WO2002038121A1

WO2002038121A1 - Cosmetic skin treatment, care or protection composition

Info

Publication number: WO2002038121A1
Application number: PCT/EP2001/012672
Authority: WO
Inventors: Thomas Gerke; Kirsten Hoyer; Ulf Karsten; Oliver Nixdorf
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2000-11-09
Filing date: 2001-11-02
Publication date: 2002-05-16
Also published as: AU2002224822A1; DE10055558A1

Abstract

The invention relates to a cosmetic skin treatment, care or protection composition. The composition comprises an excipient and is characterized by containing an extract from the green alga Prasiola crispa ssp. antarctica.

Description

Cosmetic composition for treatment, care or for

Protection of the skin

The invention relates to a cosmetic composition for the treatment, care or protection of the skin and the use of an extract from the green algae Prasiola crispa ssp. antarctica and a UV-absorbing substance from an extract of this green algae and their use.

Under the influence of solar radiation, skin pigmentation occurs through the formation of melanins. Irradiation with long-wave UV-A light causes the melanin bodies already present in the epidermis to darken, while short-wave UV-B radiation causes the formation of new melanins. Before the protective pigment can be formed, the skin is exposed to the unfiltered radiation. Depending on the duration of exposure, this can lead to reddening of the skin, skin inflammation (sunburn) or even blisters. Stresses on the organism associated with such skin lesions, for example in connection with the release of histamines, can additionally lead to headache, weariness, fever, cardiovascular disorders and the like. Long-term exposure to UV rays can also lead to cumulative DNA damage, which can result in skin cancer.

For the consumer who wants to protect himself from the harmful aspects of solar radiation, the market offers a large number of products, most of which are oils and milky emulsions, which, in addition to some care substances, mainly contain synthetic UV light protection filters.

However, a large number of the available sunscreens cause skin intolerance or allergies, such as Mallorca acne. However, the consumer desires formulations that are highly compatible with skin cosmetics even when applied to sensitive skin. There Skin intolerance or allergic reactions often occur depending on certain skin types, there is an increasing need in the market for new and different formulations, in particular products with natural active ingredients being desired by customers.

Another problem is that in many sunscreens several UV light protection filters are required to cover a sufficient absorption area. However, the various UV light protection filters are often not optimally compatible with one another, so that segregation or even chemical reactions of the individual components can occur, which leads to a decrease in shelf life. For this reason, too, there is a need for novel substances that have a sun protection effect.

An increasing need for new types of sunscreen is also caused by the fact that the ozone layer of the stratosphere has been increasingly degraded by anthropogenic influences in recent years. Further depletion of the ozone layer is expected in the future. However, the ozone layer is responsible for ensuring that a large part of the UV light from the sun's radiation does not reach the earth's surface, so that degradation of this ozone layer leads to an increase in the proportion of UV light that reaches the earth's surface. The affected people are thus exposed to a higher exposure to UV rays, so that if they do not protect themselves effectively, an increased risk of cancer must be expected. Although long-wave UV-A light (characteristic wavelength range from 315 to 400 nm) presumably plays an important role in the development of skin cancer, typical sunscreens often pass very easily, since these sunscreens often only contain the UV-B- that is the main cause of sunburn. Filter out light effectively. This explains in particular the need for novel substances that absorb in the area of UV-A light. In green algae there are substances with suitable absorption spectra. It is known (Post and Larkum (1993), Aquat. Bot., 45, pp. 231-243) that the methanolic extract from Prasiola crispa ssp. antarctica shows an absorption band at 325 nm. It is probably a mycosporin-like amino acid (MAA). However, these MAAs are unstable after extraction (Takano, Uemura and Hirata (1978), Tetrahedron Lett, 26, pp. 2299-2300; Tsujino, Yabe, Sekikawa and Hamanaka, (1978), Tetrahedron Lett., 26, p. 1401 -1402) and can therefore not be used effectively in cosmetic compositions.

It is therefore an object of the present invention to provide a novel sunscreen which, in particular, absorbs the long-wave UV-A light and has good skin tolerance and sufficient stability in cosmetic formulations.

Surprisingly, it was found that extracts from the green alga Prasiola crispa ssp. antarctica have sufficient stability to be processed in cosmetic compositions which also have an absorption spectrum which is suitable for use in sunscreens and which at the same time have a high skin tolerance.

The invention relates to a cosmetic composition for the treatment, care or protection of the skin, which comprises a carrier, and which is characterized in that it contains an extract from the green algae Prasiola crispa ssp. contains antarctica.

Another object of the invention is the use of an extract from the green algae Prasiola crispa ssp. antarctica in cosmetic compositions.

The invention further relates to a UV-absorbing substance with an absorption maximum of 324 nm, which by HPLC on a Phenomenex Sphereclone RP-8 column (5 μm, 250 x 4mm ID) with 5 vol.% Aqueous methanol, to which 0.1 vol.% Acetic acid was added, as the mobile phase and a flow rate of 0.7 ml min ^"1 is obtainable from an aqueous methanol extract of the green algae Prasiola crispa ssp.antarctica with a retention time of 3.4 minutes.

Another object of the present invention is the use of this UV-absorbing substance or a derivative thereof in cosmetic preparations.

Of particular advantage is the fact that the cosmetic composition according to the invention for the treatment, care or protection of the skin, in contrast to many known sunscreens which predominantly absorb UV-B light, has in particular a UV-A blocking effect. This is all the more important since UV-A light is suspected to play an important role in the development of cancer. This results in a particularly effective protection of the skin from the harmful effects of solar radiation. This effect cannot be achieved simply by combining known sun protection factors.

Another advantage of the cosmetic composition according to the invention is that it has good skin tolerance. The composition contains an extract from the green algae Prasiola crispa ssp. antarctica and includes a carrier. With a suitable choice of the carrier, it is possible to obtain a composition that can only be produced on the basis of natural raw materials. This is particularly important with regard to the compatibility of the end products. The cosmetic composition is also characterized by phase stability and storage stability. This composition can advantageously be used not only to protect the skin, but also to treat or care for the skin. If the cosmetic composition is used as a sunscreen, the focus is on the particularly effective protection of the skin from the harmful effects of sun exposure. The cosmetic However, the composition can also be used as an after-sun product or as a sunburn treatment or treatment for the skin.

As a rule, the cosmetic composition is used for topical application on the skin. Topical preparations are to be understood here as those preparations which are suitable for applying the active substances to the skin in a fine distribution and preferably in a form which can be absorbed by the skin. For this, e.g. aqueous and aqueous-alcoholic solutions, sprays, foams, foam aerosols, ointments, aqueous gels, emulsions of the O / W or W / O type, microemulsions or cosmetic stick preparations.

According to a preferred embodiment of the cosmetic composition according to the invention, the carrier is water, a gas, a water-based liquid, an oil, a gel, an emulsion or microemulsion, a dispersion or a mixture thereof. The carriers mentioned show good skin tolerance. Aqueous gels, emulsions or microemulsions are particularly advantageous for topical preparations.

Nonionic surfactants, zwitterionic surfactants, ampholytic surfactants or anionic emulsifiers can be used as emulsifiers. The emulsifiers can be contained in the composition according to the invention in amounts of 0.1 to 10, preferably 1 to 5,% by weight, based on the composition.

For example, a surfactant from at least one of the following groups can be used as the nonionic surfactant:

Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear fatty alcohols with 8 to 22 carbon atoms, with fatty acids with 12 to 22 carbon atoms and with alkylphenols with 8 to 15 carbon atoms in the alkyl group; • Cι _{2 /} i ₈ fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol;

• glycerol monoesters and diesters and sorbitan monoesters and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and their ethylene oxide addition products;

• alkyl mono- and oligoglycosides with 8 to 22 carbon atoms in the alkyl radical and their ethoxylated analogues;

• Addition products of 15 to 60 mol ethylene oxide onto castor oil and / or hardened castor oil;

Polyol and especially polyglycerol esters, e.g. Polyglycerol polyricinoleate, polyglycerol poly-12-hydroxystearate or polyglycerol dimerate. Mixtures of compounds from several of these classes of substances are also suitable;

• Addition products of 2 to 15 moles of ethylene oxide with castor oil and / or hardened castor oil;

• Partial esters based on linear, branched, unsaturated or saturated C _6/22 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (eg sorbitol), alkyl glucosides (eg methyl glucoside, butyl glucoside, glucoside) and polyglucosides (eg cellulose);

• mono-, di- and trialkyl phosphates as well as mono-, di- and / or tri-PEG-alkyl phosphates and their salts;

• wool wax alcohols;

• polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;

• Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE-PS 1165574 and / or mixed esters of fatty acids with 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol or polyglycerol and

• polyalkylene glycols

• Betaines

• esterquats

Zwitterionic surfactants can also be used as emulsifiers. Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one carboxylate or sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinates, for example that Cocoalkyldimethylammonium glycinate, N-acylamino-propyl-N, N-dimethylammonium glycinate, for example the cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxylmethyl-3-hydroxyethylimidazolines each with 8 to 18 C atoms in the alkyl or acyl group and that Coconut acylaminoethyl hydroxyethyl carboxymethyl glycinate. The fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine is particularly preferred.

Suitable emulsifiers are ampholytic surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a Cβ _/ iβ-alkyl or -acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylamino-butyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkyl sarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are the N-cocoalkyl aminopropionate, the coco acylaminoethyl aminopropionate and the C _12/18 acyl sarcosine. In addition to the ampholytic emulsifiers, quaternary emulsifiers are also suitable, those of the esterquat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, being particularly preferred. Furthermore, alkyl ether sulfates, monoglyceride sulfates, fatty acid sulfates, sulfosuccinates and / or ether carboxylic acids can be used as anionic emulsifiers.

Guerbet alcohols based on fatty alcohols with 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C ₆ -C ₂₂ fatty acids with linear C ₆ -C ₂₂ fatty alcohols, esters of branched C ₆ -C- * ₃ - come as oil bodies. Carboxylic acids with linear C ₆ -C ₂₂ fatty alcohols, esters of linear C ₆ -C ₂₂ fatty acids with branched alcohols, especially 2-ethylhexanol, esters of linear and / or branched fatty acids with polyhydric alcohols (such as propylene glycol, dimer diol or trimer triol) and / or Guerbet alcohols, triglycerides based on C ₆ - C-io fatty acids, liquid mono- / di- / triglyceride mixtures based on C ₆ -Cι ₈ - fatty acids, esters of C ₆ -C ₂₂ fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of C ₂ -Cι ₂ - dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 Hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear C ₆ -C ₂₂ fatty alcohol carbonates, Guerbet carbonates, esters of benzoic acid with linear and / or branched C ₆ -C ₂₂ alcohols (e.g. Finsolv® TN), dialkyl ethers, ring opening products from epoxidized fatty acid esters with polyols, silicone oils and / or aliphatic or naphthenic hydrocarbons. Silicone compounds can also be used as oil bodies, for example dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones and amino, fatty acid, alcohol, polyether, epoxy, fluorine, alkyl and / or glycoside-modified silicone compounds which are both liquid and at room temperature can be resinous. The oil bodies can be present in the agents according to the invention in amounts of 1 to 90, preferably 5 to 80, and in particular 10 to 50,% by weight, based on the composition.

According to a particularly preferred embodiment, the composition according to the invention contains further UV light protection filters, in particular UV-B filters.

The extract from the green algae Prasiola crispa ssp. antarctica advantageously absorbs UV-A radiation in particular. Thus, the dangerous UV-A rays are filtered out of sunlight, which are suspected of causing cancer. The absorption range of the composition can be increased by adding further UV light protection filters. Both additional UV-A and UV-B sun protection factors can be added. However, it is particularly preferred to add UV-B sun protection factors, since the extract from the green algae Prasiola crispa ssp. antarctica ensures absorption in the UV-A range and thus both UV-A and UV-B light is filtered out of the sun's rays. Advantageously, a sunscreen is thus created which blocks the harmful UV radiation in a wide absorption range and thus ensures effective protection of the skin. One or more further UV light protection filters can be added to the composition according to the invention. The further UV light protection filters that can be added to the cosmetic composition are preferably soluble compounds or insoluble pigments or mixtures thereof. In the case of soluble compounds, UV light protection filters are understood to mean organic substances which are able to absorb ultraviolet rays and release the absorbed energy in the form of longer-wave radiation, for example heat. The organic substances can be oil-soluble or water-soluble.

As oil-soluble UV-B filters e.g. the following substances are used:

3-benzylidene camphor and its derivatives, e.g. 3- (4-methylbenzylidene) camphor;

4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate;

Esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, 4-

Isopentyl methoxy cinnamate, 2-ethylhexyl 2-cyano-3-phenyl-cinnamate (octocrylene);

• esters of salicylic acid, preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropylbenzyl ester, salicylic acid homomethyl ester;

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

2-hydroxy-4-meth-oxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone;

• Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate;

• triazine derivatives, such as 2,4,6-trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1, 3,5 ~ triazin (Octyltriazone) and Dioctyl Butamido Triazone (Uvasorb HEB ^®).

Propane-1,3-dione, e.g. 1- (4-tert-butylphenyl) -3- (4'methoxyphenyl) propane-1,3-dione.

Possible water-soluble substances are:

• 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts; • Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts;

Sulfonic acid derivatives of 3-benzylidene camphor, e.g. 4- (2-oxo-3-bornylidene methyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and their salts.

The use of esters of cinnamic acid is particularly preferred, preferably

2-ethylhexyl 4-methoxycinnamate, isopentyl 4-methoxycinnamate, 2-

2-ethylhexyl cyano-3-phenyl-cinnamic acid (octocrylene). Furthermore, it is

Use of derivatives of benzophenone, in particular 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-

Dihydroxy-4-methoxybenzophenone and the use of propane-1,3-dions, such as 1- (4-tert-Butylphenyl) -3- (4'methoxyphenyl) propane-1,3-dione preferred. Surprisingly, it was found that the presence of the UV-B filter, in particular the cinnamic acid ester, leads to a synergistic increase in the stability of the green algae extract in the formulations according to the invention.

Derivatives of benzoylmethane, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl, are particularly suitable as typical UV-A filters -4'-methoxydibenzoylmethane or 1-phenyl-3- (4 '~ isopropylphenyl) propane-1,3-dione. The UV-A and UV-B filters can of course also be used in mixtures.

Insoluble pigments, e.g. finely dispersed metal oxides or salts such as titanium dioxide, zinc oxide, iron oxide, aluminum oxide, cerium oxide, zirconium oxide, silicates (talc), barium sulfate and zinc stearate can be used. The particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm.

In addition to the two aforementioned groups of primary light stabilizers, secondary light stabilizers of the antioxidant type can also be used, which interrupt the photochemical reaction chain which is triggered when

UV radiation penetrates the skin. Typical examples are superoxide

Dismutase, tocopherols (vitamin E) and ascorbic acid (vitamin C). Surprisingly, the addition of ascorbic acid and / or tocopherols or their derivatives improves the stability of the cosmetic composition. In particular, the stability of the green algae extract in the formulations according to the invention is improved. The total proportion of light stabilizers in the composition according to the invention is usually 1 to 20, preferably 5 to 15% by weight. The composition according to the invention as such can contain 1 to 95, preferably 5 to 80, and in particular 10 to 60% by weight of water.

According to a particularly preferred embodiment, the cosmetic composition according to the invention further contains nourishing substances, further cosmetic active ingredients and / or auxiliaries and additives. Skin moisturizers, antimicrobial substances and / or deodorant or antiperspirant substances are used in particular as further cosmetic active ingredients. This has the advantage that further desired effects can be achieved which contribute to the care or treatment of the skin or, for example, increase the well-being of the user of the cosmetic composition when using this composition.

Thus, in addition to the carrier, the green algae extract, water and physiologically suitable solvents, the cosmetic composition can also contain, among other things, caring components such as oils, waxes, fats, lipid-replenishing substances, thickeners, emulsifiers and fragrances. A high proportion of nourishing substances is particularly advantageous for topical prophylactic or cosmetic treatment of the skin. It is particularly advantageous if, in addition to the animal and vegetable fats and oils, which in many cases also have a care effect, the composition also contains further care components. The group of nourishing active ingredients that can be used includes, for example: fatty alcohols with 8 - 22 carbon atoms, in particular fatty alcohols from natural fatty acids; animal and vegetable protein hydrolyzates, in particular elastin, collagen, keratin, milk protein, soy protein, silk protein, oat protein, pea protein, almond protein and wheat protein hydrolyzates; Vitamins and vitamin precursors, especially those of vitamin groups A and B; Mono-, di- and oligosaccharides; Plant extracts; Honey extracts; ceramides; phospholipids; Petroleum jelly, paraffin and silicone oils; Fatty acid and fatty alcohol esters, especially the monoesters of fatty acids with alcohols with 3 to 24 carbon atoms. The vitamins, provitamins or vitamin precursors to be used preferably in the composition according to the invention include, among others:

• Vitamins, provitamins and vitamin precursors from groups A, C, E and F, in particular 3,4-didehydroretinol (vitamin A ₂ ), ß-carotene (provitamin of vitamin Ai), ascorbic acid (vitamin C), and the palmitic acid esters, glucosides or phosphates of ascorbic acid, tocopherols, especially α-tocopherol and its esters, e.g. B. the acetate, nicotinate, phosphate and succinate; also vitamin F, which is understood to mean essential fatty acids, in particular linoleic acid, linolenic acid and arachidonic acid; Fl mi Ayϊϊd its derivatives un rovijttjn eϊgeii vdrtellhifemiϊsi ^" a special ^! Skin smoothing effect]

The vitamins, provitamins or vitamin precursors of the vitamin B group or their derivatives and the derivatives of 2-furanone which are preferably to be used in the composition according to the invention include:

• Vitamin Bi, trivial name thiamine, chemical designation 3 - [(4'-amino-2'-methyl-5 ^{'-pyrimidinyl)} methyl] -5- (2-hydroxyethyl) -4-methylthiazolium chloride. Thiamine hydrochloride is preferably used in amounts of 0.05 to 1% by weight, based on the total agent.

• Vitamin B ₂ , common name riboflavin, chemical name 7,8-dimethyl-10- (1-D-ribityl) -benzo [g] pteridine-2,4 (3H, 10H) -dione. In free form, riboflavin comes e.g. B. in whey before, other riboflavin derivatives can be isolated from bacteria and yeast. A stereoisomer of riboflavin which is also suitable according to the invention is lyxoflavin which can be isolated from fishmeal or liver and which carries a D-arabityl radical instead of D-ribityl. Riboflavin or its derivatives are preferably used in amounts of 0.05 to 1% by weight, based on the total agent. • Vitamin B ₃ . The compounds nicotinic acid and nicotinamide (niacinamide) are often listed under this name. According to the invention, preference is given to nicotinamide, which is preferably present in the agents according to the invention in amounts of 0.05 to 1% by weight, based on the total agent.

• Vitamin B ₅ (pantothenic acid and panthenol). Panthenol is preferably used. Derivatives of panthenol which can be used according to the invention are, in particular, the esters and ethers of panthenol and cationically derivatized panthenols. In a further preferred embodiment of the invention, instead of and in addition to pantothenic acid or panthenol, derivatives of 2-furanone with the general structural formula (I) can also be used.

(I)

Preferred are the 2-furanone derivatives in which the substituents R ¹ to R ⁶ independently of one another are a hydrogen atom, a hydroxyl radical, a methyl, methoxy, aminomethyl or hydroxymethyl radical, a saturated or mono- or di-unsaturated, linear or branched C ₂ -C ₄ - hydrocarbon residue, a saturated or mono- or di-unsaturated, branched or linear mono-, di- or trihydroxy-C ₂ -C ₄ - hydrocarbon residue or a saturated or mono- or di-unsaturated, branched or linear mono- , Di- or triamino-C ₂ -C ₄ - represent hydrocarbon radical. Particularly preferred derivatives are the commercially available substances dihydro-3-hydroxy-4,4-dimethyl-2 (3H) -furanone with the common name pantolactone (Merck), 4-hydroxymethyl-γ-butyrolactone (Merck), 3.3 -Dimethyl-2-hydroxy-γ-butyrolactone (Aldrich) and 2.5- Dihydro-5-methoxy-2-furanone (Merck), all stereoisomers being expressly included. The 2-furanone derivative which is extremely preferred according to the invention is pantolactone (dihydro-3-hydroxy-4,4-dimethyl-2 (3H) - furanone), where in formula (I) R ^{1 is} a hydroxyl group, R ^{2 is} a hydrogen atom, R ³ and R ^{4 represent} a methyl group and R ⁵ and R ^{6 represent} a hydrogen atom. The stereoisomer (R) -pantolactone is formed when pantothenic acid is broken down.

These compounds advantageously impart moisturizing and skin-calming properties to the cosmetic composition according to the invention.

The compounds of the vitamin B ₅ type mentioned and the 2-furanone derivatives are preferably present in the agents according to the invention in a total amount of 0.05 to 10% by weight, based on the agent as a whole. Total amounts of 0.1 to 5% by weight are particularly preferred.

• Vitamin B ₆ , which does not mean a uniform substance, but rather the derivatives of 5-hydroxymethyl-2-methylpyridin-3-ol known under the trivial names pyridoxine, pyridoxamine and pyridoxal. Vitamin B ₆ is contained in the agents according to the invention preferably in amounts of 0.0001 to 1.0% by weight, in particular in amounts of 0.001 to 0.01% by weight.

• Vitamin B ₇ (biotin), also known as vitamin H or "skin vitamin". Biotin is (3aS, 4S, 6aR) -2-oxohexahydrothienol [3,4-d] - imidazole-4-valeric acid. Biotin is contained in the agents according to the invention preferably in amounts of 0.0001 to 1.0% by weight, in particular in amounts of 0.001 to 0.01% by weight.

Panthenol, pantolactone, nicotinamide and biotin are very particularly preferred according to the invention. Auxiliaries and additives are understood to mean substances which are suitable for improving the aesthetic, application technology and / or cosmetic properties, such as, for example, co-emulsifiers, organic solvents, superfatting agents, stabilizers, antioxidants, waxes or fats, consistency agents, thickeners, browning agents, Vitamins, cationic polymers, biogenic agents, preservatives, hydrotopes, solubilizers, colors and fragrances.

For example, the following auxiliaries and additives can be used:

- allantoin,

- aloe vera,

Bisabolol,

Ceramides and pseudoceramides,

Antioxidants advantageously improve the stability of the compositions according to the invention. Antioxidants are, for example, amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazole and imidazole derivatives (e.g. urocanic acid), peptides such as e.g. B. D, L-carnosine, D-carnosine, L-carnosine and their derivatives (z. B. Anserin), carotenoids, carotenes (z. B. α-carotene, ß-carotene, lycopene) and their derivatives, lipoic acid and their derivatives (e.g. dihydroliponic acid), aurothioglucose, propylthiouracil and other thio compounds (e.g. thioglycerin, thiosorbitol, thioglycolic acid, thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl -, Propyl, amyl, butyl, lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters) and 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. buthioninsulfoximines, homocysteine sulfoximine, buthioninsulfones, penta-, hexa-, heptathioninsulfoximine) in very low tolerable dosages (e.g. pmol / kg to μmol / kg) , furthermore metal chelators (e.g. α-hydroxy fatty acids, EDTA, EGTA, phytic acid right, lactoferrin), α-hydroxy acids (e.g. B. citric acid, lactic acid, malic acid), Humic acids, bile acid, bile extracts, gallic acid esters (e.g. propyl, octyl and dodecyl gallate), flavonoids, catechins, bilirubin, biliverdin and their derivatives, unsaturated fatty acids and their derivatives (e.g. γ-linolenic acid, linoleic acid, Arachidonic acid, oleic acid), folic acid and its derivatives, hydroquinone and its derivatives (e.g. arbutin), ubiquinone and ubiquinol and its derivatives, vitamin C and its derivatives (e.g. ascorbyl palmitate, stearate, dipalmitate, acetate, Mg ascorbyl phosphate, sodium and magnesium ascorbate, disodium ascorbyl phosphate and sulfate, potassium ascorbyl tocopheryl phosphate, chitosan ascorbate), isoascorbic acid and its derivatives, tocopherols and their derivatives (e.g. tocopheryl acetate, tocopheryl acetate, tocopheryl acetate, tocopheryl acetate, tocopheryl acetate, 5, tocophereth-10, tocophereth-12, tocophereth-18, tocophereth-50, tocopher sol), vitamin A and derivatives (e.g. vitamin A palmitate), the coniferyl benzoate of benzoin, rutin, rutinic acid and their derivatives, Disodium rutinyl disulfate, cinnamic acid and their derivatives (e.g. B. ferulic acid, ethyl ferulate, caffeic acid), kojic acid, chitosan glycolate and - salicylate, for butylhydroxytoluene, butylhydroxyanisole, Nordihydroguajakharzsäure, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and derivatives thereof, mannose and derivatives thereof, zinc and zinc derivatives (for example, ZnO, ZnSO. ₄ ), Selenium and selenium derivatives (e.g. selenium methionine), stilbenes and stilbene derivatives (e.g. stilbene oxide, trans-stilbene oxide). According to the invention, suitable derivatives (salts, esters, sugars, nucleotides, nucleosides, peptides and lipids) as well as mixtures of these active substances mentioned or plant extracts (e.g. tea tree oil, rosemary extract and rosemary acid) which contain these antioxidants can be used. Preferred lipophilic, oil-soluble antioxidants from this group are tocopherol and its derivatives, gallic acid esters, flavonoids and carotenoids, and butylated hydroxytoluene / anisole. As water-soluble antioxidants are amino acids, e.g. B. tyrosine and cysteine and their derivatives and tannins, especially those of plant origin are preferred. The total amount of the antioxidants in the cosmetic compositions according to the invention is 0.001-20% by weight, preferably 0.05-10% by weight, in particular 0.1-5% by weight and very particularly preferably 0.1-2% by weight. -%. Triterpenes, especially triterpenic acids such as ursolic acid, rosmaric acid, betulinic acid, boswellic acid and bryonolic acid,

Monomeric catechins, especially catechin and epicatechin, leucoanthocyanidins, catechin polymers (catechin tannins) and gallotannins,

- Thickeners, e.g. B. gelatin, vegetable gums such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum or locust bean gum, natural and synthetic clays and layered silicates, e.g. B. bentonite, hectorite, montmorillonite or Laponite ^® , fully synthetic hydrocolloids such. B. polyvinyl alcohol, and also Ca, Mg or Zn soaps of fatty acids,

- plant glycosides,

- structurants such as maleic acid and lactic acid,

- dimethyl isosorbide,

Alpha, beta and gamma cyclodextrins, in particular for stabilizing retinol,

- Solvents, swelling and penetration substances such as ethanol, isopropanol, ethylene glycol, propylene glycol, propylene glycol monoethyl ether, glycerin and diethylene glycol, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates

- perfume oils, pigments and dyes for coloring the agent,

- Substances for adjusting the pH, e.g. B. α- and ß-hydroxy carboxylic acids,

Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids,

Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers,

Pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate,

- Blowing agents such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air.

The addition of allantoin, bisabolol and / or aloe vera also in the form of extracts to the cosmetic compositions according to the invention further improves the skin-soothing, moisturizing and skin-care properties of the formulations and is therefore particularly preferred.

As additional ingredients, the cosmetic composition according to the invention can contain minor amounts of further surfactants that are compatible with the other ingredients. Typical examples of anionic surfactants are soaps, alkyl benzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxymidyl ether ether sulfates, mono Dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acyl amino acids such as, for example, acyl lactylate, acyl tartrate and acyl glucate glate fatty acid products, acyl glucosate fate Wheat base) and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, these can have a conventional, but preferably a narrow, homolog distribution. Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, optionally partially oxidized alk (en) yl oligoglycosides or especially glucoramides, , Polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution. Typical examples of cationic surfactants are quaternary ammonium compounds and ester quats, in particular quaternized fatty acid trialkanolamine ester salts. Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines.

According to a particularly preferred embodiment of the cosmetic composition according to the invention, the one used for the composition is Extract from the green algae Prasiola crispa ssp. antarctica an aqueous or aqueous-alcoholic extract. The use of water or water / alcohol, in particular ethanol, is particularly advantageous since water or water / alcohol are preferred extraction agents which are both easy and gentle to use and also have a high yield and selectivity with regard to the UV-absorbing substances in Prasiola crispa antarctica ssp. demonstrate. In addition, topical preparations, for example aqueous and aqueous / alcoholic solutions, aqueous gels, sprays, foams, foam aerosols, ointments, emulsions of the O / W or W / O type or microemulsions, can be prepared in a simple manner from the extracts mentioned ,

According to a further preferred embodiment of the composition according to the invention, the composition contains at least one mycosporin-like amino acid (MAA). Prasiola crispa ssp. antarctica contains traces of mycosporin-glycine and a large amount of a structurally not yet elucidated UV-absorbing substance, which shows an absorption maximum at 324 nm and which is determined by HPLC analysis (5 vol.% aqueous methanol, 0.1 vol. % Acetic acid; flow rate: 0.7 ml min ^"1 ; Phenomenex Sphereclone RP-8 column, 5 μm, 250 x 4 mm ID) is available with a retention time of 3.4 min. Detection in the HPLC analysis is carried out between Shinorin (Retention time: 3.2 min) and Porphyra-334 (Retention time: 4.0 min.) Presumably, the structurally as yet unidentified UV-absorbing substance is also a mycosporin-like amino acid.

The composition according to the invention preferably contains 0.01 to 10% by weight of the extract, based on the dry mass of the extract. Contents of 0.05 to 1% by weight, in particular 0.1 to 0.5% by weight, based on the dry mass of the extract, are particularly preferred.

According to a further embodiment of the invention, the cosmetic composition is in the form of an emulsion, a dispersion, a suspension, an aqueous surfactant preparation, a milk, a lotion, a cream, a balm, an ointment, a gel, a granulate, a powder, one Stick preparations such as a lipstick, a foam, an aerosol or a spray. Such formulations are well suited for topical preparations. Suitable emulsions are oil-in-water emulsions and W / O emulsions or microemulsions. Another object of the present invention is the use of an extract from the green algae Prasiola crispa ssp. antarctica in cosmetic compositions. Such cosmetic compositions can be used, inter alia, as sunscreens, after-sun products or as agents against sunburn. The use according to the invention has the advantages already described.

Another object of the present invention is the use of an extract from the green algae Prasiola crispa ssp. antarctica as a sunscreen. A sunscreen means cosmetic preparations for application to the skin and non-cosmetic compositions, for example for UV protection of surfaces, e.g. of containers or foils, e.g. Packaging films that can be used. The extract from the green algae Prasiola crispa ssp. antarctica can also be used in combination with other UV light protection filters. A good UV-absorbing effect can advantageously be achieved even by using relatively small amounts of the green algae extract.

According to a preferred embodiment of the use according to the invention of the extract from the green algae Prasiola crispa ssp. antarctica as a sunscreen, the sunscreen is applied to the surface of the body to be treated or protected. In the case of a cosmetic composition, the sunscreen is applied topically, i.e. applied to the skin. This form of application is particularly advantageous since it is easy to handle, so that incorrect dosing is largely excluded. An additional skin care effect can also be achieved. If only individual parts of the body are exposed to solar radiation, the sunscreen can only be applied specifically to these parts of the body.

According to a further preferred embodiment, the sunscreen is used orally. This has the advantage that the sunscreen can already be taken prophylactically and offers protection for a longer period of time. For example, there is no risk of the protective effect of the sunscreen caused by sweating or prolonged contact with water or other substances that are applied to the surface Wash off sunscreen can lose. This eliminates the often annoying re-dosing of the sunscreen by repeated application after a few hours.

Another object of the present invention is a UV-absorbing substance with an absorption maximum of 324 nm, which was added by HPLC with 5% by volume aqueous methanol to which 0.1% by volume acetic acid was added as the mobile phase and a flow rate of 0.7 ml min ^"1 on a Phenomenex Sphereclone RP-8 column (5 μm, 250 x 4 mm ID) from an aqueous methanol extract of the green alga Prasiola crispa ssp. antarctica is available with a retention time of 3.4 min.

The retention time of 3.4 min is between that of Shinorin (retention time: 3.2 min) and Porphyra-334 (retention time: 4.0 min). It is therefore assumed that this structurally as yet unidentified substance is a mycosporin-like amino acid (MAA). This MAA advantageously shows an absorption maximum at 324 nm, which means that it absorbs in the region of the long-wave UV-A light, which is suspected of causing cancer. Since this UV-absorbing substance is also characterized by good biological compatibility and is sufficiently stable, this UV-absorbing substance or derivatives thereof can be used in cosmetic preparations which are used in particular as sunscreens, after-sun products or agents against sunburn , Such sunscreens using the UV absorbing substance described can be applied cutan or orally.

The invention is described in more detail below with the aid of examples.

example 1

Extracts from the green algae Prasiola crispa ssp. antarctica were obtained as follows:

50 g of algae dry matter were crushed and stirred at 40 ° C with 300 ml of 25% methanol for 2 hours. It was then centrifuged (5000 rpm) and the supernatant solution separated. The remaining pellet was again stirred as described with 25% methanol for 2 hours. The mixture was then centrifuged again (5000 rpm) and the supernatant solution was separated off.

The supernatant solutions separated in the two centrifugations were combined. The solvent was then distilled off under reduced pressure and the remaining residues were dried in vacuo. The dry matter yield was 1.5% by weight, based on the algae dry matter used.

The dry substance obtained was dissolved in 30 ml of ethanol for further use and for further investigations.

The extract obtained from the green algae Prasiola crispa ssp. antarctica was determined by HPLC analysis with 5% by volume aqueous methanol to which 0.1% by volume acetic acid was added as the mobile phase and a flow rate of 0.7 ml min ^"1 on a Phenomenex Sphereclone RP-8 column (5 μm, 250 x 4 mm ID) with a retention time of 3.4 min, a substance with an absorption maximum of 324 nm was obtained.

Example 2

Phase A components wt%

Methoxy PEG-22 / Dodecyl Glycol Copolymer (Elfacos ^® E 200) (Akzo, Düren) 1

PEG-45 / dodecyl glycol copolymer

(Elfacos ^® ST 9) (Akzo, Düren) 3

Hydroxyoctacosanyl hydroxystearate

(Elfacos ^® C 26) (Akzo, Düren) 5

Paraffin oil, liquid 8

Isopropyl stearate 9

Tocopherol acetate 0.5 Phase B Eusolex ^® 232 (Merck, Darmstadt) 3

Prasiola extract 10

Tris (hydroxymethyl) aminomethane 1,33

1.1.1 Disodium EDTA 0.1

Glycerin 3

Water, demineralized ad

100.00

Eusolex ^® 232 = 2-phenylbenzimidazole-5-sulfonic acid and its potassium, sodium and triethanolamine salts

To neutralize the Eusolex ^® 232, the tris (hydroxymethyl) aminomethane was dissolved in the water of phase B and Eusolex ^® 232 was added with stirring. After complete dissolution, the remaining raw materials of phase B were added and heated to 80 ° C. Phase A was heated to 75 ° C. Phase B was then slowly stirred into phase A and homogenized. The mixture was then cooled with stirring.

The sunscreen cream produced according to Example 2 was tested by 10 test persons between the ages of 30 and 60 years with regard to their skin tolerance. For this purpose, the cream was applied to the inside of one arm, the application being repeated after 90 minutes. After 120 minutes, skin tolerance was assessed on the basis of the following parameters: occurrence of allergic reactions or itching, and subjective feeling of the "skin feeling" of the test subjects. In no case were allergic reactions or itching observed. The test subjects rated the "skin feel" as very pleasant.

Subsequently, the inside of the arms of the test subjects were exposed to sunlight for 90 minutes, with sun protection cream being applied again to the inside of the arms, which had already been creamed on, after 60 minutes. Here too, no allergic reactions or itching were observed and the "skin feeling" was rated as very pleasant by all test subjects. A comparison of the inside of the creamed arms with that of the not creamed arms showed a slightly lower degree of browning of the creamed inside in 8 out of 10 test persons.

Example 3

Phase A components wt%

2-ethylhexyl-4-methoxy-cinnamate

(Eusolex ^® 2292) (Merck, Darmstadt)

1.1.2 Polyoxyethylene-40-glycerolsorbitan isostearate 1.1.3 (Arlacel 582) (ICI, Essen) 2.75 1.1.4 Polyoxyethylene-40-sorbitol septaoleate 1.1.5 (Arlatone T) (ICI, Essen) 1

Paraffin oil, viscous 11

Isopropyl myristate 5

Isooctyl stearate (Cetiol 868) (Cognis, Düsseldorf) 6

Phase B Prasiola extract 10

polyoxyethylene

(Atlas G-2330) (ICI, Essen) 1, 25

Propanediol-1, 2 1, 25

Magnesium sulfate x 7 H ₂ O 0.7

methyldibromoglutaronitrile

(Euxyl K 400) (Schülke and Meier) 0.05

Water, demineralized ad

100.00

Phase C SiO ₂ (Aerosil R 972) (Degussa, Frankfurt) 1

Phase A was heated to 75 ° C and phase B was heated to 80 ° C. First, phase B was slowly stirred into phase A. Then phase C slowly stirred into phase A. The combined phases were homogenized with stirring and also cooled to room temperature with stirring.

The test method already described under Example 2 was used.

Here, too, an allergic reaction or the occurrence of an itch was never observed, and the feeling on the skin was perceived as very pleasant. When comparing the tanning effect, it was found in 9 out of 10 test subjects that the creamed inside of the arms had less browning than the untreated inside.

Claims

claims

1. Cosmetic composition for the treatment, care or protection of the skin, which comprises a carrier, characterized in that it contains an extract from the green algae Prasiola crispa ssp. contains antarctica.

2. Composition according to claim 1, characterized in that the carrier is water, a gas, a water-based liquid, an oil, a gel, an emulsion or microemulsion, a dispersion or a mixture thereof.

3. Composition according to claim 1 or 2, characterized in that it contains further UV light protection filters, in particular UV-B filters.

4. Composition according to claim 3, characterized in that it contains soluble compounds or insoluble pigments or mixtures thereof as further light protection filters.

5. Composition according to one of the preceding claims, characterized in that it contains nourishing substances, further cosmetic active substances, in particular vitamins, skin moisturizers, antioxidants, antimicrobial active substances, deodorant or antiperspirant substances, and / or auxiliaries and additives.

6. Composition according to one of the preceding claims, characterized in that the extract from the green algae Prasiola crispa ssp. antarctica is watery or watery-alcoholic.

7. Composition according to one of the preceding claims, characterized in that the composition comprises a mycosporin-like amino acid (MAA).

8. Composition according to one of the preceding claims, characterized in that the composition contains 0.01-10% by weight of the extract, based on the dry mass of the extract.

9. Composition according to claim 8, characterized in that the composition contains 0.05-1% by weight of the extract, in particular 0.1-0.5% by weight, based on the dry mass of the extract.

10. Composition according to one of the preceding claims, characterized in that the composition in the form of an emulsion, a dispersion, a suspension, an aqueous surfactant preparation, a milk, a lotion, a cream, a balm, an ointment, a gel, a granulate , a powder, a stick preparation, a foam, an aerosol or a spray.

11. Use of an extract from the green algae Prasiola crispa ssp. antarctica in cosmetic compositions.

12. Use of an extract from the green algae Prasiola crispa ssp. antarctica as a sunscreen.

13. Use according to claim 12, characterized in that the sunscreen is applied topically.

14. Use according to claim 12, characterized in that the sunscreen is used orally.

15. UV-absorbing substance with an absorption maximum of 324 nm, which was added by HPLC with 5 vol .-% aqueous methanol, to which 0.1 vol .-% acetic acid, as the mobile phase and a flow rate of 0.7 ml min ^{"1 is available} on a Phenomenex Sphereclone RP-8 column (5 μm, 250 x 4 mm ID) from an aqueous methanol extract of the green algae Prasiola crispa ssp. Antarctica with a retention time of 3.4 minutes.

16. Use of the UV-absorbing substance according to claim 15 or a derivative thereof in cosmetic preparations.

17. Use of the UV-absorbing substance according to claim 15 or a derivative thereof as a sunscreen.

18. Use according to claim 17, characterized in that the sunscreen is applied topically or orally.