DE10349666A1 - Aqueous or aqueous-alcoholic insect repellent cosmetic formulation, useful on skin and/or hair, contains combination of repellent(s) and Aloe vera extract, Hammamelis extract and/or extracts of oyster and sea silt - Google Patents

Abstract

Aqueous or aqueous-alcoholic cosmetic formulation contains a combination (a) of repellent(s) selected from ethyl 3-(N-n-butyl-N-acetyl-amino)propionate, N,N-diethyltoluamide, N,N-diethylbenzamide, 2-(2-hydroxyethyl)-1-methylpropyl 1-piperidinecarboxylate and 1-(3-cyclohexen-1-yl-carbonyl)-2-methylpiperidine; and (b) extract(s) selected from Aloe vera extract, Hammamelis extract and sea extract. ACTIVITY : Insect Repellent.

Description

The The present invention relates to an aqueous or aqueous-alcoholic cosmetic preparation containing a combination of one or selected several repellents from the group 3- (N-n-butyl-N-acetylamino) propionic acid ethyl ester, N, N-diethyltoluolamide, N, N-diethylbenzamide, 1-piperidinecarboxylic acid 2- (2-hydroxyethyl) -1-methylpropyl ester, 1- (3-cyclohexen-1-yl-carbonyl) -2-methylpiperidine and one or more extracts selected from the group Aloe Vera, Hammamelis, sea extract and their use.

insects repellent (insect repellent, insect repellent, Insect repellents, insect repellents, repellents, Repellents) are preparations, for the defense and / or expulsion of insects, but also ticks and mites externally be applied and prevent insects, ticks and Mites become active on the skin. Insect repellents are said to be Skin from harassment by blood sucking or biting Protecting insects and other parasites and / or pests by repelling them before settling on the skin, so it does not sting or bite comes. Accordingly, the funds do not act as contact poisons, but only as a repellent, because they do not kill the animals, but just drive away.

Accordingly, in Meaning of the present invention under the term "insects dismissive means "not only to understand those formulations that are effective against insects are. Rather, the following is of course also true for such Preparations, the other blood sucking or biting parasites and / or pests (For example, spiders) ward off or distribute, even if in individual cases not mentioned like.

prints or bites from insects and other parasites usually cause wheals, reddening and itching as well as in isolated cases to mostly harmless running Infections. Insects, especially mosquitoes, can also parasitic and transducers viral infections (such as malaria, yellow fever or dengue) be. Overall, there are e.g. not less than 3000 different Mosquito species, of which about 100 diseases can spread. The defense or expulsion Therefore, these insects are also used to protect against such Infections.

insects orient themselves optically and with the help of "chemical senses" for light, form and color, heat and Humidity and the content of carbon dioxide and perfume in the air. These include different amino acids as well as ammonia, lactic and butyric acid. They "recognize" for promising host organisms, in particular their body temperature, the carbon dioxide emissions and the odorants produced and emitted by the cutaneous microflora. The attractants are visited in the direction of increasing concentration (Finkel, E. Siemer, "Repellents dermal application ", Apoth. J. 8, 1986, p. 32-37).

Nice Since time immemorial, people are stinging or biting insects or other parasites. Accordingly, the need is the old Humanity after insect repellents. One since the early history well-known method, annoying or harmful Insects make their stay near man unattractive or to make unpleasant, is the lighting of aromatic or aromatic fires strong smelling herbs or woods and heavy smoke. Also the treatment of the skin with strong smelling substances to repel insects has been around since Ancient known. At the turn of the last century, a series was more natural essential oils as an insect repellent in use, such as aniseed oil, bergamot oil, birch wood tar, Camphor, citronella oil, eucalyptus oil, geranium, Pine oils, coconut oil, lavender oil, nutmeg oil, clove oil, orange blossom oil, peppermint oil, pollen oils (pennyroyal oil), pyrethrum, thyme oil and cinnamon oil.

you the mode of action of repellent active ingredients is so prevalent that these slowly evaporate after application and thus close above the Skin form a scent coat that repels the insects, by putting the active ingredients on the for the "sense of smell" responsible Address sensors of insects. They interfere with it the lock mechanism. After applying an insect repellent The insects already fly away from the skin at some distance again off; they make "a bow" to the treated ones Skin. With decreasing effect, they are approaching more and more, until finally the Concentration of repellents has dropped so far that the first Contact or stitch takes place. The mode of action of the repellents limited So be it, the body's own To mask odors and with a repulsive Fragrance component to provide.

Because of their despite intense odor predominantly insufficient effectiveness and their part lacking compatibility at higher concentrations, natural repellents in today's insect repellents have been largely displaced by better-acting synthetic substances. These are predominantly high-boiling liquids or low-melting or subliming crystalline substances which slowly evaporate at room temperature. Most repellent agents belong to the classes of amides, alcohols, esters and ethers.

One A widely used all-round repellent is, for example, N, N-diethyl-3-methylbenzamide (DEET), which against mosquitoes, Brakes, sandflies, ticks, biting flies, mites, fleas and bugs is effective. Also in use is dimethylphthalate (Palatinol M, DMP) which is used against mosquitoes (in particular Aedes and Anopheles species) acts.

Another common repellent active ingredient is ethyl 3- (Nn-butyl-N-acetylamino) propionate (also referred to as ethylbutylacetylaminopropionate or Repellent 3535), which is characterized by the following structural formula:

repellent 3535 is against mosquitoes (Aedes aegypti, Anopheles albimanus), Tsetse flies (Glossinae) and brakes (Tabanidae).

und kann unter dem Namen Bayrepel^® (bei der Bayer AG) im Handel erworben werden.More recently, the 1-piperidinecarboxylic acid 2- (2-hydroxyethyl) -1-methylpropyl ester has also been developed as a versatile repellent agent. This has the following structure

and can be purchased commercially (from Bayer AG) under the name Bayrepel ^®.

• • Wässrige Repellent-Zubereitungen setzen den Repellent-Wirkstoff nur langsam frei, so dass eine gewisse Zeit vergeht, bevor die Insekten abweisende Wirkung nach dem Auftragen auf die Haut eintritt.
• • Um dieses Problem zu lösen werden die Zubereitungen meist mit Ethanol versetzt. Die wässrig-alkoholischen oder alkoholischen Zubereitungen haben aufgrund ihrer hohen Wirkstoff-Freisetzungsrate nur eine äußerst begrenzte Wirkungszeit. In der Regel beträgt die wirksame Schutzdauer weniger als 2 Stunden.
• • Die hydrolytische Stabilität von Repellentien, insbesondere von 3-(N-n-Butyl-N-acetyl-amino)propionsäureethylester, ist nur begrenzt. Das heißt, dass die Zubereitungen ihre Wirksamkeit mit zunehmenden (Lagerungs-) Alter einbüßen und die Haltbarkeit der Zubereitungen nur begrenzt ist.
• • Die Anwendung herkömmlicher Zubereitungen führt, bedingt durch einen hohen Alkohol- und/oder Repellentienanteil, bei empfindlichen Anwendern zu Hautirritationen.

According to the prior art, a variety of insect repellents are known. However, these have a number of disadvantages:

• • Aqueous repellent preparations release the repellent agent only slowly, so that a certain amount of time passes before the insect repellent effect occurs after application to the skin.
• • To solve this problem, the preparations are usually mixed with ethanol. The aqueous-alcoholic or alcoholic preparations have due to their high drug release rate only a very limited duration of action. As a rule, the effective protection period is less than 2 hours.
• • The hydrolytic stability of repellents, especially ethyl 3- (Nn-butyl-N-acetylamino) propionate, is limited. This means that the preparations lose their effectiveness with increasing (storage) age and the shelf life of the preparations is limited.
• • The use of conventional preparations leads, due to a high alcohol and / or Repellentienanteil, with sensitive users to skin irritation.

• • hoch wirksam ist auch gegen besonders aggressive Insekten (z.B. Aedes aegypti, Anopheles albimanus).
• • eine besonders lang anhaltende Wirkung aufweist.
• • besonders schnell nach dem Auftragen seine Wirkung entfaltet.
• • besonders mild/verträglich gegenüber der Haut ist.

It was therefore the object of the present invention to eliminate or at least alleviate the disadvantages of the prior art. Furthermore, it was the object of the present invention to develop an insect repellent, which

• • highly effective against particularly aggressive insects (eg Aedes aegypti, Anopheles albimanus).
• • has a particularly long-lasting effect.
• • unfolds its effect particularly quickly after application.
• • is particularly mild / tolerated to the skin.

• a) einem oder mehreren Repellentien gewählt aus der Gruppe 3-(N-n-Butyl-N-acetyl-amino)propionsäureethylester, N,N-Diethyltoluolamid, N,N-Diethylbenzamid, 1-Piperidincarbonsäure-2-(2-hydroxyethyl)-1-methylpropylester, 1-(3-Cyclohexen-1-yl-carbonyl)-2-methylpiperidin und
• b) einem oder mehreren Extrakten gewählt aus der Gruppe Aloe vera-Extrakt, Hammamelis-Extrakt, Meeresextrakt.

Surprisingly, the objects are achieved by an aqueous or aqueous-alcoholic cosmetic preparation containing a combination of

• a) one or more repellents selected from the group 3- (Nn-butyl-N-acetyl-amino) propionic acid ethyl ester, N, N-diethyltoluolamide, N, N-diethylbenzamide, 1-piperidinecarboxylic acid 2- (2-hydroxyethyl) -1-methylpropyl ester, 1- (3-cyclohexen-1-yl-carbonyl) -2-methylpiperidine, and
• b) one or more extracts selected from the group Aloe vera extract, Hammamelis extract, sea extract.

Although the describes US 6,300,324 Repellent preparations with aloe vera, but this document could not point the way to the present invention, as in her only mixtures of plant extracts and vitamins are disclosed.

It is advantageous according to the invention, if one or more repellents of group a) in a total concentration from 2 to 60% by weight, preferably at a concentration of 5 to 40% by weight and most preferably in one concentration from 10 to 20% by weight, based in each case on the total weight the preparation contained in the preparation.

Also it is advantageous for the purposes of the present invention, when the inventive preparation characterized characterized in that they contain extracts of group b) in a total concentration from 0.1 to 35% by weight, preferably in a concentration of 0.2 to 15% by weight and most preferably in one concentration from 0.2 to 2.5% by weight, based in each case on the total weight the preparation contains.

When according to the invention preferred Repellents are 3- (N-n-butyl-N-acetylamino) propionic acid ethyl ester and 1-piperidinecarboxylic acid 2- (2-hydroxyethyl) -1-methylpropyl ester used, with 3- (N-n-butyl-N-acetyl-amino) propionate particularly according to the invention is preferred.

According to the invention advantageous embodiments the preparation according to the invention are characterized in that as an extract aloe vera and / or Witch hazel is used.

When Aloe according to the invention Vera extract can be, for example, aloe vera gel from Madi Botanical Inc., Aloe S1020 V from Bioextracto and Aloe Vera Terra from Terry Lab. Inc. (CAS No. 8001-97-6) can be advantageously used.

When Hammamelis extract according to the invention For example, the extract with the CAS number 84696-19-5 can be used advantageously become. Such an extract is for example the company Amerivan Distilling available under the trade name With Hazel (14% Alcohol).

The sea extract according to the invention represents an aqueous extract of mineral salts and trace elements of sea sediments and oyster shells. It is known to the cosmetic specialist under the INCI "Water (and) Propylene Glycol (and) Oyster Extract (and) Sea Silt Extract" and example, under the trade name Oligoceane ^® be purchased at the company Sederma.

Also It has proven to be beneficial for you the invention is pointed out, when in the preparation according to the invention the weight ratio the total amount of repellents [a)] to the total amount of extracts [b)] is from 10: 1 to 50: 1 and preferably from 25: 1 to 50: 1.

In one for the invention advantageous embodiment contains the preparation according to the invention additionally one or more oils chosen from the group iris oil, sandalwood oil, mint oil, Lime oil.

The iris oil according to the invention can, for example under the trade name iris oil (CAS 8002-73-1) are acquired from Symrise.

The sandalwood oil according to the invention can, for example under the trade name sandalwood oil (CAS 8006-87-9) at the company Nature can be purchased.

The Mint oil according to the invention, for example under the trade name Mint oil (CAS 8006-90-4) are acquired from Symrise.

The Lime oil according to the invention can, for example under the trade name lime oil (CAS 8008-26-2) are purchased from the company Nature.

Further it is particularly according to the invention preferably lime oil-containing To use perfume oils.

According to the invention advantageous be one or more oils chosen from the group iris oil, sandalwood oil, mint oil, lime oil in a total concentration of 1 to 10% by weight and preferred in a concentration of 1.5 to 5% by weight, in each case used on the total weight of the preparation.

According to the invention, the preparation according to the invention can advantageously contain one or more further repellents. According to the invention, such further repellents can advantageously be selected from the list of the following compounds:

Further advantageous according to the invention additional Repellents are dimethyl phthalate (Palatinol M, DMP) and emu oil.

One or more of these additional ones Repellents can According to the invention advantageous in a concentration of 1 to 10% by weight, based on the Total weight of the preparation can be used.

The Water phase of the preparation according to the invention can be beneficial usual contain cosmetic excipients, such as alcohols, in particular such low C number, preferably ethanol and / or Isopropanol, diols or polyols of low C number and their ethers, preferably propylene glycol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, Diethylene glycol monomethyl or monoethyl ether and analogous products, Polymers, foam stabilizers, electrolytes, self-tanning agents (e.g. DHA), depigmenting agents and in particular one or more thickeners, which or which can be chosen advantageously from the group silicon dioxide, aluminum silicates, polysaccharides or their derivatives, e.g. hyaluronic acid, Xanthan gum, hydroxypropyl methylcellulose, particularly advantageous from the group of polyacrylates, preferably a polyacrylate from the Group of so-called carbopols, for example carbopols of the types 980, 981, 1382, 2984, 5984, each alone or in combination.

Also advantageous are copolymers of C _10-30 alkyl acrylates and one or more monomers of acrylic acid, methacrylic acid or their esters.

Advantageous compounds are those bearing the INCI name "Acrylates / C _10-30 Alkyl Acrylate Crosspolymer." Particularly advantageous are those available under the trade names Pemulen TR1 and Pemulen TR2 from the BF Goodrich Company.

Advantageous are compounds which have the INCI name Ammoniumacryloyldimethyltaurate / Vinylpyrrolidoncopolymere wear.

According to the invention, the ammoniumacryloyldimethyltaurate / vinylpyrrolidone copolymer (s) has the empirical formula [C ₇ H ₁₆ N ₂ SO ₄ ] _n [C ₆ H ₉ NO] _m , corresponding to a statistical structure as follows

Advantageous species for the purposes of the present invention are listed in Chemical Abstracts under the registry numbers 58374-69-9, 13162-05-5 and 88-12-0 stored and available under the trade name Aristoflex ^® AVC from Clariant GmbH.

Also advantageous are copolymers / crosspolymers comprising Acryloyldimethyl Taurate such as Simugel® ^® EC or EC Simugel® ^® from Seppic SA

Further According to the invention advantageous Thickeners to be used are also soluble in water or dispersible anionic polyurethanes. Advantageous in terms of present invention are e.g. Polyurethane-1 and / or polyurethane-4.

Advantageous polyurethanes for the purposes of the present invention are the types available under the trade name Avalure ^™ UR from BF Goodrich Company, such as Avalure ^™ UR 445, Avalure ^™ UR 450 and the like. Also advantageous for the purposes of the present invention is the polyurethane available under the trade name Luviset Pur from BASF.

Very particular according to the invention preferred are thickeners based on polyacrylates. thickener can according to the invention in one Concentration of 0.05 to 1% by weight and more preferred in a concentration of 0.1 to 0.5% by weight based on the total weight of Preparation can be used.

The inventive preparation is according to the invention as aqueous or aqueous alcoholic Preparation before. It is inventively preferred if the preparation a watery-alcoholic Preparation represents. The preferred mixing ratio of Water to alcohol is 55:45% by weight. As inventively preferred Alcohol is used ethanol.

According to the invention advantageous contains the preparation according to the invention one or more solubilizers. As an advantageous solubilizer all polyethylene glycol-containing compounds come into question. All PPG-1-PEG-9-lauryl glycol ethers (Eumulgin L; Cognis) and polyethylene glycol (40) hydrogenated castor oil (Cremophor RH 40; Fa. BASF).

According to the invention advantageous can also pharmaceutically or dermatologically active substances such as For example, the skin soothing, anti-inflammatory substances incorporated be. Which includes for example, allantoin, tannin, antihistamines, antiphlogistics, Glucocorticoids (e.g., hydrocortisone) as well as plant agents such as Azulene bisabolol, glycyrrhizin, hamamelin and plant extracts such as Chamomile and / or licorice root.

Advantageously according to the invention, the preparation according to the invention may contain one or more antioxidants. Advantageously, the antioxidants are selected from the group consisting of amino acids (eg, giycin, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (eg urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L-carnosine and their derivatives (eg anserine), carotenoids, carotenes (eg α-carotene, β-carotene, lycopene) and their derivatives, lipoic acid and its derivatives (eg dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols (eg thioredoxin, glutathione, cysteine, cystine , Cystamine and its glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-Li noleyl, cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (eg buthionine sulfoximines, homocysteinesulfoximine, buthionine sulfones, penta, hexa). , Heptathioninsulfoximin) in very low tolerated dosages (eg pmol to μmol / kg), furthermore (metal) chelators (eg α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (eg 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 (eg γ-linolenic acid, linoleic acid, oleic acid), folic acid and its derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and derivatives (eg ascorbyl palmitate , Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (eg vitamin E acetate), vitamins A and Derivatives (vitamin A - palmitate) as well as Konyferylbenzoat of Benzoeharzes, Rutinsäure and their derivatives, Ferulasäure and their derivatives, Butylhydroxytoluol, Butylhydroxyanisol, Nordihydroguajakharzsäure, Nordihydroguajaretsäure, Trihydroxybutyrophenon, uric acid and their derivatives, Mannose and their derivatives, zinc and its derivatives (eg ZnO, ZnSO ₄ ) selenium and its derivatives (eg selenium methionine), stilbenes and their derivatives (eg stilbene oxide, trans-stilbene oxide) and the inventively suitable derivatives (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these active substances.

The Amount of antioxidants (one or more compounds) in the Preparations is preferably from 0.001 to 30% by weight, particularly preferably from 0.05 to 20 Wt .-%, in particular 1 to 10 wt .-%, based on the total weight the preparation.

Provided Vitamin E and / or derivatives thereof are the antioxidant (s), is advantageous, their respective concentrations from the field from 0.001 to 10% by weight, based on the total weight of the formulation, to choose.

Provided Vitamin A, or vitamin A derivatives, or carotenes or their derivatives the one or more antioxidants are advantageous, their respective Concentrations from the range of 0.001 to 10 wt .-%, based on the total weight of the formulation to choose.

It is particularly advantageous if the cosmetic and / or dermatological Preparations according to the present invention Contain cosmetic or dermatological active ingredients, preferred agents being antioxidants which are the skin protect against oxidative stress can.

Further advantageous active ingredients in the context of the present invention natural Active ingredients and / or their derivatives, such as. Alpha-lipoic acid, phytoene, D-biotin, coenzyme Q10, alpha-glucosylrutin, carnitine, carnosine, natural and / or synthetic isoflavonoids, creatine, creatinine, taurine and / or β-alanine.

The inventive preparation can be advantageous according to the invention one or more self-tanner contain. As a self-tanner become advantageous according to the invention used inter alia: glycerol aldehyde, hydroxymethylglyoxal, γ-dialdehyde, Erythrulose, 6-aldo-D-fructose, Ninhydrin, 5-hydroxy-1,4-naphthoquinone (juglone), 2-hydroxy-1,4-naphthoquinone (Lawson).

The inventive preparation can be advantageous according to the invention contain one or more depigmenting agents. As inventively advantageous Depigmenting agents can for example, dicarboxylic acids such as 8-hexadecene-1,16-dicarboxylic acid (Dioic acid, CAS number 20701-68-2), kojic acid, ascorbic acid and azelaic acid and their derivatives are used.

The inventive preparation can be advantageous according to the invention one or more UV sunscreen filters contain. As inventively advantageous UV sunscreen filters can For example, the following compounds are used:

Inorganic pigments

Preferred inorganic pigments are metal oxides and / or other water-insoluble or insoluble metal compounds, in particular oxides of titanium (TiO ₂ ), zinc (ZnO), iron (eg Fe ₂ O ₃ ), zirconium (ZrO ₂ ), silicon (SiO ₂ ) , Manganese (eg MnO), aluminum (Al ₂ O ₃ ), cerium (eg Ce ₂ O ₃ ), mixed oxides of the corresponding metals and mixtures of such oxides, as well as the barium sulfate (BaSO ₄ ).

The titanium dioxide pigments can be present in both the rutile and anatase crystal modification and For the purposes of the present invention, they may advantageously be surface-treated ("coated"), in which case a hydrophilic, amphiphilic or hydrophobic character is to be formed or retained, for example hydrophilic and / or hydrophobic inorganic and / or organic layer.The various surface coating can also contain water for the purposes of the present invention.

described Coated and uncoated titanium dioxides may be used in the context of the present invention Invention also in the form of commercially available oily or aqueous Predispersions are used. These predispersions can be beneficial Dispersing aids and / or solubilization promoters added be.

The Titanium dioxides according to the invention are characterized by a primary particle size between 10 nm to 150 nm.

in the The meaning of the present invention are particularly preferred titanium dioxides the MT-100 Z and MT-100 TV from Tayca Corporation, Eusolex T-2000 and Eusolex TS from Merck and the titanium dioxide T 805 from Degussa.

For the purposes of the present invention, zinc oxides may also be used in the form of commercially available oily or aqueous predispersions. According to the invention suitable zinc oxide particles and Predispersions of zinc oxide particles are characterized by a primary particle size of <300 nm and are available from the following companies under the following trade names:

special Preferred zinc oxides in the context of the invention are the Z-Cote HP1 from BASF and the zinc oxide NDM from Haarmann & Reimer.

The Total amount of one or more inorganic pigments in the Finished cosmetic preparation will be beneficial in the field 0.1% by weight to 25% by weight, preferably 0.5% to 18% by weight.

Organic pigments

Advantageous organic pigment in the context of the present invention is the 2,2'-methylenebis (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) -phenol) [INCI :, which is available under the trade name Tinosorb ^® M from CIBA-Chemikalien GmbH Bisoctyltriazol].

Further UV sunscreen filters

Advantageous UV-A filter substances for the purposes of the present invention are dibenzoylmethane derivatives, in particular 4- (tert-butyl) -4'-methoxydibenzoylmethane (CAS-Nr. 70356-09-1), marketed by Givaudan under the trade name Parsol ^® 1789 and is sold by Merck under the trade name Eusolex ^® 9020th

Further advantageous UV-A filter substances are the phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and their salts, especially the corresponding sodium, potassium or Triethanolammonium salts, in particular the phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid bis-sodium salt with the INCI name Bisimidazylate, which, for example, under the Trade name Neo Heliopan AP available from Haarmann & Reimer.

Further advantageous are 1,4-di (2-oxo-10-sulfo-3-bornylidenemethyl) benzene and its salts (especially the corresponding 10-sulfato compounds, in particular the corresponding sodium, potassium or triethanolammonium salt), also referred to as benzene-1,4-di (2-oxo-3-bomylidenemethyl-10-sulfonic acid) becomes.

worin

• • R¹ und R² unabhängig voneinander Wasserstoff, C₁-C₂₀-Alkyl, C₃-C₁₀-Cycloalkyl oder C₃-C₁₀-Cycloalkenyl bedeuten, wobei die Substituenten R¹ und R² gemeinsam mit dem Stickstoffatom, an das sie gebunden sind, einen 5- oder 6-Ring bilden können und
• • R³ einen C₁-C₂₀-Alkyl Rest bedeutet.

Further advantageous UV-A filter substances are hydroxybenzophenones, which are distinguished by the following structural formula:

wherein

• • R ¹ and R ² independently of one another are hydrogen, C ₁ -C ₂₀ -alkyl, C ₃ -C ₁₀ -cycloalkyl or C ₃ -C ₁₀ -cycloalkenyl, where the substituents R ¹ and R ² together with the nitrogen atom to which they are bound to form a 5- or 6-ring and
• • R ^{3 is} a C ₁ -C ₂₀ -alkyl radical.

A particularly advantageous hydroxybenzophenone in the context of the present invention is the 2- (4'-diethylamino-2'-hydroxybenzoyl) -benzoesäurehexylester (also: aminobenzophenone), which is available under the trade name Uvinul A Plus from BASF. Advantageous UV filter substances for the purposes of the present invention are also so-called broadband filters, ie filter substances which absorb both UV-A and UV-B radiation.

wobei R¹, R² und R³ unabhängig voneinander gewählt werden aus der Gruppe der verzweigten und unverzweigten Alkylgruppen mit 1 bis 10 Kohlenstoffatomen bzw. ein einzelnes Wasserstoffatom darstellen. Insbesondere bevorzugt sind das 2,4-Bis-{[4-(2-Ethyl-hexyloxy)- 2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazin (INCI: Aniso Triazin), welches unter der Handelsbezeichnung Tinosorb^® S bei der CIBA-Chemikalien GmbH erhältlich ist.Advantageous broadband filters or UV-B filter substances are, for example, bis-resorcinyl triazine derivatives having the following structure:

wherein 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 represent a single hydrogen atom. Particularly preferred are 2,4-bis - {[4- (2-ethyl-hexyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine (INCI: aniso triazine , which is available under the trade name Tinosorb ^® S from CIBA-Chemikalien GmbH).

Especially advantageous preparations according to the present invention, which are characterized by a high or very high UV-A protection, contain preferably several UV-A and / or broadband filters, especially dibenzoylmethane derivatives [e.g. 4- (tert-butyl) -4'-methoxydibenzoylmethane], Benzotriazole derivatives [for example, the 2,2'-methylenebis (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol)], Phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and / or their salts, the 1,4-di (2-oxo-10-sulfo-3-bomylidenemethyl) benzene and / or its Salts and / or the 2,4-bis - {[4- (2-ethyl-hexyl-oxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine, each individually or in any combination with each other.

aufweisen, sind vorteilhafte UV-Filtersubstanzen im Sinne der vorliegenden Erfindung, beispielsweise die in der Europäischen Offenlegungsschrift EP 570 838 A1 beschriebenen s-Triazinderivate, deren chemische Struktur durch die generische Formel

wiedergegeben wird, wobei
R einen verzweigten oder unverzweigten C₁-C₁₈-Alkylrest, einen C₅-C₁₂-Cycloalkylrest, gegebenenfalls substituiert mit einer oder mehreren C₁-C₄- Alkylgruppen, darstellt,
X ein Sauerstoffatom oder eine NH-Gruppe darstellt,
R₁ einen verzweigten oder unverzweigten C₁-C₁₈-Alkylrest, einen C₅-C₁₂-Cycloalkylrest, gegebenenfalls substituiert mit einer oder mehreren C₁-C₄- Alkylgruppen, oder ein Wasserstoffatom, ein Alkalimetallatom, eine Ammoniumgruppe oder eine Gruppe der Formel

bedeutet, in welcher
A einen verzweigten oder unverzweigten C₁-C₁₈-Alkylrest, einen C₅-C₁₂-Cycloalkyl- oder Arylrest darstellt, gegebenenfalls substituiert mit einer oder mehreren C₁-C₄-Alkylgruppen,
R₃ ein Wasserstoffatom oder eine Methylgruppe darstellt,
n eine Zahl von 1 bis 10 darstellt,
R₂ einen verzweigten oder unverzweigten C₁-C₁₈-Alkylrest, einen C₅-C₁₂-Cycloalkylrest, gegebenenfalls substituiert mit einer oder mehreren C₁-C₄- Alkylgruppen, darstellt, wenn X die NH-Gruppe darstellt, und
einen verzweigten oder unverzweigten C₁-C₁₈-Alkylrest, einen C₅-C₁₂-Cycloalkylrest, gegebenenfalls substituiert mit einer oder mehreren C₁-C₄- Alkylgruppen, oder ein Wasserstoffatom, ein Alkalimetallatom, eine Ammoniumgruppe oder eine Gruppe der Formel

bedeutet, in welcher
A einen verzweigten oder unverzweigten C₁-C₁₈-Alkylrest, einen C₅-C₁₂-Cycloalkyl- oder Arylrest darstellt, gegebenenfalls substituiert mit einer oder mehreren C₁C₄-Alkylgruppen,
R₃ ein Wasserstoffatom oder eine Methylgruppe darstellt,
n eine Zahl von 1 bis 10 darstellt,
wenn X ein Sauerstoffatom darstellt.Other UV filter substances, which are the structural motif

have advantageous UV filter substances in the sense of the present invention, for example, those in the European published patent application EP 570 838 A1 described s-triazine derivatives, their chemical structure by the generic formula

is reproduced, wherein
R is a branched or unbranched C ₁ -C ₁₈ -alkyl radical, a C ₅ -C ₁₂ -cycloalkyl radical, optionally substituted by one or more C ₁ -C ₄ -alkyl groups,
X represents an oxygen atom or an NH group,
R _{1 is} a branched or unbranched C ₁ -C ₁₈ -alkyl radical, a C ₅ -C ₁₂ -cycloalkyl radical, optionally substituted by one or more C ₁ -C ₄ -alkyl groups, or a hydrogen atom, an alkali metal atom, an ammonium group or a group of formula

means in which
A is a branched or unbranched C ₁ -C ₁₈ -alkyl radical, a C ₅ -C ₁₂ -cycloalkyl or aryl radical, optionally substituted by one or more C ₁ -C ₄ -alkyl groups,
R _{3 represents} a hydrogen atom or a methyl group,
n represents a number from 1 to 10,
R _{2 is} a branched or unbranched C ₁ -C ₁₈ alkyl radical, a C ₅ -C ₁₂ cycloalkyl radical optionally substituted with one or more C ₁ -C ₄ alkyl groups, when X represents the NH group, and
a branched or unbranched C ₁ -C ₁₈ alkyl radical, a C ₅ -C ₁₂ cycloalkyl radical optionally substituted with one or more C ₁ -C ₄ alkyl groups, or a hydrogen atom, an alkali metal atom, an ammonium group or a group of the formula

means in which
A is a branched or unbranched C ₁ -C ₁₈ -alkyl radical, a C ₅ -C ₁₂ -cycloalkyl or aryl radical, optionally substituted by one or more C ₁ C 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.

wiedergegeben wird, welches im Folgenden auch als Dioctylbutylamidotriazon (INCI: Dioctylbutamidotriazone) bezeichnet wird und unter der Handelsbezeichnung UVASORB HEB bei Sigma 3V erhältlich ist.Particularly preferred UV filter substance in the context of the present invention is also an unsymmetrically substituted s-triazine whose chemical structure is represented by the formula

which is also referred to below as Dioctylbutylamidotriazon (INCI: Dioctylbutamidotriazone) and is available under the trade name UVASORB HEB in Sigma 3V.

Also advantageous in the context of the present invention is a symmetrically substituted s-triazine which comprises 4,4 ', 4 "- (1,3,5-triazine-2,4,6-triyltrimino) -tris-benzoic acid tris (2 ethylhexyl ester), synonym: 2,4,6-tris [anilino- (p-carbo-2'-ethyl-1'-hexyloxy)] - 1,3,5-triazine (INCI: octyl triazone), which was obtained from BASF Aktiengesellschaft under the trade name Uvinul ^® T is marketed 150th

wiedergegeben wird, wobei R₁, R₂ und A₁ verschiedenste organische Reste repräsentieren.Also in the European patent application 775,698 preferred bis-Resorcinyltriazinderivate be described whose chemical structure by the generic formula

is reproduced, wherein R ₁ , R ₂ and A _{1 represent a} variety of organic radicals.

Advantageous For the purposes of the present invention are also the 2,4-bis - {[4- (3-sulfonato) -2-hydroxy-propyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3 , triazine-5 Sodium salt containing 2,4-bis - {[4- (3- (2-propyloxy) -2-hydroxy-propyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1,3,5 triazine, the 2,4-bis - {[4- (2-ethyl-hexyloxy) -2-hydroxy] phenyl} -6- [4- (2-methoxyethylcarboxyl) phenylamino] -1,3,5-triazine, 2,4-bis - {[4- (3- (2-propyloxy) -2-hydroxy-propyloxy) -2-hydroxy] -phenyl} -6- [4- (2-ethylcarboxyl) -phenylamino] 1,3,5-triazine, 2,4-bis - {[4- (2-ethyl-hexyloxy) -2-hydroxy] -phenyl} -6- (1-methylpyrrol-2-yl) -1,3,5-triazine 2,4-bis - {[4-tris (trimethylsiloxy-silylpropyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine, 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-triazine.

An advantageous broadband filter in the context of the present invention is 2,2'-methylenebis (6- (2N-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) -phenol), which available under the trade name Tinosorb ^® M from CIBA-Chemikalien GmbH.

Advantageous broadband filter according to the present invention is further the 2- (2H-benzotriazol-2-yl) -4-methyl-6- [2-methyl-3- [1,3,3,3-tetramethyl-1 - [( trimethylsilyl) oxy] disiloxanyl] propyl] phenol (CAS No .: 155633-54-8) with the INCI name Drometrizole Trisiloxane.

• • 3-Benzylidencampher-Derivate, vorzugsweise 3-(4-Methylbenzyliden)campher, 3-Benzylidencampher;
• • 4-Aminobenzoesäure-Derivate, vorzugsweise 4-(Dimethylamino)-benzoesäure(2-ethylhexyl)ester, 4-(Dimethylamino)benzoesäureamylester;
• • 2,4,6-Trianilino-(p-carbo-2'-ethyl-1'-hexyloxy)-1,3,5-triazin;
• • Ester der Benzalmalonsäure, vorzugsweise 4-Methoxybenzalmalonsäuredi(2-ethylhexyl)-ester;
• • Ester der Zimtsäure, vorzugsweise 4-Methoxyzimtsäure(2-ethylhexyl)ester, 4-Methoxyzimtsäureisopentylester;
• • Derivate des Benzophenons, vorzugsweise 2-Hydroxy-4-methoxybenzophenon, 2-Hydroxy-4-methoxy-4'-methylbenzophenon, 2,2'-Dihydroxy-4-methoxybenzophenon
• • sowie an Polymere gebundene UV-Filter.

The UV-B and / or broadband filters may be oil-soluble or water-soluble. Advantageous oil-soluble UV-B and / or broadband filter substances are, for example:

• 3-benzylidene camphor derivatives, preferably 3- (4-methylbenzylidene) camphor, 3-benzylidene camphor;
• 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 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-bound polymers.

• • Salze der 2-Phenylbenzimidazol-5-sulfonsäure, wie ihr Natrium-, Kalium- oder ihr Triethanolammonium-Salz, sowie die Sulfonsäure selbst;
• • Sulfonsäure-Derivate des 3-Benzylidencamphers, wie z.B. 4-(2-Oxo-3-bomylidenmethyl)benzolsulfonsäure, 2-Methyl-5-(2-oxo-3-bornylidenmethyl)sulfonsäure und deren Salze.

Advantageous water-soluble UV-B and / or broadband filter substances are, for example:

• Salts of 2-phenylbenzimidazole-5-sulphonic acid, such as its sodium, potassium or triethanolammonium salt, and the sulphonic acid itself;
• Sulfonic acid derivatives of 3-Benzylidencamphers, such as 4- (2-oxo-3-bomylidenmethyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bomylidenemethyl) sulfonic acid and salts thereof.

Particularly advantageous UV filter substances which are liquid at room temperature for the purposes of the present invention are homomenthyl salicylate (INCI: homosalates), 2-ethylhexyl 2-hydroxybenzoate (2-ethylhexyl salicylate, octyl salicylate, INCI: octyl salicylates), 4-isopropylbenzyl salicylate and esters of tin- nic acid, preferably 4-Methoxycinnamate (2-ethylhexyl) ester (2-ethylhexyl-4-methoxycinnamate, INCI: octyl methoxycinnamate) and 4-methoxycinnamic acid isopentyl ester (isopentyl 4-methoxycinnamate, INCI: isoamyl p-methoxycinnamate), 3- (4- (2, 2-bis ethoxycarbonylvinyl) phenoxy) propenyl) -methoxysiloxan / dimethylsiloxane - copolymer (INCI: dimethicodiethylbenzalmalonate) which is, for example, under the trade name Parsol ^® SLX available from Hoffmann La Roche.

A further light protection filter substance according to the invention to be used advantageously is ethylhexyl-2-cyano-3,3-diphenylacrylate, obtainable (octocrylene) from BASF under the name Uvinul ^® N 539th

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

The List of said UV filters, for the purposes of the present invention can be used Of course not limiting.

Advantageous contain the preparations according to the invention the substances that UV radiation in the UV-A and / or UV-B range absorb, in a total amount of e.g. 0.1% by weight to 30% by weight, preferably 0.5 to 20% by weight, in particular 1.0 to 15.0% by weight, each based on the total weight of the preparations to cosmetic Preparations available to put the hair or the skin in front of the entire area protect the ultraviolet radiation. You can also as a sunscreen for Hair or the skin serve.

According to the invention, the preparation according to the invention can advantageously contain moisturizing or moistening agents. Advantageous moistening or moisturizing agents (so-called moisturizers) for the purposes of the present invention are, for example, glycerol, lactic acid and / or lactates, in particular sodium lactate, butylene glycol, propylene glycol, biosaccharide gum-1, glycine soya, ethylhexyloxyglycerol, pyrrolidonecarboxylic acid and urea. Furthermore, it is particularly advantageous to use polymeric moisturizers from the group of water-soluble and / or water-swellable and / or water-gellable polysaccharides. Are particularly advantageous, for example, hyaluronic acid, chitosan and / or a fucose-rich polysaccharide, which is filed in Chemical Abstracts under the registry number 178463-23-5 and is available, for example from SOLABIA SA under the name ^® Fucogel 1000th

The cosmetic preparations according to the invention may contain cosmetic adjuvants such as are conventionally used in such preparations, for example antioxidants, preservatives, par foams, antimicrobial agents, antifoaming agents, dyes, pigments which have a coloring effect, self-tanning agents, bleaching agents, thickeners, surface-active substances, emulsifiers, softening substances, moisturizing and / or moisturizing substances, fats, oils, waxes or other common ingredients of a cosmetic formulation such as alcohols, polyols, polymers, foam stabilizers, electrolytes, organic solvents or silicone derivatives.

Erfindungsgmäß is the Use of one or more extracts selected from the group Aloe vera, Hammamelis, sea extract for the stabilization of ethyl 3- (N-n-butyl-N-acetylamino) propionate in aqueous or aqueous-alcoholic Preparations.

The cosmetic according to the invention and / or dermatological preparations may be composed as usual and to protect the skin and / or hair from nuisance by blood sucking or biting Insects and other parasites are used. But you can also primarily for protection the skin from UV radiation and / or skin aging or as skin care products for skin moisturizing, skin care after sunbathing (so-called after-sun or apres-sun products) can be advantageously used according to the invention.

According to the invention Use of the preparation according to the invention insect repelling agent (insect repelling cosmetic).

According to the invention Use of the preparation according to the invention as an after sun, sunscreen anti-wrinkle, anti-acne preparation or as a moisturizing preparation, day or night cream.

to Application are the cosmetic and / or dermatological according to the invention Formulations in the for Cosmetics and dermatological usual Applied to the skin and / or hair in sufficient quantity.

According to the invention advantageous is the preparation of the invention in a storage vessel (e.g. a plastic bottle) and used out of this. According to the invention advantageous can the preparation of the invention but also in the form of a pump spray or aerosol spray, being all commercial Product forms are advantageously applicable.

Therefore is the use of the preparation according to the invention as a sprayable preparation in a spray according to the invention.

The inventive preparation but can also be advantageous according to the invention with the help of an insoluble Substrates (e.g., paper, cloth, cotton ball, "pad") are applied to the body are non-woven textiles (especially fleeces made from viscose fibers and polyester and optionally cotton fibers) are preferred according to the invention. In a preferred according to the invention embodiment The present invention is already the consumer pre-soaked with the preparation Textiles offered.

Therefore is the use of the preparation according to the invention as impregnation for a textile according to the invention.

Comparative test

The surprising effect of the present invention could be demonstrated inter alia with the following comparative experiment:
In each case, 300-400 mosquitoes of the aedes aegypti type (males and females) in a cubic cage (30 × 30 × 30 cm) were used for the tests. To make sure the mosquitoes were "hungry" when they ran the test, they did not receive any more sugar than food from the eve of the test The tests were run the following day between 8 and 11 am The tests were performed under standard conditions (27 ° C, 70% -80% relative humidity) performed.

The tests were performed on 4 subjects (2 males, 2 females who volunteered). For this purpose, 2 ml of test substance were distributed on an area of 500 cm ² on their forearms. The test substance used was a preparation (A) according to the invention and a preparation (B) which differed from the preparation according to the invention in that it contained no extracts selected from the group Aloe vera extract, Hammamelis extract, sea extract. The hand of the test person became protected by a glove, the upper arm with a plastic cuff protected from mosquitoes.

• a) Bereitschaft zum Stechen (Positiv-Kontrolle)
• b) Annäherung an die behandelte Hautfläche auf einen Abstand von weniger als 3 cm
• c) Niederlassen auf der behandelten Hautfläche über einen Zeitraum von mehr als 2 Sekunden.

To carry out the test, the prepared forearm of the subject was held in the mosquito cage for a test period of 10 minutes, in such a way that only the skin area treated with the preparation was accessible to the mosquitoes. For the test period, which was carried out at intervals of one and three hours, the number of mosquitoes was recorded which had the following behavior:

• a) readiness for stinging (positive control)
• b) approach the treated skin area to a distance of less than 3 cm
• c) settling on the treated skin area for a period of more than 2 seconds.

When Control measurements also included the untreated forearms of subjects measure. The values were rounded to a gnat.

Type of application: spray

Type of application: with the help of a cloth

In These tests have shown that the addition of extracts for example, to halve the mosquito attacks led.

The The following examples are intended to illustrate the compositions according to the invention, without but it is intended that the invention be accorded these examples restrict. The numerical values in the examples mean percentages by weight on the total weight of the respective preparations.

Examples

Pump spray with repellent

Pump spray with repellent

Spray with repellent

O / W emulsion with repellent

Claims (10)

aqueous or aqueous-alcoholic cosmetic preparation containing a combination of a) one or more repellents selected from the group 3- (N-n-butyl-N-acetylamino) propionic acid ethyl ester, N, N-diethyltoluolamide, N, N-diethylbenzamide, 1-piperidinecarboxylic acid 2- (2-hydroxyethyl) -1-niethylpropyl ester, 1- (3-cyclohexen-1-yl-carbonyl) -2-methylpiperidine and b) one or more extracts selected from the group aloe vera extract, Hammamelis extract, sea extract. Preparation according to claim 1, characterized in that that they contain one or more repellents of group a) in a total concentration from 2 to 60% by weight, based on the total weight of the preparation, contains. Preparation according to one of claims 1 or 2, characterized that they contain extracts of group b) in a total concentration of 0.1 to 35% by weight, based on the total weight of the preparation, contains. Preparation according to one of claims 1 to 3, characterized that as a repellent 3- (N-n-butyl-N-acetyl-amino) propionate is used. Preparation according to one of claims 1 to 4, characterized that in addition one or more oils chosen from the group iris oil, sandalwood oil, mint oil, lime oil contains. Preparation according to one of claims 1 to 5, characterized that Aloe Vera and Hammamelis are used as extract. Preparation according to one of claims 1 to 6, characterized that the weight ratio of Total amount of repellents [a)] to the total amount of extracts [b)] from 10: 1 to 50: 1. Use of a preparation according to one of the preceding claims as an insect repelling cosmetic. Use of a preparation according to one of the preceding claims as a sprayable preparation in a pump-spray, aerosol spray or as impregnation for a textile. Use of one or more extracts selected from the group aloe vera extract, Hammamelis extract, sea extract for the stabilization of ethyl 3- (N-n-butyl-N-acetylamino) propionate in aqueous or aqueous-alcoholic Preparations.