WO2002053118A2 - Cosmetic and dermatological light-protective formulation containing surface-active saccharose esters - Google Patents

Abstract

Light-protective, cosmetic or dermatological emulsions are characterised in comprising (a) one or several saccharose esters and (b) phenylen-1,4-bis-(2-benzimidazolyl)-3,3',5,5'-tetrasulphonic acid and/or salts thereof. The invention further relates to the use thereof.

Description

 description

Cosmetic and dermatological light protection formulations containing phenylene-1,4-bis (2-benzimidazyl) -3.3'-5.5'-tetrasulfonic acid and / or its salts and surface-active sucrose esters

The present invention relates to cosmetic and dermatological light protection preparations, in particular it relates to sand-repellent cosmetic and dermatological light protection preparations.

The damaging effect of the ultraviolet part of solar radiation on the skin is generally known. Depending on their respective wavelengths, the rays have different effects on the skin organ: The so-called UV-C radiation with a wavelength that is less than 290 nm is absorbed by the ozone layer in the earth's atmosphere and therefore has no physiological significance. In contrast, rays in the range between 290 nm and 320 nm, the so-called UV-B range, cause erythema, simple sunburn or even more or less severe burns. The narrower range around 308 nm is given as a maximum of the erythema effectiveness of sunlight.

Numerous compounds are known for protection against UV-B radiation, which are, for example, derivatives of 3-benzylidene camphor, 4-aminobenzoic acid, cinnamic acid, salicylic acid, benzophenone and s-triazine.

It has long been incorrectly assumed that the long-wave UV-A radiation with a wavelength between 320 nm and 400 nm only a negligible biological ^¬ having specific effect. In the meantime, however, numerous studies have shown that UV-A radiation is far more dangerous than UV-B radiation in terms of triggering photodynamic, especially phototoxic reactions and chronic changes in the skin. Radiation is. The damaging influence of UV-B radiation can also be increased by UV-A radiation.

So it is u. a. have proven that even UV-A radiation under normal everyday conditions is sufficient to damage collagen and elastin fibers, which are essential for the structure and firmness of the skin, within a short period of time. This leads to chronic light-induced skin changes - the skin "ages" prematurely. The clinical appearance of skin aged by light includes, for example, wrinkles and fine lines and an irregular, furrowed relief. Furthermore, the areas affected by light-induced skin aging can have irregular pigmentation Brown spots, keratoses and even carcinomas or malignant melanomas are possible, and skin that has aged prematurely due to everyday UV exposure is also characterized by less activity of the Langerhans cells and a mild, chronic inflammation.

About 90% of the ultraviolet radiation reaching the earth consists of UV-A rays. While UV-B radiation varies greatly depending on numerous factors (e.g. time of year and time of day or latitude), UV-A radiation remains relatively constant day by day, irrespective of the time of year or day or geographical factors. At the same time, the majority of UV-A radiation penetrates the living epidermis, while around 70% of UV-B rays are retained by the horny layer.

It is therefore of fundamental importance that cosmetic and dermatological light protection preparations offer adequate protection against both UV-B and UV-A radiation.

In general, the light absorption behavior of light protection filter substances is very well known and documented, especially since in most industrialized countries there are positive lists for the use of such substances, which apply very strict standards to the documentation.

However, the use concentration of known light protection filter substances known as solids is frequently - especially in combination with other substances to be dissolved - borders. It therefore presents certain formulation difficulties to achieve higher sun protection factors or UV-A protection performance.

The sunburn or the light erythema are the acute manifestations of the influence of light. In addition to the effects of UV rays already described, the subsequent reaction of the skin also leads to reduced sebum production and drying out of the skin. To alleviate and care for these phenomena, the prior art knows products that are used after sunbathing and usually contain special active ingredients, such as, for example, ^■ moisturizing and moisturizing agents,

^■ anti-inflammatory and cooling substances,

^■ locally anesthetic substances and / or

^■ disinfectants to prevent possible skin infections.

These so-called aftersun or apres-soleil preparations are intended to cool the skin after sunbathing and to improve its moisturizing ability, whereby the imparting of the cooling effect plays a central role. However, the state of the art lacks products that protect the skin from drying out during UV radiation and provide sufficient care.

Another disadvantage of the prior art is that conventional light protection formulations leave a mostly sticky film on the skin. This has e.g. B. when such products are used on a sandy beach, the result is that the sand sticks to the body, which is perceived by the user as unpleasant and, in the worst case, can lead to the sunscreen being used too little or not at all. Since there is usually a more or less strong wind at the sea, this disadvantage usually occurs even when the body does not come into direct contact with the sand - for example when sunbathing on a deck chair - because the sand dust whirling around in the wind also occurs adheres to the creamed areas of the skin.

A further object of the present invention was therefore to find light protection formulations which, after use, do not leave any sand stuck to the creamy skin, which are therefore to be described as sand-repellent.

It was surprising and unforeseeable for the person skilled in the art that cosmetic or dermatological emulsions effective in protecting against light, characterized in that they

(a) one or more sucrose esters and

(b) Phenylene-1, 4-bis- (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and / or their salts, alleviate the disadvantages of the prior art.

The emulsions according to the invention are preferably O / W emulsions.

In all respects, the emulsions according to the invention are extremely satisfactory preparations, which are not limited to a restricted selection of raw materials. Accordingly, they are particularly suitable to serve as the basis for forms of preparation with a variety of uses. The preparations according to the invention show very good sensory and cosmetic properties, such as, for example, the spreadability on the skin or the ability to be absorbed into the skin, and are furthermore distinguished by very good sun protection effectiveness and, at the same time, excellent skin care data.

It was particularly surprising that the skin moisturizing performance of these preparations is higher than the same preparations which do not contain sucrose esters. A measure of the skin moisturizing performance in the sense of the present invention is, for example, the results of corneometer measurements.

The invention also provides light-protective cosmetic or dermatological preparations, characterized in that they contain synergistic combinations of substances

(a) one or more sucrose esters and

(b) Phenylene-1, 4-bis- (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and / or their salts, the UV protection performance of these preparations being higher than the same preparations which contain no substances according to (a).

A measure of the UV protection performance in the sense of the present invention is, for example, the sun protection factor (SPF or SPF). The cosmetic and dermatological preparations in the sense of the present invention do not leave a greasy or sticky impression on the skin, are extremely skin-friendly and, furthermore, are surprisingly distinguished by the fact that they are sand-repellent.

The invention therefore also relates to sand-repellent cosmetic or dermatological sunscreen preparations, characterized in that they

(a) one or more sucrose esters and

(b) Phenylene-1, 4-bis- (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and / or their salts.

Preferred sucrose esters for the purposes of the present invention are esters of fatty acids and sucrose (sometimes also called “sucrose” in this document), simply to completely esterified, and commercially available cosmetic raw materials containing the same.

Sucrose has the following structure:

Their esters, which can advantageously be used according to the invention, are characterized by the structure

where R ¹ to R ^{8 can} advantageously be selected independently of one another from the group consisting of hydrogen atoms and branched and unbranched alkanoyl groups having 1 to 24 carbon atoms. It is particularly advantageous if up to seven of the Residues R ¹ to R ⁸ hydrogen atoms and one to eight of the residues R ¹ to R ^{8 are} selected from the group of branched and unbranched alkanoyl groups with 8 to 20 carbon atoms.

Particularly preferred sucrose esters are sucrose tetrastearate triacetate, sucrose laurate, sucrose dilaurate, sucrose stearate, sucrose distearate, sucrose caprylate, sucrose myristate, sucrose pa- imitate, sucrose oleate, sucrose behenate, sucrose or sucrose / sucrose / sucrose / sucrose / sucrose / sucrose / sucrose / sucrose / sucrose / sucrose / sucrose / sucrose / sucrose / sucrose / sucrose / sucrose-sucrose / sucrose-sucrose / sucrose-sucrose / sucrose-sucrose.

Sugar esters made from sucrose and fatty acids are available, for example, from Grillo Cosmetics [e.g. Grilloten LSE 65 K (esters from sucrose and coconut fatty acids), Grilloten LSE 65 K soft (esters from sucrose and coconut fatty acids), Grilloten LSE 87 K (esters from sucrose and coconut fatty acids), Grilloten LSE 87 K soft (esters from sucrose and coconut fatty acids) or Grilloten PSE 141 G (esters of sucrose and palmitic acid / stearic acid)] as well as those listed below:

The total amount of one or more sascharo esters used according to the invention in the finished cosmetic or dermatological preparations is advantageously chosen from the range from 0.1 to 10.0% by weight, preferably from 0.5 to 6.0% by weight on the total weight of the preparations.

It may be advantageous to incorporate further emulsifiers or co-emulsifiers into the cosmetic or dermatological preparations according to the invention, for example in order to further improve the stability of the preparations.

Advantageous further emulsifiers within the meaning of the present invention are Example ^¬ as silicone emulsifiers, phosphate emulsifiers and / or ethoxylated emulsifiers. Coemulsifiers which are advantageous according to the invention are fatty alcohols, in particular fatty alcohols with a chain length of 10 to 30 carbon atoms. Cetyl, stearyl and / or cetearyl alcohol are particularly preferred.

Phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid is characterized by the following structure:

The corresponding sodium, potassium or triethanolammonium salts, in particular phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid, are also advantageous in the sense of the present invention. bis-sodium salt

with the INCI name bisimidazylate, which is available, for example, from Haarmann & Reimer under the trade name Neo Heliopan AP.

The UV filter substance (s) according to the invention is / are advantageously incorporated into the water phase - particularly at a pH of more than 4.5 - of the cosmetic or dermatological formulations.

The cosmetic or dermatological light protection formulations according to the invention can be composed as usual and can be used for cosmetic or dermatological light protection, also for the treatment, care and cleaning of the skin and / or hair and as a make-up product in decorative cosmetics.

For use, the cosmetic and dermatological preparations are applied to the skin and / or the hair in a sufficient amount in the manner customary for cosmetics. The cosmetic and dermatological preparations according to the invention can contain cosmetic auxiliaries as are usually used in such preparations, e.g. B. preservatives, preservation aids, bactericides, perfumes, anti-foaming substances, dyes, pigments that have a coloring effect, thickeners, moisturizing and / or moisturizing substances, fillers that improve the feeling on the skin, fats, oils, waxes or other usual Components of a cosmetic or dermatological formulation such as alcohols, polyols, polymers, foam stabilizers, electrolytes, organic solvents or silicone derivatives.

Advantageous preservatives for the purposes of the present invention are, for example, formaldehyde releasers (such as, for example, DMDM hydantoin), iodopropyl butyl carbamates (for example those available under the trade names Koncyl-L, Koncyl-S and Konkaben LMB from Lonza), parabens, Phenoxyethanol, ethanol, benzoic acid and the like. According to the invention, the preservation system usually also advantageously comprises preservation aids, such as, for example, octoxyglycerol, glycine soya, etc.

Particularly advantageous preparations are also obtained if antioxidants are used as additives or active ingredients. According to the invention, the preparations advantageously contain one or more antioxidants. All of the antioxidants suitable or customary for cosmetic and / or dermatological applications can be used as inexpensive, but nevertheless optional, antioxidants.

The antioxidants are advantageously selected from the group consisting of amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (e.g. urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L-camosine and their derivatives (e.g. anserine), carotenoids, carotenes (e.g. α-carotene, ß-carotene, lycopene) and their derivatives, lipoic acid and their derivatives (e.g. dihydroliponic acid ), Aurothioglucose, propylthiouracil and other thiols (e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl, and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters) as well as their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as sulfoximine Compounds (e.g. buthionine sulfoximines, homocysteine sulfoximine, buthionine sulfones, pen- ta-, hexa-, heptathioninsulfoximine) in very low tolerable doses (e.g. pmol to μmol / kg), also (metal) chelators (e.g. α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (e.g. γ-linolenic acid, linoleic acid, oleic acid), folic acid and their derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and derivatives (e.g. ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and derivatives (vitamin A - palmitate) and konyferylbenzoate of benzoin, rutinic acid and its derivatives, ferrous acid and its derivatives, butylhydroxytoluene, butylhydroxyanisole, nordihydroguajak resin acid, nordihydroguajaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and their derivatives, zinc and its derivatives (e.g. B. ZnO, ZnSθ4) selenium and its derivatives (e.g. selenium methionine), stilbenes and their derivatives (e.g. stilbene oxide, trans-stilbene oxide) and the derivatives suitable according to the invention (salts, esters, ethers, sugars, nucleotides, nucleosides , Peptides and lipids) of these active ingredients.

For the purposes of the present invention, water-soluble antioxidants, such as vitamins, e.g. B. ascorbic acid and its derivatives.

An astonishing property of the preparations according to the invention is that they are very good vehicles for cosmetic or dermatological active ingredients in the skin, preferred active ingredients being antioxidants which can protect the skin against oxidative stress. Preferred antioxidants are vitamin E and its derivatives and vitamin A and its derivatives.

The amount of the antioxidants (one or more compounds) in the preparations is preferably 0.001 to 30% by weight, particularly preferably 0.05 to 20% by weight, in particular 0.1 to 10% by weight, based on the total weight the preparation.

If vitamin E and / or its derivatives represent the antioxidant (s), it is advantageous to choose their respective concentrations from the range from 0.001 to 10% by weight, based on the total weight of the formulation. If vitamin A or vitamin A dehvate or carotenes or their derivatives represent the antioxidant or antioxidants, it is advantageous to add their respective concentrations in the range from 0.001 to 10% by weight, based on the total weight of the formulation choose.

According to the invention, the active ingredients (one or more compounds) can also be selected very advantageously from the group of lipophilic active ingredients, in particular from the following group:

Acetylsalicylic acid, atropine, azulene, hydrocortisone and its derivatives, e.g. B. hydrocortisone-17-valerate, vitamins of the B and D series, very cheap the vitamin B ^ the vitamin B ₁₂ the vitamin D ^ but also bisabolol, unsaturated fatty acids, especially the essential fatty acids (often called vitamin F) ), in particular gamma-oleolenic acid, oleic acid, eicosapentaenoic acid, docosahexaenoic acid and its derivatives, chloramphenicol, caffeine, prostaglandins, thymol, camphor, extracts or other products of plant and animal origin, e.g. B. evening primrose oil, borage oil or currant seed oil, fish oils, cod liver oil but also ceramides and ceramide-like compounds and so on.

It is also advantageous to choose the active substances from the group of refatting substances for S (6), for example purcellin oil, Eucerit and Neocerit.

The active ingredient (s) are also particularly advantageously selected from the group of NO synthase inhibitors, in particular if the preparations according to the invention are intended for the treatment and prophylaxis of the symptoms of intrinsic and / or extrinsic skin aging and for the treatment and prophylaxis of the harmful effects of ultraviolet radiation on the skin ,

The preferred NO synthase inhibitor is nitroarginine.

The active ingredient (s) are also advantageously selected from the group comprising catechins and bile esters of catechins and aqueous or organic extracts from plants or parts of plants which contain catechins or bile esters of catechins, such as, for example, the leaves of Plant family Theaceae, especially the species Camellia sinensis (green tea). In particular their typical ingredients (such as polyphenols or catechins, caffeine, vitamins, sugar, minerals, amino acids, lipids) are in part.

Catechins are a group of compounds which are to be regarded as hydrogenated flavones or anthocyanidins and derivatives of "catechins" (catechol, 3,3 ', 4', 5,7-flavanpentaol, 2- (3,4- Dihydroxyphenyl) -chroman-3,5,7-triol) Also epicatechin ((2R, 3R) -3,3 ', 4', 5,7-flavanpentaol) is an advantageous active substance in the sense of the present invention.

Plant extracts containing catechins, in particular extracts of green tea, such as. B. extracts from leaves of the plants of the species Camellia spec, especially the teas Camellia sinenis, C. assamica, C. talien- sis or C. irrawadiensis and crosses of these with, for example, Camellia japonica.

Preferred active ingredients are also polyphenols or catechins from the group (-) - catechol, (+) - catechin, (-) - catechin gallate, (-) - gallocatechin gallate, (+) - epicatechin, (-) - epicatechin , (-) - epicatechin gallate, (-) - epigallocatechin, (-) - epigallocatechin gallate.

Flavon and its derivatives (often also collectively called "flavones") are also advantageous active substances in the sense of the present invention. They are characterized by the following basic structure (substitution positions indicated):

Some of the more important flavones, which can also preferably be used in preparations according to the invention, are listed in the table below:

In nature, flavones usually occur in glycosidated form.

According to the invention, the flavonoids are preferably selected from the group of substances of the generic structural formula

where Z to Z ₇ are selected independently of one another from the group H, OH, alkoxy and hydroxyalkoxy, where the alkoxy or hydroxyalkoxy groups are branched and ^unbranched and can have 1 to 18 carbon atoms, and wherein Gly is selected from the group of mono- and oligoglycoside residues.

According to the invention, the flavonoids can also be advantageously selected from the group of substances of the generic structural formula

where Z to Z _{6 are} independently selected from the group H, OH, alkoxy and hydroxyalkoxy, where the alkoxy or hydroxyalkoxy groups can be branched and unbranched and can have 1 to 18 carbon atoms, and wherein Gly is selected from the group Group of the mono- and oligoglycoside residues.

Such structures can preferably be selected from the group of substances of the generic structural formula

wherein Glyi, Gly ₂ and Gly ₃ independently of one another represent monoglycoside residues or. Gly ₂ or Gly ₃ can also represent, individually or together, saturations by hydrogen atoms.

Gly _! , Gly ₂ and Gly _{3 are} independently selected from the group of hexosyl residues, especially rhamnosyl residues and glucosyl residues. However, other hexosyl radicals, for example allosyl, altrosyl, galactosyl, gulosyl, idosyl, mannosyl and talosyl, may also be used advantageously. It can also be advantageous according to the invention to use pentosyl residues.

Zi to Z ₅ are advantageously selected independently of one another from the group H, OH, methoxy, ethoxy and 2-hydroxyethoxy, and the flavone glycosides have the structure

The flavone glycosides according to the invention from the group which are represented by the following structure are particularly advantageous:

where Gly ^ Gly ₂ and Gly ₃ independently of one another represent monoglycoside residues or. Gly ₂ or Gly ₃ can also represent, individually or together, saturations by hydrogen atoms.

Gly !, Gly ₂ and Gly ₃ are preferably selected independently of one another from the group of the hexosyl radicals, in particular the rhamnosyl radicals and glucosyl radicals. However, other hexosyl radicals, for example allosyl, altrosyl, galactosyl, gulosyl, idosyl, mannosyl and talosyl, may also be used advantageously. It can also be advantageous according to the invention to use pentosyl residues.

For the purposes of the present invention, it is particularly advantageous to choose the flavone glycosides from the group α-glucosyl rutin, α-glucosyl myrcetin, α-glucosyl iso-quercitrin, α-glucosyl iso-quercetin and α-glucosyl-quercitrin.

According to the invention, α-glucosylrutin is particularly preferred. Also advantageous according to the invention are naringin (aurantiin, naringenin-7-rhamnoglucosid), hesperidin (3 ', 5,7-trihydroxy-4'-methoxyflavanon-7-rutinoside, hesperidoside, hesperetin-7-O-rutinoside). Rutin (3,3 ', 4', 5,7-pentahydroxyflyvon-3-rutinosid, quercetin-3-rutinosid, Sopho n, Birutan, Rutabion, taurutin, phytomelin, Melin), troxerutin (3,5-dihydroxy- 3 ', 4', 7-tris (2-hydroxyethoxy) flavon-3- (6-O- (6-deoxy-α-L-mannopyranosyl) -ß-D-glucopyranoside)), monoxerutin (3, 3 ', 4', 5-tetrahydroxy-7- (2-hydroxyethoxy) flavon-3- (6-O- (6-deoxy-α-L-mannopyranosyl) -ß-D-glucopyranoside)), dihydrorobinetin (3,3 ', 4', 5 ', 7-pentahydroxyflavanone), taxifolin (3,3', 4 ', 5,7-pentahydroxyflavanone), eriodictyol-7-glucoside (3', 4 ', 5, 7-tetrahydroxyflavanone-7-glucoside), flavanomareϊn (3 ', 4', 7,8-tetrahydroxyflava- non-7-glucoside) and isoquercetin (3,3 ', 4', 5,7-pentahydroxyflavanone-3- (ß -D-glucopyrano-sid).

It is also advantageous to choose the active ingredient (s) from the group of ubiquinones and plastoquinones.

Ubiquinones are characterized by the structural formula

and represent the most widespread and thus best studied biochinones. Depending on the number of isoprene units linked in the side chain, ubiquinones are classified as Q-1, Q-2, Q-3 etc. or according to the number of C- Atoms referred to as U-5, U-10, U-15, etc. They preferably occur with certain chain lengths, e.g. B. in some microorganisms and yeasts with n = 6. Q10 predominates in most mammals, including humans.

Coenzyme Q10, which is characterized by the following structural formula, is particularly advantageous:

Plastoquinones have the general structural formula

on. Plastoquinones differ in the number n of isoprene residues and are named accordingly, e.g. B. PQ-9 (n = 9). There are also other plastoquinones with different substituents on the quinone ring.

Creatine and / or creatine derivatives are also preferred active substances for the purposes of the present invention. Creatine is characterized by the following structure:

Preferred derivatives are creatine phosphate and creatine sulfate, creatine acetate, creatine ascorbate and the derivatives esterified on the carboxyl group with mono- or polyfunctional alcohols.

Another advantageous active ingredient is L-carnitine [3-hydroxy-4- (trimethylammonio) -butter-acid-betaine]. Also acyl-carnitine, which is selected from the group of substances of the following general structural formula \\

+ I

(H ₃ C) ₃ N-CH ₂ - C - CH ₂ - COO ^'

H where R is selected from the group of branched and unbranched alkyl radicals having up to 10 carbon atoms are advantageous active substances in the sense of the present invention. Propionylcarnitine and in particular acetylcarnitine are preferred. Both entantiomers (D- and L-form) can be used advantageously for the purposes of the present invention. It can also be advantageous to use any mixture of enantiomers, for example a racemate of D and L form.

Other advantageous active ingredients are Se cosid, pyridoxol, vitamin K, biotin and flavorings.

The list of the active substances or combinations of active substances mentioned which can be used in the preparations according to the invention is of course not intended to be limiting. The active ingredients can be used individually or in any combination with one another.

In addition, selected recipes according to the invention are suitable, which e.g. B. known anti-wrinkle active ingredients such as flavone glycosides (especially α-glycosylrutin), coenzyme Q10, vitamin E and / or derivatives and the like, particularly advantageous for the prophylaxis and treatment of cosmetic or dermatological skin changes such as z. B. occur during skin aging. They are also advantageous against the appearance of dry or rough skin.

Skin aging is e.g. B. caused by endogenous, genetically determined factors. In the epidermis and dermis it occurs due to aging e.g. B. the following structural damage and malfunctions, which may also fall under the term "senile xerosis":

a) dryness, roughness and formation of (dryness) wrinkles, b) itching and c) reduced regreasing by sebum glands (e.g. after washing). Exogenous factors, such as UV light and chemical noxae, can have a cumulative effect and, for example, accelerate or complement endogenous aging processes. In the epidermis and dermis, exogenous factors in particular lead to the following structural damage and functional disorders in the skin, which are excessive and quality of damage go beyond chronological aging

d) Visible vasodilation (telangiectasias, cuperosis), e) flaccidity and the formation of wrinkles, f) local hyper-, hypo- and incorrect pigmentation (e.g. age spots) and g) increased susceptibility to mechanical stress (e.g. cracking)

In a special embodiment, the present invention relates in particular to products for the care of the naturally aged skin and for the treatment of the consequential damage caused by light aging, in particular the phenomena listed under a) to g)

The oil phase of the formulations according to the invention is advantageously selected from the group of the polar oils, for example from the group of the lecithins and the fatty acid triglycides, in particular the glycine esters of saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 8 to 24, in particular 12 to 18 carbon atoms The fatty acid triglycene ends can, for example, advantageously be selected from the group of synthetic, semisynthetic and natural oils, such as cocoglycend, olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palmol, coconut oil, castor oil, and wheat germ oil , Grape seed oil, thistle oil, evening primrose oil, macadamia nut oil and the like

For the purposes of the present invention, further advantageous polar oil components can also be selected from the group of esters from saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids having a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 C atoms and from the group of esters from aromatic carboxylic acids and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 C atoms. Such esterols can then be selected advantageously from the group octyl palmitate, octyl co- coat, octyl isostearate, octyldodeceyl myristate, cetearyl isononanoate, isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononylyl stylate ethyl, isononylyl stylate 2-octyldodecyl palmitate, stearyl heptanoate, oleyl oleate, olerlerucate, erucyl oleate, erucylerucate, tridecyl stearate, tridecyl trimellitate, and synthetic, semisynthetic and natural mixtures of such esters, such as, for. B. Jojoba oil.

Furthermore, the oil phase can advantageously be selected from the group of dialkyl ethers and dialkyl carbonates. B. dicaprylyl ether (Cetiol OE) and / or dicaprylyl carbonate, for example that available under the trade name Cetiol CC from Cognis.

It is further preferred that the oil component or components from the group isoeikosan, neopentyl glycol diheptanoate, propylene glycol dicaprylate / dicaprate, caprylic / capric / diglyceryl succinate, butylene glycol caprylate / caprate, C ₁₂ . ₁₃ alkyl lactate, di-Cι ₂ _ι ₃ alkyl tartrate, triisostearin, dipentaerythrityl hexacaprylate / hexacaprate, propylene glycol monoisostearate, tricapryline, dimethyl isosorbide. It is particularly advantageous if the oil phase of the formulations according to the invention contains C ₁₂ . ₁₅ alkyl benzoate or consists entirely of this.

Any mixtures of such oil and wax components can also be used advantageously for the purposes of the present invention.

Furthermore, the oil phase can also advantageously also contain non-polar oils, for example those which are selected from the group of branched and unbranched hydrocarbons and waxes, in particular mineral oil, petroleum jelly (petrolatum), paraffin oil, squalane and squalene, polyolefins, hydrogenated polyisobutenes and Isohexadecane. Among the polyolefins, polydecenes are the preferred substances.

The oil phase can advantageously also have a content of cyclic or linear silicone oils or consist entirely of such oils, although it is preferred to use an additional content of other oil phase components in addition to the silicone oil or the silicone oils. Silicone oils are high-molecular synthetic polymeric compounds in which silicon atoms are linked in a chain and / or network manner via oxygen atoms and the remaining valences of silicon by hydrocarbon residues (mostly methyl, more rarely ethyl, propyl, phenyl groups etc.) are saturated. The silicone oils are systematically referred to as polyorganosiloxanes. The methyl-substituted polyorganosiloxanes, which are the most important compounds of this group in terms of quantity and are characterized by the following structural formula

are also known as polydimethylsiloxane or dimethicone (INCI). Dimethicone is available in different chain lengths or with different molecular weights.

Particularly advantageous polyorganosiloxanes for the purposes of the present invention are, for example, dimethylpolysiloxanes [poly (dimethylsiloxane)], which are available, for example, under the trade names Abil 10 to 10,000 from Th. Goldschmidt. Also advantageous are phenylmethylpolysiloxanes (INCI: phenyl dimethicone, phenyl trimethicone), cyclic silicones (octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane), which according to INCI are also referred to as cyclomethicones, amino-modified silicones (INCI: amodimethanes), z. B. polysiloxane-polyalkylene copolymers (INCI: stearyl dimethicone and cetyl dimethicone) and dialkoxydimethyl polysiloxanes (stearoxy dimethicone and behenoxy stearyl dimethicone), which are available as different Abil-Wax types from Th. Goldschmidt. However, other silicone oils can also be used advantageously for the purposes of the present invention, for example cetyldimethicone, hexamethylcyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane).

According to the invention, z. B. natural waxes of animal and vegetable origin, such as beeswax, china wax, bumblebee wax and other insect waxes and shea butter.

Furthermore, the preparations according to the invention can advantageously also be in the form of so-called oil-free cosmetic or dermatological emulsions, which contain a water phase and at least one UV filter substance liquid at room temperature as a further phase.

Particularly advantageous UV filter substances which are liquid at room temperature for the purposes of the present invention are homomenthyl salicylate, 2-ethylhexyl-2-cyano-3,3-diphenyl-acrylate, 2-ethylhexyl-2-hydroxybenzoate and esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester and 4-methoxycinnamic acid isopentyl ester.

Homomenthyl salicylate (INCI: Homosalate) is characterized by the following structure:

2-Ethylhexyl-2-cyano-3,3-diphenylacrylate (INCI: Octocrylene) is available from BASF under the name Uvinul ^® N 539 and is characterized by the following structure:

2-ethylhexyl-2-hydroxybenzoate (2-ethylhexyl salicylate, octyl salicylate, INCI: octyl salicylate) is available, for example, from Haarmann & Reimer under the trade name Neo Heliopan OS and is characterized by the following structure:

4-methoxycinnamic acid (2-ethylhexyl) ester (2-ethylhexyl-4-methoxycinnamate, INCI: octyl methoxycinnamate) is available, for example, from Hoffmann-La Röche under the trade name Parsol MCX and is characterized by the following structure:

Isopentyl 4-methoxycinnamate (isopentyl 4-methoxycinnamate, INCI: isoamyl p-methoxycinnamate) is available, for example, from Haarmann & Reimer under the trade name Neo Heliopan E 1000 and is distinguished by the following structure:

The total amount of one or more UV filter substances which are liquid at room temperature in the finished cosmetic or dermatological preparations is advantageously selected from the range from 0.1% by weight to 30% by weight, preferably from 0.5 to 20% by weight , each based on the total weight of the preparations.

For the purposes of the present invention, such oil-free emulsions can furthermore, although not necessarily, also contain silicone oils and / or silicone waxes, in particular the abovementioned ones.

The water phase of the preparations according to the invention can advantageously contain customary cosmetic auxiliaries, such as, for example, alcohols, in particular those having a low C number, preferably ethanol and / or isopropanol, diols or polyols having a low C number, and their ethers, preferably propylene glycol, glycerol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and analog products, polymers, foam stabilizers, electrolytes and in particular one or more thickeners, which one or more can advantageously be selected from the group consisting of silicon dioxide and aluminum silicates. Polysaccha de or their derivatives, e.g. B. hyaluronic acid, xanthan gum, hydroxypropylmethyl cellulose, particularly advantageously from the group of polyacrylates, preferably a polyacrylate from the group of so-called carbopoles, for example carbopoles of types 980, 981, 1382, 2984, 5984, each individually or in combination. Moisturizers can also be used with preference. Moistunters are substances or mixtures of substances that give cosmetic or dermatological preparations the property of reducing the release of moisture from the horny layer (also called trans-epidermal water loss (TEWL)) and / or the hydration of the horn after application or distribution on the skin surface - to influence the layer positively

Advantageous Moistunzer for the purposes of the present invention are, for example, Glycene, lactic acid, pyrrohdonecarboxylic acid and urea. It is also particularly advantageous to use polymeric Moistunzer from the group of water-soluble and / or water-swellable and / or water-gelable Polysacchande in particular For example, hyaluronic acid, chitosan and / or a fucose-rich polysacchand, which is filed in the Chemical Abstracts under the registration number 178463-23-5 and are available, for example, under the name Fucogel®1000 from the company SOLABIA SA, are advantageous

The cosmetic or dermatological preparations according to the invention can furthermore advantageously, although not necessarily, contain fillers which, for example, further improve the sensory and cosmetic properties of the formulations and, for example, produce a velvety or silky feeling on the skin or intensify advantageous fillers in the sense of the present invention are strong and starch derivatives (such as tapioca starch, distark phosphate, aluminum or sodium starch octenyl succat and the like), pigments that have neither a primary UV filter nor coloring effect (such as boron nitride etc.) and / or Aerosile ^® (CAS no 7631-86-9)

Aerosile ^® , which are available from DEGUSSA AG / Frankfurt, are silicon oxides and are characterized by a small particle size (e.g. between 5 and 40 nm), whereby the particles can be regarded as spherical particles of very uniform dimensions. Macroscopically, Aerosile ^{® are} loose white powder recognizable advantageous Aerosil ^® - grades are, for example, Aerosil ^® OX50, Aerosil ^® 130, Aerosil ^® 150, Aerosil ^® 200, Aerosil ^® 300, Aerosil ^® 380, Aerosil ^® MOX 80 Aerosil ^® MOX 170 Aerosil ^® COK 84, Aerosil ^® R 202, Aerosil ^® R 805, Aerosil ^® R 812, Aerosil ^® R 974, Aerosil ^® R976

Depending on their structure, cosmetic or topical dermatological compositions within the meaning of the present invention can be used, for example, as skin protection cream, cleansing milk, day or night cream, etc. if possible and advantageous, to use the compositions according to the invention as the basis for pharmaceutical formulations.

The cosmetic and dermatological preparations according to the invention can contain dyes and / or color pigments, in particular if they are in the form of decorative cosmetics. The dyes and pigments can be selected from the corresponding positive list in the Cosmetics Ordinance or the EC list of cosmetic colorants. In most cases, they are identical to the colorants approved for food. Advantageous color pigments are, for example, titanium dioxide, mica, iron oxides (for example Fe ₂ O ₃ , Fe ₃ O, FeO (OH)) and / or tin oxide. Advantageous dyes are, for example, carmine, Berlin blue, chrome oxide green, ultramarine blue and / or manganese violet. It is particularly advantageous to choose the dyes and / or color pigments from the list below. The Color Index Numbers (CIN) are taken from the Rowe Color Index, 3rd edition, Society of Dyers and Colorists, Bradford, England, 1971.

Chemical or other name CIN color

Pigment Green 10006 green

Acid Green 1 10020 green

2,4-dinitrohydroxynaphthalene-7-sulfonic acid 10316 yellow

Pigment Yellow 1 1 1680 yellow

Pigment Yellow 3 1 1710 yellow

Pigment Orange 1 11725 orange

2,4-dihydroxyazobenzene 11920 orange

Solvent Red 3 12010 red

1 - (2'-chloro-4'-nitro-1 '-phenylazo) -2-hydroxynaphthalene 12085 red

Pigment Red 3 12120 red

Ceresrot; Sudan Red; Fat red G 12150 red

Pigment Red 112 12370 red

Pigment Red 7 12420 red

Pigment Brown 1 12480 brown

4- (2'-methoxy-5'-sulfonic acid diethylamide-1'-phenylazo) -3-hydroxy-5 "- 12490 red chloro-2", 4 "-dimethoxy-2-naphthoic acid anilide

Disperse Yellow 16 12700 yellow Chemical or other name CIN color

1 - (4-Sulfo-1-phenylazo) -4-amino-benzene-5-sulfonic acid 13015 yellow

2,4-Dihydroxy-azobenzene-4'-sulfonic acid 14270 orange

2- (2,4-Dimethylphenylazo-5-sulfonic acid) -1-hydroxynaphthalene-4-sulfo-14700 red foic acid

2- (4-sulfo-1-naphthylazo) -1-naphthol-4-sulfonic acid 14720 red

2- (6-sulfo-2,4-xylylazo) -1-naphthol-5-sulfonic acid 14815 red

1- (4'-Sulfophenylazo) -2-hydroxynaphthalene 15510 orange

1- (2-sulfonic acid-4-chloro-5-carboxylic acid-1-phenylazo) -2-hydroxy- 15525 red naphthalene

1- (3-methyl-phenylazo-4-sulfonic acid) -2-hydroxynaphthalene 15580 red

1- (4 ', (8') - sulfonic acid naphthylazo) -2-hydroxynaphthalene 15620 red

2-hydroxy-1, 2'-azonaphthalene-1 'sulfo acid 15630 red

3-hydroxy-4-phenylazo-2-naphthylcarboxylic acid 15800 red

1 - (2-sulfo-4-methyl-1-phenylazo) -2-naphthylcarboxylic acid 15850 red

1- (2-sulfo-4-methyl-5-chloro-1-phenylazo) -2-hydroxy-naphthalene-3- 15865 red carboxylic acid

1 - (2-sulfo-1-naphthylazo) -2-hydroxynaphthalene-3-carboxylic acid 15880 red

1 - (3-Sulfo-1-phenylazo) -2-naphthol-6-sulfonic acid 15980 orange

1 - (4-Sulfo-1-phenylazo) -2-naphthol-6-sulfonic acid 15985 yellow

Allura Red 16035 red

1 - (4-Sulfo-1-naphthylazo) -2-naphthol-3,6-disulfonic acid 16185 red

Acid Orange 10 16230 orange

1 - (4-Sulfo-1-naphthylazo) -2-naphthol-6,8-disulfonic acid 16255 red

1 - (4-Sulfo-1-naphthylazo) -2-naphthol-3,6,8-thsulfonic acid 16290 red

8-amino-2-phenylazo-1-naphthol-3,6-disulfonic acid 17200 red

Acid Red 1 18050 red

Acid Red 155 18 130 red

Acid Yellow 121 18690 yellow

Acid Red 180 18736 red

Acid Yellow 11 18820 yellow

Acid Yellow 17 18965 yellow

4- (4-Sulfo-1-phenylazo) -1- (4-sulfophenyl) -5-hydroxy-pyrazolon-3- 19140 yellow carboxylic acid Chemical or other name CIN color

Pigment Yellow 16 20040 yellow

2,6- (4'-Sulfo-2 ", 4" -dimethyl) bis-phenylazo) 1, 3-dihydroxybenzene 20170 orange

Acid Black 1 20470 black

Pigment Yellow 13 21 100 yellow

Pigment Yellow 83 21108 yellow

Solvent Yellow 21230 yellow

Acid Red 163 24790 red

Acid Red 73 27 290 red

2- [4 '- (4 "-sulfo-1" -phenylazo) -7'-sulfo-1' -naphthylazo] -1-hydroxy-7- 27755 black aminonaphthalene-3,6-disulfonic acid

4 '- [(4 "-sulfo-1" -phenylazo) -7'-sulfo-1'-naphthylazo] -1-hydroxy-8-28440 black acetyl-aminonaphthalene-3,5-disulfonic acid

Direct Orange 34, 39, 44, 46, 60 40215 orange

Food Yellow 40800 orange trans-ß-apo-8'-carotenaldehyde (C ₃₀ ) 40820 orange trans-apo-δ'-carotenic acid (C ₃₀ ) ethyl ester 40825 orange

Canthaxanthin 40850 orange

Acid Blue 1 42045 blue

2,4-disulfo-5-hydroxy-4'-4 "-bis- (diethylamino) triphenyl-carbinol 42051 blue

4 - [(- 4-N-ethyl-p-sulfobenzylamino) phenyl- (4-hydroxy-2-sulfophe- 42053 green nyl) - (methylene) -1- (N-ethylN-p-sulfobenzyl) -2, 5-cyclohexadienimine]

Acid Blue 7 42080 blue

(N-ethyl-p-sulfobenzylamino) phenyl- (2-sulfophenyl) -methylene- (N- 42090 blue ethyl-Np-sulfo-benzyl) Δ ^2.5 -cyclohexadienimine

Acid Green 9 42 100 green

Diethyl-di-sulfobenzyl-di-4-amino-2-chloro-di-2-methyl-fuchsonim-42170 green monium

Basic Violet 14 42510 violet

Basic Violet 2 42520 violet

2'-Methyl-4 '- (N-ethyl-N-m-sulfobenzyl) amino-4 "- (N-diethyl) amino- 42735 blue

2-methyl-N-ethylN-m-sulfobenzyl-fuchsonimmonium

4 '- (N-Dimethyl) -amino-4 "- (N-phenyl) -aminonaphtho-N-dimethyl-44045 blue foxsonimmonium Chemical or other name CIN color

2-Hydroxy-3,6-disulfo-4,4'-bis-dimethylaminonaphthofuchsonimmo 44090 green nium

Acid Red 52 45 100 red

3- (2'-Methylphenylamino) -6- (2'-methyl-4'-sulfophenylamino) -9- (2 "- 45190 violet carboxyphenyl) xanthenium salt

Acid Red 50 45 220 red

Phenyl-2-oxyfluoron-2-carboxylic acid 45350 yellow

4,5-dibromofluorescein 45370 orange

2,4,5,7-tetrabromofluorescein 45380 red

Solvent Dye 45396 orange

Acid Red 98 45405 red

3 ', 4', 5 ', 6'-tetrachloro-2,4,5,7-tetrabromofluorescein 45410 red

4,5-diiodofluorescein 45425 red

2,4,5,7-tetraiodofluorescein 45430 red

Quinophthalone 47000 yellow

Quinophthalone disulfonic acid 47005 yellow

Acid Violet 50 50325 violet

Acid Black 2 50420 black

Pigment Violet 23 51319 violet

1, 2-dioxyanthraquinone, calcium-aluminum complex 58000 red

3-oxypyrene-5,8, 10-sulfonic acid 59040 green

1-Hydroxy-4-N-phenylaminoanthraquinone 60724 violet

1-Hydroxy-4- (4'-methylphenylamino) anthraquinone 60725 purple

Acid Violet 23 60730 violet

1, 4-Di (4'-methylphenylamino) anthraquinone 61565 green

1,4-bis (o-sulfo-p-toluidino) anthraquinone 61570 green

Acid Blue 80 61585 blue

Acid Blue 62 62045 blue

N, N'-dihydro-1, 2, r, 2'-anthraquinonazine 69800 blue

Vat Blue 6; Pigment Blue 64 69825 blue

Vat Orange 7 71105 orange

Indigo 73000 blue

Indigo-disulfonic acid 73015 blue Chemical or other name CIN color

4,4'-dimethyl-6,6'-dichlorothioindigo 73360 red

5,5'-dichloro-7,7'-dimethylthioindigo 73385 purple

Quinacridone Violet 19 73900 violet

Pigment Red 122 73915 red

Pigment Blue 16 74 100 blue

Phthalocyanine 74160 blue

Direct Blue 86 74 180 blue

Chlorinated phthalocyanine 74260 green

Natural Yellow 6.19; Natural Red 1 75 100 yellow

Bixin, Nor-Bixin 75120 orange

Lycopene 75125 yellow trans-alpha, beta or gamma carotene 75130 orange

Keto and / or hydroxyl derivatives of carotene 75135 yellow

Guanine or pearlescent 75170 white

1,7-bis (4-hydroxy-3-methoxyphenyl) 1,6-heptadiene-3,5-dione 75300 yellow

Complex salt (Na, Al, Ca) of carminic acid 75470 red

Chlorophyll a and b; Copper compounds of chlorophyll and 75810 green

chlorophyllins

Aluminum 77000 white

Alumina hydrate 77002 white

Water-containing aluminum silicate 77004 white

Ultramarine 77007 blue

Pigment Red 101 and 102 77015 red

Barium sulfate 77120 white

Bismuth oxychloride and its mixtures with mica 77163 white

Calcium carbonate 77220 white

Calcium sulfate 77231 white

Carbon 77266 black

Pigment Black 9 77267 black

Carbo medicinalis vegetabilis 77268: 1 black

Chromium oxide 77288 green

Chromium oxide, containing 77289 green

Pigment Blue 28, Pigment Green 14 77346 green Chemical or other name CIN color

Pigment Metal 2 77400 brown

Gold 77480 brown

Iron oxides and hydroxides 77489 orange

Iron oxide 77491 red

Iron oxide hydrate 77492 yellow

Iron oxide 77499 black

Mixtures of iron (II) and iron (III) hexacyanoferrate 77510 blue

Pigment White 18 77713 white

Manganese ammonium diphosphate 77742 violet

Manganese phosphate; Mn ₃ (PO ₄ ) ₂ ^• 7 H20 77745 red

Silver 77820 white

Titanium dioxide and its mixtures with mica 77891 white

Zinc oxide 77947 white

6,7-dimethyl-9- (1 '-D-ribityl) isoalloxazine, lactoflavin yellow

Caramel brown

Capsanthin, Capsorubin orange

Betanine red

Benzopyrylium salts, anthocyanins red

Aluminum, zinc, magnesium and calcium stearate white

Bromothymol blue blue

Bromocresol green green

Acid Red 195 red

If the formulations according to the invention are in the form of products which are used on the face; it is favorable to choose one or more substances from the following group as the dye: 2,4-dihydroxyazobenzene, 1- (2'-chloro-4'-nitro-1'-phenylazo) -2-hydroxynaphthalene, ceres red, 2- (4-sulfo-1-naphthylazo) -1 -naphthol-4-sulfonic acid, calcium salt of 2-hydroxy-1, 2'-azonaphthalene-1'-sulfonic acid, calcium and barium salts of 1- (2-sulfo 4-methyl-1-phenylazo) -2-naphthylcarboxylic acid, calcium salt of 1- (2-sulfo-1-naphthylazo) -2-hydroxynaphthalene-3-carboxylic acid, aluminum salt of 1- (4-sulfo-1-phenylazo) -2 -naphthol-6-sulfonic acid, aluminum salt of 1- (4-sulfo-1-naphthyl-azo) -2-naphthol-3,6-disulfonic acid, 1- (4-sulfo-1-naphthylazo) -2-naphthol-6 , 8-disulfonic acid, aluminum salt of 4- (4-sulfo-1-phenylazo) -1 - (4-sulfophenyl) -5-hydroxy-pyrazolon-3-carboxylic acid, aluminum and zirconium salts of 4,5-dibromofluorescein, Aluminum and Zirconium salts of 2,4,5,7-tetrabromofluorescein, 3 ', 4', 5 ', 6'-tetrachloro-2,4,5,7-tetrabromofluorescein and its aluminum salt, aluminum salt of 2,4,5,7 -Tetraiodofluorescein, aluminum salt of quinophthalone disulfonic acid, aluminum salt of indigo disulfonic acid, red and black iron oxide (CIN: 77 491 (red) and 77 499 (black)), iron oxide hydrate (CIN: 77 492), manganese ammonium diphosphate and titanium dioxide.

Also advantageous are oil-soluble natural dyes, such as. B. paprika extracts, ß-carotene or cochineal.

Formulations containing pearlescent pigments are also advantageous for the purposes of the present invention. The types of pearlescent pigments listed below are particularly preferred:

1. Natural pearlescent pigments, such as. B.

^■ "fish silver" (guanine / hypoxanthine mixed crystals from fish scales) and ^■ "mother-of-pearl" (ground mussel shells)

2. Monocrystalline pearlescent pigments such as B. Bismuth oxychloride (BiOCI)

3. Layer-substrate pigments: e.g. B. mica / metal oxide

Pearlescent pigments are based, for example, on powdered pigments or castor oil dispersions of bismuth oxychloride and / or titanium dioxide and bismuth oxychloride and / or titanium dioxide on mica. Z is particularly advantageous. B. the gloss pigment listed under CIN 77163.

The following pearlescent pigment types based on mica / metal oxide are also advantageous:

Fe ₂ 0 ₃ | Red Green

^' Fe ₂ 0 ₃ j black

Combination pigments Ti0 ₂ / Fe ₂ Ö ₃ | golds

Tiδ ₂ Cr ₂ 0 ₃ I green f i0 ₂ / Berlin blue | deep blue

,

TiÖ ₂ / Carmin

For example, particular preference is given to the pearlescent pigments available from Merck under the trade names Timi ron, Colorona or Dichrona.

The list of the pearlescent pigments mentioned is of course not intended to be limiting. Pearlescent pigments which are advantageous in the sense of the present invention are obtainable in numerous ways known per se. For example, other substrates besides mica can be coated with other metal oxides, such as. B. silica and the like. Are advantageous for. B. with Ti0 ₂ and Fe ₂ 0 ₃ coated Si0 ₂ particles ("Ronaspheren"), which are sold by Merck and are particularly suitable for the optical reduction of fine wrinkles.

It can also be advantageous to do without a substrate such as mica. Iron pearlescent pigments which are produced without the use of mica are particularly preferred. Such pigments are e.g. B. available under the trade name Sicopearl copper 1000 from BASF.

Also particularly advantageous are effect pigments, which are available from Flora Tech under the trade name Metasomes Standard / Glitter in various colors (yello, red, green, blue). The glitter particles are present in mixtures with various auxiliaries and dyes (such as, for example, the dyes with the Color Index (Cl) numbers 19140, 77007, 77289, 77491).

The dyes and pigments can be present both individually and in a mixture and can be mutually coated, different color effects generally being produced by different coating thicknesses. The total amount of dyes and coloring pigments is advantageously from the range of z. B. from 0.1% by weight to 30% by weight, preferably from 0.5 to 15% by weight, in particular from 1.0 to 10% by weight, in each case based on the total weight of the preparations , It is also advantageous for the purposes of the present invention to produce cosmetic and dermatological preparations, the main purpose of which is not protection from sunlight, but which nevertheless contain UV protection substances. So z. For example, UV-A or UV-B filter substances are usually incorporated into day creams or makeup products. UV protection substances, like antioxidants and, if desired, preservatives, also provide effective protection of the preparations themselves against spoilage. Cosmetic and dermatological preparations which are in the form of a sunscreen are also favorable.

Accordingly, in the sense of the present invention, the preparations preferably contain, in addition to one or more UV filter substances according to the invention, at least one further UV-A and / or UV-B filter substance. The formulations may, although not necessary, optionally also contain one or more organic and / or inorganic pigments as UV filter substances, which may be present in the water and / or the oil phase.

Preferred inorganic pigments are metal oxides and / or other metal compounds which are sparingly soluble or insoluble in water, in particular oxides of titanium (Tiö ₂ ), zinc (ZnO), iron (e.g. Fe ₂ 0 ₃ ), zirconium (Zr0 ₂ ), silicon ( Si0 ₂ ), manganese (e.g. Mnö), aluminum (Al ₂ 0 ₃ ), cerium (e.g. Ce ₂ O ₃ ), mixed oxides of the corresponding metals and mixtures of such oxides.

For the purposes of the present invention, such pigments can advantageously be surface-treated (“coated”), with an amphiphilic or hydrophobic character, for example, being formed or maintained be provided with a hydrophobic layer.

According to the invention, z. B. titanium dioxide pigments coated with octylsilanol. Suitable titanium dioxide particles are available under the trade name T805 from Degussa. Also particularly advantageous are Ti0 ₂ pigments coated with aluminum stearate, e.g. B. those available under the trade name MT 100 T from TAYCA. Another advantageous coating of the inorganic pigments consists of dimethylpolysiloxane (also: dimethicone), a mixture of fully methylated, linear siloxane polymers which are blocked at the end with trimethylsiloxy units. Zinc oxide pigments which are coated in this way are particularly advantageous for the purposes of the present invention.

It is also advantageous to coat the inorganic pigments with a mixture of dimethylpolysiloxane, in particular dimethylpolysiloxane with an average chain length of 200 to 350 dimethylsiloxane units, and silica gel, which is also referred to as simethicone. It is particularly advantageous if the inorganic pigments are additionally coated with aluminum hydroxide or aluminum oxide hydrate (also: alumina, CAS no .: 1333-84-2). Titanium dioxides coated with simethicone and alumina are particularly advantageous, the coating also being able to contain water. An example of this is the titanium dioxide available from Merck under the trade name Eusolex T2000.

An advantageous organic pigment for the purposes of the present invention is 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol) [INCI: bisoctyl-triazole], which is characterized by the chemical structural formula

is marked and is available under the trade name Tinosorb® M from CIBA-Chemical GmbH.

Preparations according to the invention advantageously contain substances which absorb UV radiation in the UV-A and / or UV-B range, the total amount of the filter substances, for. B. 0.1 wt .-% to 30 wt .-%, preferably 0.5 to 20 wt .-%, in particular 1, 0 to 15.0 wt .-%, based on the total weight of the preparations to kos - To provide metallic preparations that protect the hair or skin from the entire range of ultraviolet radiation. They can also serve as a sunscreen for the hair or skin.

Advantageous further UV-A filter substances for the purposes of the present invention are di-benzoylmethane derivatives, in particular 4- (tert-butyl) -4'-methoxydibenzoylmethane (CAS No. 70356-09-1), which is sold by Givaudan under the brand name Parsol ^® 1789 and is sold by Merck under the trade name Eusolex® 9020.

Also advantageous are the 1,4-di (2-oxo-10-sulfo-3-bornylidenemethyl) benzene and its salts (especially the corresponding 10-sulfato compounds, especially the corresponding sodium, potassium or triethanolammonium salt) , which is also called benzene-1,4-di (2-oxo-3-bornylidenemethyl-10-sulfonic acid) and is characterized by the following structure:

Advantageous UV filter substances in the sense of the present invention are also so-called broadband filters, i.e. Filter substances that absorb both UV-A and UV-B radiation.

Advantageous broadband filters or UV-B filter substances are, for example, bis-resorcinyltriazine derivatives with the following structure:

^J

where R ¹ , R ² and R ^{3 are} independently selected from the group of branched and unbranched alkyl groups having 1 to 10 carbon atoms or a single hydrogen atom. Particularly preferred are the 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine (INCI: Aniso triazine ), which is available under the trade name Tinosorb® S from CIBA-Chemicals GmbH.

Particularly advantageous preparations in the sense of the present invention, which are distinguished by a high or very high UV-A protection, preferably contain, in addition to the filter substance or substances according to the invention, further UV-A and / or broadband filters, in particular dibenzoylmethane derivatives [for example the 4th - (tert-Butyl) -4'- methoxydibenzoylmethane], the 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1, 1, 3,3-tetramethylbutyl) -phenol), the 1,4-di (2-oxo-10-sulfo-3-bomylidenemethyl) benzene and / or its salts and / or the 2,4-bis - {[4- (2-ethylhexyloxy ) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1, 3,5-triazine, in each case individually or in any combination with one another.

Also other UV filter substances, which the structural motif

are advantageous UV filter substances for the purposes of the present invention, for example the s-triazine derivatives described in European patent application EP 570 838 A1, the chemical structure of which is given by the generic formula

is reproduced, whereby

R represents a branched or unbranched dC ^ alkyl radical, a C ₅ -C ₁₂ cycloalkyl radical, optionally substituted by one or more C _r C alkyl groups,

X represents an oxygen atom or an NH group,

Ri is a branched or unbranched CC ₁₈ alkyl radical, a C ₅ -C ₁₂ cycloalkyl radical, optionally substituted with one or more CC ₄ alkyl groups, or a hydrogen atom, an alkali metal atom, an ammonium group or a group of the formula

means in which

A represents a branched or unbranched d-Ciβ-alkyl radical, a C ₅ -C ₂ cycloalkyl or aryl radical, optionally substituted with one or more C, -C - alkyl groups, R _{3 represents} a hydrogen atom or a methyl group, n is a Number from 1 to 10 represents a branched or unbranched CC ₁₈ alkyl radical, a C ₅ -C ₁₂ cycloalkyl radical, optionally substituted with one or more dC - alkyl groups, when X represents the NH group, and a branched or unbranched d-Ci ₈ alkyl radical, a C ₅ -C ₂ cycloalkyl radical, optionally substituted with one or more CC alkyl groups, or a hydrogen atom, an alkali metal atom, an ammonium group or a group of the formula

means in which

A represents a branched or unbranched d-dβ-alkyl radical, a C ₅ -C ₁₂ -cycloalkyl or aryl radical, optionally substituted with one or more CC ₄ -alkyl groups,

R _{3 represents} a hydrogen atom or a methyl group, n represents a number from 1 to 10 when X represents an oxygen atom.

A particularly preferred UV filter substance in the sense of the present invention is also an asymmetrically substituted s-triazine, the chemical structure of which is represented by the formula

is reproduced, which is also referred to below as dioctylbutylamidotriazon (INCI: dioctylbutamidotriazone) and is available under the trade name UVASORB HEB from Sigma 3V.

For the purposes of the present invention, a symmetrically substituted s-triazine which is 4,4 ', 4 "- (1,3,5-triazine-2,4,6-triyltriimino) tris-benzoic acid tris (2- ethylhexyl ester), synonymous: 2,4,6-tris [anilino- (p-carbo-2'-ethyl-1'-hexyloxy)] - 1, 3,5-thazine (INCI: octyl triazone), which is marketed by BASF Aktiengesellschaft under the trade name UVINUL® T 150.

European laid-open specification 775 698 also describes bis-resorcinyltriazine derivatives which are to be used with preference, the chemical structure of which is represented by the generic formula

is reproduced, wherein R, R ₂ and A represent a wide variety of organic radicals.

Also advantageous in the sense of the present invention are the 2,4-bis - {[4- (3-sulfonato) - 2-hydroxypropyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1, 3,5-triazine sodium salt, the 2,4-bis - {[4- (3- (2-propyloxy) -2-hydroxypropyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl ) -1, 3,5-triazine, the 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- [4- (2-methoxyethyl carboxyl ) -phenylamino] -1, 3,5-triazine, the 2,4-bis - {[4- (3- (2-propyloxy) -2-hydroxypropyloxy) -2-hydroxy] phenyl} -6- [4- (2-ethyl-carboxyl) phenylamino] -1, 3,5-triazine, the 2,4-bis - {[4- (2-ethyl-hexyloxy) -2-hydroxy] phenyl} -6 - (1-methyl-pyrrol-2-yl) -1, 3,5-triazine, the 2,4-bis - {[4-tris (trimethylsiloxysilylpropyloxy) -2-hydroxy] phenyl} -6- ( 4-methoxyphenyl) - 1, 3,5-thazine, the 2,4-bis - {[4- (2 "-methylpropenyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1 , 3,5-triazine and 2,4-bis - {[4- (1 ', 1', 1 ', 3', 5 ', ^{5, 5,} -Heptamethylsiloxy-2 "-methyl-propyloxy) - 2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1, 3,5-thazine.

An advantageous broadband filter for the purposes of the present invention is 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol), which through the chemical structural formula

is marked and is available under the trade name Tinosorb® M from CIBA-Chemical GmbH.

Another advantageous broadband filter for the purposes of the present invention is 2- (2H-benzotriazol-2-yl) -4-methyl-6- [2-methyl-3- [1, 3,3,3-tetramethyl-1- [(trimethylsilyl) oxy] disiloxa- nyl] propyl] -phenol (CAS no .: 155633-54-8) with the INCI name Dromethzole Trisiloxane, which is characterized by the chemical structural formula

is marked.

The UV-B and / or broadband filters can be oil-soluble or water-soluble. Advantageous oil-soluble UV-B and / or broadband filter substances are e.g. B .:

3-benzylidene camphor derivatives, preferably 3- (4-methylbenzylidene) camphor, 3-

benzylidenecamphor;

4-aminobenzoic acid derivatives, preferably 4- (dimethylamino) benzoic acid (2-ethylhexyl) ester, 4- (dimethylamino) benzoic acid amyl ester;

2,4,6-trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1, 3,5-triazine;

Esters of benzalmalonic acid, preferably 4-methoxybenzalmalonic acid di (2-ethylhexyl) ester;

Esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester, 4-methoxycinnamic acid isopentyl ester;

Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-

Hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone as well as UV filters bound to polymers.

Advantageous water-soluble UV-B and / or broadband filter substances are e.g. B .:

^■ salts of 2-phenylbenzimidazole-5-sulfonic acid, such as its sodium, potassium or triethanolammonium salt, and the sulfonic acid itself;

■ sulfonic acid derivatives of 3-benzylidene camphor, such as. B. 4- (2-oxo-3-bornylidene methyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bornylidene methyl) sulfonic acid and salts thereof.

Another light protection filter substance which can be used advantageously according to the invention is ethylhexyl-2-cyano-3,3-diphenylacrylate (octocrylene), which is available from BASF under the name Uvinul ^® N 539 and is distinguished by the following structure:

It can also be of considerable advantage to use polymer-bound or polymeric UV filter substances in preparations according to the present invention, in particular those as described in WO-A-92/20690.

It may also be advantageous, if appropriate, to incorporate further UV-A and / or UV-B filters into cosmetic or dermatological preparations, for example certain salicylic acid derivatives such as 4-isopropylbenzyl salicylate, 2-ethylhexyl salicylate (= octyl salicylate), homomenthyl salicylate.

The list of the UV filters mentioned, which can be used in the sense of the present invention, should of course not be limiting.

The preparations according to the invention advantageously contain the substances which absorb UV radiation in the UV-A and / or UV-B range in a total amount of, for. B. 0.1 wt .-% to 30 wt .-%, preferably 0.5 to 20 wt .-%, in particular 1, 0 to 15.0 wt .-%, each based on the total weight of the preparations to cosmetic To provide preparations which protect the hair or the skin from the entire range of ultraviolet radiation. They can also serve as a sunscreen for the hair or skin.

It may also be advantageous to incorporate film formers into the cosmetic or dermatological preparations according to the invention, for example in order to improve the water resistance of the preparations or to increase the UV protection performance (UV-A and / or UV-B boosting). Both water-soluble or dispersible and fat-soluble film formers are suitable, in each case individually or in combination with one another. Advantageous water-soluble or dispersible film formers are e.g. B. Polyurethanes (e.g. Avalure® types from Goodrich), Dimethicone Copolyol Polyacrylate (Silsoft Surface® from the Witco Organo Silicones Group), PVP / VA (VA = vinyl acetate) copolymer (Luviscol VA 64 Powder from BASF) etc ,

Advantageous fat-soluble film formers are e.g. B., the film formers from the group of polymers based on polyvinylpyrrolidone (PVP)

Particularly preferred are copolymers of polyvinylpyrrolidone, for example the PVP hexadecene copolymer and the PVP eicosen copolymer, which are available under the trade names Antaron V216 and Antaron V220 from GAF Chemicals Cooperation, as well as Tricontayl PVP and the like.

The following examples are intended to illustrate the present invention without restricting it. The numerical values in the examples mean percentages by weight, based on the total weight of the respective preparations.

Examples:

Claims

claims

1. Sunscreen-effective cosmetic or dermatological emulsions, characterized in that they (a) one or more sucrose esters and

(b) Phenylene-1, 4-bis- (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and / or their salts.

2. Preparation according to claim 1, characterized in that it is sand-repellent.

3. Sunscreen-effective cosmetic or dermatological preparations, characterized in that they contain synergistic combinations of substances

(a) one or more sucrose esters and

(b) contain phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and / or its salts, the UV protection performance of these preparations being higher than the same preparations which do not contain any substances according to (a).

4. Light-protective cosmetic or dermatological preparations, characterized in that they contain synergistic combinations of substances

(a) one or more sucrose esters and

(b) Phenylene-1, 4-bis- (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and / or their salts, the skin moisturizing performance of these preparations being higher than the same preparations which are not substances according to (a) included.

5. Preparation according to one of claims 1 or 2, characterized in that the sucrose ester or sucrose esters from the group sucrose tetrastearate triacetate, sucrose laurate, sucrose dilaurate, sucrose stearate, sucrose distearate, sucrose secaprylate, sucrose myristate, sucrose paiitate, sucrose sucrose, sucrose sucrose, sucrose sucrose Sucrose polypalmitate is chosen.

6. Preparation according to one of the preceding claims, characterized in that it contains at least one UV filter substance which is liquid at room temperature.

7. Preparation according to one of the preceding claims, characterized in that it is oil-free.

8. Preparation according to one of the preceding claims, characterized in that it contains at least one further UV filter substance, selected from the group triazines, camphor derivatives and organic and / or inorganic pigments.

9. Preparation according to one of the preceding claims, characterized in that it contains at least one further UV-A filter substance and / or a broadband filter, selected from the group dibenzoylmethane dehvate [in particular 4- (tert-butyl) - 4'-methoxydibenzoylmethane] , 2,2'-methylene-bis- (6- (2H-benzothazol-2-yl) -4- (1, 1, 3,3-tetramethylbutyl) phenol), 1, 4-di (2-oxo- 10-sulfo-3-bornylidenemethyl) benzene and its salts and 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) - 1, 3,5-triazine, and the further filter substances can be present individually or in any combination with one another.

10. Preparation according to one of the preceding claims, characterized in that it contains at least one flavone glycoside, in particular α-glucosylrutin, and / or vitamin E and / or its derivatives.

1 1. Use of preparations according to claim 9 or 10 for protecting the skin against premature aging.

12. Preparation according to one of the preceding claims, which causes or enhances a velvety or silky feeling on the skin, characterized in that it contains at least one substance selected from the group starch and starch derivatives, in particular distarch phosphate, aluminum and / or sodium starch octenyl succinate ,