3 0.5 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 2.1 1 .95

B. Examples for cosmetic formulations

The formulation is prepared as follows: Parts A and B are prepared and separately heated to 80°C. Then part A is added to part B under stirring. After short homogenization part C is added under stirring. After cooling down to room temperature the ingredients of part D are added in the listed order. P A_ta_r

The formulation is prepared as follows: Part A is heated to 80°C, cooled down to room temperature and incorporated into part B under stirring. After homogenization (with an ultra-turrax type device) part C is added, again followed by homogenization. Finally the ingredients of part D are added and the formulation is homogenized again.

Example B3: Tvoe 2.3, SPF = 15

% w/w, as

Trade Name INCI Name

supplied

Parsoll® 1789 Butyl Methoxy Dibenzoyl Methane 3.00

Uvinul® A plus Diethylamino Hydroxybenzoyl Hexyl Benzoate 10.00

Cetiol® AB C12-15 Alkyl Benzoate 8.00

Water Aqua Qs to 100

CD Butylene glycol Butylene glycol 2.50

^■c

03 Mais P04 PH "B" Distarch phosphate 2.00

D. Acrylates/beheneth-25 methylacrylate copol¬

Tinovis® GTC 1 .50

ymer D_ta_r

EC P_t _•a_rxample B3: Type 2.3, SPF = 15

% w/w, as

Trade Name INCI Name

supplied

Sodium hydroxide

Water (and) sodium hydroxide Qs to pH 7 (30% solution)

Methylene Bis-Benzotriazolyl Tetramethylbutyl-

Tinosorb® M 3.10

phenol

Li-

Ethanol 96% Alcohol 5.00

The formulation is prepared as follows: Parts A and B are prepared and separately heated to 80°C. Then part A is added to part B under stirring. After short homogenization part C is added under stirring. After cooling down to room temperature the ingredients of part D are added in the listed order.

Example B7: Tvoe 3.4, SPF = 30

Methylene Bis-Benzotriazolyl Tetramethyl-

Tinosorb® M 7.40

butylphenol

Ethanol 96% Alcohol 3.00

Claims

1 . A sunscreen formulation comprising at least one of the UV filters (A) selected from

(a) triazine derivatives;

(b) cinnamic acid derivatives;

(c) bis-resorcinyl triazines;

(f) benzimidazole derivatives;

(i₅) 4-Methylbenzylidene Camphor;

(h) benzoyl piperazine derivatives;

(j) benzoxazole derivatives;

(k) diarylbutadiene derivatives;

(I) phenyl benzotriazole derivatives;

(n) benzylidene malonates;

(o₃) TEA-Salicylate;

(r) imidazoline derivatives;

(u) inorganic UV filters selected from metal oxides;

(v) naphthalates; and

(w) merocyanine derivatives; and

optionally comprising at least one of the UV filters (B) selected from

(d) aminobenzophenone derivatives;

(e) dibenzoylmethane derivatives;

(g) β,β-Diphenylacrylate derivatives;

(i₅) camphor derivatives different from;

(o₃) salicylate derivatives different from;

(p) anthranilate derivatives; and

(s) benzalmalonate derivatives;

wherein

the ratio R of the effective irradiance for previtamin D₃ formation E_pvd to the effective irradi- ance for erythema formation E_er on the skin is at least 1.8,

for increasing the transmittance of UV radiation on human skin for the production of cholecalcif- erol (previtamin D₃) and simultaneously for the use in a method for protecting the human skin against UV radiation when exposed to the sun, which method comprises applying said sunscreen formulation to the skin.

2. Sunscreen formulation according to claim 1 , wherein the sun screen formulation has an SPF of at least 2.

3. Sunscreen formulation according to claim 1 , wherein the sun screen formulation has an SPF of at least 6.

4. Sunscreen formulation according to any of claims 1 to 3, wherein the UV filters are selected from

(ai Ethylhexyl Triazone.

(a₂ Tris-Bephenyl Triazine;

(a₃ Diethylhexyl Butamido Triazone;

(c Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine;

(C; Aqueous dispersion of Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine / Polymethyl Methacrylate;

(d Diethylamino Hydroxybenzoyl Hexyl Benzoate;

(e Butyl Methoxy Dibenzoyl Methane;

(fi Phenyl Benzimidazole Sulfonic Acid;

(f₂ Disodium Phenyl Dibenzimidazole Tetrasulfonate;

(9 Octocrylene;

(h 1 ,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)piperazine;

(li Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol;

(l₂ Drometrizole trisiloxane ;

(le 2-(2H-Benzotriazol-2-yl)-6-(2-ethylhexyloxymethyl)-4-methyl-phenol;

(ii Terephthalylidene Dicamphor Sulfonic Acid;

(ni Compound of formula (BM9);

(Oi Ethylhexyl Salicylate;

(o₄ Homosalate;

(P Menthyl Anthranilate;

(s Polysilicone-15;

(Ui Zinc Oxide; and

(u₃ Titanium Dioxide;

5. Sunscreen formulation according to any of claims 1 to 4, wherein the UV filters are selected from

(a-i) Ethylhexyl Triazone;

(bi) Ethylhexyl Methoxy Cinnamate;

(Ci ) Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine;

(di) Diethylamino Hydroxybenzoyl Hexyl Benzoate;

(l-i) Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol;

(e-i) Butyl Methoxy Dibenzoyl Methane; Phenyl Benzimidazole Sulfonic Acid;

Octocrylene; and

Titanium Dioxide.

6. Sunscreen formulation according to any of claims 1 to 5, wherein the UV filters are selected from

(bi) Ethylhexyl Methoxy Cinnamate;

(Cl ) Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine;

(di) Diethylamino Hydroxybenzoyl Hexyl Benzoate.

( ) Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol

(ei ) Butyl Methoxy Dibenzoyl Methane;

(fi ) Phenyl Benzimidazole Sulfonic Acid; and

(gi) Octocrylene.

7. Sunscreen formulation according to any of claims 1 to 6, wherein the UV filters are selected from

(Ci ) Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine;

(di) Diethylamino Hydroxybenzoyl Hexyl Benzoate;

(l-i ) Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol; and

(ei ) Butyl Methoxy Dibenzoyl Methane.

8. Sunscreen formulation according to any of claims 5 to 7, wherein the sun screen formulation has an SPF of at least 6.

9. Sunscreen formulation according to any of claims 1 to 8, wherein the UV filters are selected from

(a) 0.1 -40 % b.w. triazine derivatives;

(b) 0.1 - 30 % b.w. cinnamic acid derivatives;

(c) 0.1 - 10 % b.w. bis-resorcinyl triazines;

(f) 0.1 - 10 % b.w. benzimidazole derivatives;

(is) 0.1 - 10 % b.w. 4-Methylbenzylidene Camphor;

(h) 0.1 - 10 % b.w. benzoyl piperazine derivatives;

(j) 0.1 - 10 % b.w. benzoxazole derivatives;

(k) 0.1 - 20 % b.w. diarylbutadiene derivatives;

(I) 0.1 - 30 % b.w. phenyl benzotriazole derivatives;

(n) 0.1 - 20 % b.w. benzylidene malonates;

(o₃) 0.1 - 15 % b.w. TEA-Salicylate; (r) 0.1 - 10 % b.w. imidazoline derivatives;

(u) 0.1 - 50 % b.w. inorganic UV filters selected from metal oxides;

(v) 0.1 - 20 % b.w. naphthalates; and

(w) 0.1 - 20 % b.w. merocyanine derivatives; and

optionally comprising at least one of the UV filters (B) selected from

(d) 0.1 - 20 % b.w. aminobenzophenone derivatives;

(e) 0.1 - 5 % b.w. dibenzoylmethane derivatives;

(g) 0.1 - 1 % b.w. β,β-Diphenylacrylate derivatives;

(i) 0.1 - 10 % b.w. camphor derivatives different from (i₅);

(o) 0.1 - 35 % b.w. salicylate derivatives different from (o₃);

(p) 0.1 - 10 % b.w. anthranilate derivatives; and

(s) 0.1 - 10 % b.w. benzalmalonate derivatives.

10. Sunscreen formulation according to any of claims 1 to 9, wherein the sunscreen comprises the UV filters selected from

(a-i ) 1 - 3 % b.w. Ethylhexyl Triazone;

(bi) 1 - 3.5 % b.w. Ethylhexyl Methoxycinnamate;

(Ci ) 0.6 - 10 % b.w. Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine;

(di) 0.8 - 10 % b.w. Diethylamino Hydroxybenzoyl Hexyl Benzoate;

(ei ) 2 - 3 % b.w. Butyl Methoxydibenzoylmethane;

(f-i ) 2 - 3 % b.w. Phenyl Benzimidazole Sulfonic Acid;

(gi) 2.0 - 2.5 % b.w. Octocrylene;

( ) 2 - 7.5 % b.w. Methylene Bis-Benzotriazolyl Tetramethylbutylphenol; and

(u₃) 3.0 - 3.5 % b.w. Titanium Dioxide.

1 1 . Sunscreen formulation according to any of claims 1 to 10, wherein the sun screen comprises the UV filter combination of

(di) Diethylamino Hydroxybenzoyl Hexyl Benzoate;

(l-i ) Methylene Bis-benzotriazolyl Tetramethyl Butylphenol; and

(ei ) Butyl Methoxy Dibenzoyl Methane;

wherein the sun screen has a SPF of > 15.

12. Sunscreen formulation according to any of claims 1 to 10, wherein the sun screen comprises the UV filter combination of

(Ci ) Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine;

(di) Diethylamino Hydroxybenzoyl Hexyl Benzoate;

(l-i ) Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol; and (e-ι) Butyl Methoxy Dibenzoyl Methane;

wherein the sun screen has a SPF > 30.

13. Sunscreen formulation according to any of claims 1 to 12, wherein the UV filters are select- ed from the broadband (spectrum of 340 to 400 nm) UV filters

(Ci ) Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine;

(f₂) Disodium Phenyl Dibenzimidazole Tetrasulfonate;

( ) Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol;

(l₂) Drometrizole trisiloxane;

(ui) Zinc Oxide; and optionally

(e-i) Butyl Methoxy Dibenzoyl Methane;

(di) Diethylamino Hydroxybenzoyl Hexyl Benzoate;

(i-i) Terephthalylidene Dicamphor Sulfonic Acid; and

(Pi) Menthyl Anthranilate.

14. A sunscreen formulation according to any of claims 1 to 13 comprising a UV filter selected from

(a) triazine derivatives;

(b) cinnamic acid derivatives;

(c) bis-resorcinyl triazines;

(f) benzimidazole derivatives;

(h) benzoyl-piperazine derivatives;

(i₅) 4-Methylbenzylidene Camphor;

(I) phenyl benzotriazole derivatives;

(n) benzylidene malonates;

(o₃) TEA-Salicylate;

(r) imidazoline derivatives;

(u) inorganic UV filters selected from metal oxides;

(v) naphthalates; and

(w) merocyanine derivatives;

wherein the sunscreen formulation contains only one of the selected UV filters.

15. Sunscreen formulation according to claim 14 wherein the UV filters are selected from broadband (spectrum of 340 to 400 nm) UV filters

(f₂) Disodium Phenyl Dibenzimidazole Tetrasulfonate;

(l-i) Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol;

(11) Terephthalylidene Dicamphor Sulfonic Acid; and

(ui) Zinc Oxide;

wherein the sunscreen formulation contains only one of the selected UV filters.

16. Sunscreen formulation according to any of claims 1 to 15 wherein the UV filters are selected from particulate UV filters selected from

(a₂) Tris-Biphenyl Triazine;

(h-i) 1 ,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)piperazine;

(l-i) Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol;

(ui) Zinc Oxide; and

(u₃) Titanium Dioxide.

17. Sunscreen formulation according to any of claims 1 to 15 wherein the UV filters are selected from non-particulate UV filters selected from

(a-i) Ethylhexyl Triazone.

(a₃) Diethylhexyl Butamido Triazone;

(Ci) Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine;

(di) Diethylamino Hydroxybenzoyl Hexyl Benzoate;

(e-i) Butyl Methoxy Dibenzoyl Methane;

(f-i) Phenyl Benzimidazole Sulfonic Acid;

(f₂) Disodium Phenyl Dibenzimidazole Tetrasulfonate;

(gi) Octocrylene;

(h-i) 1 ,4-(2-(4-diethylamino-2-hydroxybenzoyl)benzoyl)piperazine;

(l-i) Methylene Bis-Benzotriazolyl Tetramethyl Butylphenol;

(1₂) Drometrizole trisiloxane ;

(l₆) 2-(2H-Benzotriazol-2-yl)-6-(2-ethylhexyloxymethyl)-4-methyl-phenol;

(i-i) Terephthalylidene Dicamphor Sulfonic Acid;

(rii) Compound of formula (BM9);

(oi) Ethylhexyl Salicylate;

(o₄) Homosalate; (Pi ) Menthyl Anthranilate; and

(Si ) Polysilicone-15.

18. Sunscreen formulation according to any of claims 1 to 17, wherein the ratio of the effective irradiance for vitamin D formation E_pvd and the effective irradiance for erythema formation E_er on the skin is > 2.0.