DE202012013357U1 - preparations - Google Patents

Abstract

Preparations containing (a) 2- (p-tolyloxy) -N- (1H-pyrazol-5-yl) -N - ((thiophen-2-yl) -methyl) -acetamides corresponding to the following formula (I) and salts thereof, and (b1) menthol and / or menthol compounds of the formulas (II), (III) and / or (IV) in which X is -OY or -COZ and Y is the following groups: (i) a linear or branched alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms or an allyl radical; (ii) a hydroxy or dihydroxyalkyl radical having 1 to 6 carbon atoms; (iii) a radical -OCR1; (iv) a residue -OCO (M) OH; (v) a residue -OCO-S; (vi) a radical -OC (CH 2) n COR 2 wherein M is a linear or branched alkyl and / or alkenyl radical having 1 to 10 carbon atoms; S is a carbohydrate moiety having from 5 to 12 carbon atoms; n is 0 or numbers from 1 to 6; R1 is a linear or branched alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms or an allyl radical; R2 represents a hydroxyl radical or a radical NR3R4; R3 and R4 independently of one another represent hydrogen or a linear or branched alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, while Z represents the following groups: (vii) a radical NR5R6 or (viii) a radical NHR7 where R5 and R6 independently of one another is hydrogen or a linear or branched alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, a phenyl radical or an alkoxyphenyl radical having 1 to 6 carbon atoms in the alkoxy radical R7 is a radical - (CH 2) n COOR 8 R 8 is a linear or branched alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms and n is 0 or numbers from 1 to 10 or (b2) flavorings.

Description

FIELD OF THE INVENTION

The invention is in the fields of cosmetics, pharmacy and foodstuffs and relates to preparations having a cooling effect on the skin or mucous membrane containing menthol compounds or flavoring agents together with selected amides.

STATE OF THE ART

Although menthol has been known as a cooling substance for many decades and is still indispensable in a variety of applications today, it has a number of disadvantages: it is volatile, has a strong odor and a bitter taste. In higher concentrations it is no longer perceived as pleasantly cooling, but as stinging and burning. After all, menthol can not be formulated arbitrarily because it can interact with other chemical components. This has led to the development of a wide variety of menthol compounds, a number of which have better taste characteristics.

From the international patent application WO 2012 061698 A2 (Senomyx) complex amides are known, which can be used as TRPM8 modulators (= Transient Receptor Potential Channel Melastin Member 8). These are substances that are able to trigger hot or cold sensations on the skin or mucosa. These fabrics are especially recommended for use in food and personal care products.

Despite the progress made in recent years and the development of more and more effective terpene-based refrigerants, there is still a need in the cosmetics and food sectors for refrigerants or synergistic mixtures of refrigerants which have improved sensory properties and ease of formulation, performance properties influence the end products advantageous and in particular cause a subjectively same strong effect on the skin or mucosa despite lower use concentrations.

The object of the present invention has therefore been to provide preparations of the type described above.

DESCRIPTION OF THE INVENTION

• (a) 2-(p-tolyloxy)-N-(1H-pyrazol-5-yl)-N-((thiophen-2-yl)methyl)acetamide entsprechend der folgenden Formel (I)
  
  sowie deren Salze, und
• (b1) Menthol und/oder Mentholverbindungen der Formeln (II), (III) und/oder (IV)
  
  in der X für -OY oder -COZ und Y für die folgenden Gruppen steht: (i) einen linearen oder verzweigten Alkyl- oder Hydroxyalkylrest mit 1 bis 6 Kohlenstoffatomen oder einen Allylrest; (ii) einen Hydroxy- oder Dihydroxyalkylrest mit 1 bis 6 Kohlenstoffatomen; (iii) einen Rest -OCR¹; (iv) einen Rest -OCO(M)OH; (v) einen Rest -CO-S (vi) einen Rest -OC(CH₂)_nCOR² wobei M für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 1 bis 10, vorzugsweise 1 bis 4 Kohlenstoffatomen; S für einen Kohlenhydratrest mit 5 bis 12 Kohlenstoffatomen, vorzugsweise einen Fructose-, Glucose oder Sucroserest; n für 0 oder Zahlen von 1 bis 6, vorzugsweise 2 bis 3; R¹ für einen linearen oder verzweigten Alkyl- oder Hydroxyalkylrest mit 1 bis 6, vorzugsweise 1 bis 2 Kohlenstoffatomen oder einen Allylrest; R² für einen Hydroxylrest oder einen Rest -NR³R⁴; R³ und R⁴ unabhängig voneinander für Wasserstoff oder einen linearen oder verzweigten Alkyl- oder Hydroxyalkylrest mit 1 bis 6, vorzugsweise 1 bis 2 Kohlenstoffatomen stehen, während Z für die folgenden Gruppen steht: (vii) einen Rest NR⁵R⁶ oder (viii) einen Rest NHR⁷ wobei R⁵ und R⁶ unabhängig voneinander für Wasserstoff oder einen linearen oder verzweigten Alkyl- oder Hydroxyalkylrest mit 1 bis 6, vorzugsweise 1 bis 2 Kohlenstoffatomen, einen Phenylrest oder einen Alkoxyphenylrest mit 1 bis 6, vorzugsweise 1 bis 2 Kohlenstoffatomen im Alkoxyrest; R⁷ für einen Rest -(CH₂)_nCOOR⁸; R⁸ für einen linearen oder verzweigten Alkyl- oder Hydroxyalkylrest mit 1 bis 6, vorzugsweise 1 bis 2 Kohlenstoffatomen und n für 0 oder Zahlen von 1 bis 10, vorzugsweise 1 bis 4 steht oder
• (b2) Aromastoffe.

A first subject of the invention relates to preparations with a cooling effect, containing

• (a) 2- (p-tolyloxy) -N- (1H-pyrazol-5-yl) -N - ((thiophen-2-yl) methyl) acetamide represented by the following formula (I)
  
  and their salts, and
• (b1) menthol and / or menthol compounds of the formulas (II), (III) and / or (IV)
  
  in which X represents -OY or -COZ and Y represents the following groups: (i) a linear or branched alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms or an allyl radical; (ii) a hydroxy or dihydroxyalkyl radical having 1 to 6 carbon atoms; (iii) a residue -OCR ¹ ; (iv) a residue -OCO (M) OH; (v) a radical -CO-S (vi) a radical -OC (CH ₂ ) _n COR ² where M is a linear or branched alkyl and / or alkenyl radical having 1 to 10, preferably 1 to 4, carbon atoms; S is a carbohydrate radical having from 5 to 12 carbon atoms, preferably a fructose, glucose or sucrose radical; n is 0 or numbers from 1 to 6, preferably 2 to 3; R ^{1 is} a linear or branched alkyl or hydroxyalkyl radical having 1 to 6, preferably 1 to 2 carbon atoms or an allyl radical; R ^{2 is} a hydroxyl radical or a radical -NR ³ R ⁴ ; R ³ and R ⁴ independently of one another represent hydrogen or a linear or branched alkyl or hydroxyalkyl radical having 1 to 6, preferably 1 to 2, carbon atoms, while Z represents the following groups: (vii) a radical NR ⁵ R ⁶ or (viii ) a radical NHR ⁷ wherein R ⁵ and R ^{6 are} independently hydrogen or a linear or branched alkyl or hydroxyalkyl radical having 1 to 6, preferably 1 to 2 carbon atoms, a phenyl radical or an alkoxyphenyl radical having 1 to 6, preferably 1 to 2 carbon atoms in the alkoxy radical; R ^{7 is} a radical - (CH ₂ ) _n COOR ⁸ ; R ^{8 is} a linear or branched alkyl or hydroxyalkyl radical having 1 to 6, preferably 1 to 2 carbon atoms and n is 0 or numbers from 1 to 10, preferably 1 to 4 or
• (b2) flavorings.

Surprisingly, it has been found that mixtures of the specific amide and menthol or menthol compounds of the type described not only bring about a synergistic enhancement of the cooling effect, but are also assessed better by the consumer in terms of taste. The same applies to the combination with a variety of flavorings.

In addition, when investigating the sensory properties of oral and dental care products, it has been found that blends of the specific amides and menthol or menthol compounds synergistically reduce the solubility of hydroxyapatite and inhibit crystal growth, such that such preparations also counter demineralization of the enamel and prevent the formation of tartar.

amide component

The specific amide of formula (I) is registered as FEMA 4809 and known in the art.

MENTHOL AND MENTHOLN COMPOUNDS

1

FEMA steht für „Flavor and Extracts Manufacturers Association” und GRAS ist definiert als „Generally Regarded As Safe”. Eine FEMA GRAS Bezeichnung bedeutet, dass die so gekennzeichnete Substanz nach Standardmethode getestet und für toxikologisch unbedenklich erachtet wird.

3807), Menthone Glyceryl Ketal (FEMA GRAS 3808), Menthyl Lactate (FEMA GRAS 3748), Menthol Ethylene Glycol Carbonate (FEMA GRAS 3805), Menthol Propylene Glycol Carbonate (FEMA GRAS 3806), Menthyl-N-ethyloxamat, Monomethyl Succinate (FEMA GRAS 3810), Monomenthyl Glutamate (FEMA GRAS 4006), Menthoxy-1,2-propanediol (FEMA GRAS 3784), Menthoxy-2-methyl-1,2-propandiol (FEMA GRAS 3849) sowie den Menthancarbonsäureestern und -amiden WS-3, WS-4, WS-5, WS-12, WS-14 und WS-30 sowie deren Gemischen.Menthol compounds which can be used in the context of the invention and form the group (b1) are - in addition to the main body menthol itself - for example selected from the group formed by menthol methyl ether, menthone glyceryl acetal (FEMA GRAS 1

1

FEMA stands for "Flavor and Extracts Manufacturers Association" and GRAS is defined as "Generally Regarded As Safe". A FEMA GRAS designation means that the substance identified in this way is tested according to the standard method and considered to be toxicologically harmless.

No. 3,807), menthone glyceryl ketal (FEMA GRAS 3808), menthyl lactate (FEMA GRAS 3748), menthol ethylene glycol carbonate (FEMA GRAS 3805), menthol propylene glycol carbonate (FEMA GRAS 3806), menthyl-N-ethyloxamate, monomethyl succinate (FEMA GRAS 3810), monomenthyl glutamate (FEMA GRAS 4006), menthoxy-1,2-propanediol (FEMA GRAS 3784), menthoxy-2-methyl-1,2-propanediol (FEMA GRAS 3849) and the menthane carboxylic acid esters and amides WS-3 , WS-4, WS-5, WS-12, WS-14 and WS-30 and their mixtures.

A first important representative of the substances constituting component (b) is the Monomenthyl Succinate (FEMA GRAS 3810), which was already used as a substance in 1963 by Brown & Williamson Tobacco Corp. been patented ( US 3,111,127 ) and as a coolant subject of the property rights US 5,725,865 and 5,843,466 (V. Mane Fils) is. Both the succinate and the analogous monomenthyl glutarate (FEMA GRAS 4006) are important representatives of monomenthyl esters based on di- and polycarboxylic acids:

Examples of applications of these substances can be found for example in the publications WO 2003 043431 (Unilever) or EP 1332772 A1 (IFF).

The next major group of the purposes of the invention, preferred menthol compounds comprising carbonate ester of menthol and polyols, such as glycols, glycerol, or carbohydrates, such as menthol ethylene glycol carbonate (FEMA GRAS 3805 = Frescolat ^® MGC), menthol propylene glycol carbonate (FEMA GRAS 3784 = Frescolat ^® MPC), menthol 2-methyl-1,2-propanediol carbonates (FEMA GRAS 3849) or the corresponding sugar derivatives:

The use of such substances as a coolant for cigarettes is for example the subject of the document US 3,419,543 (Mold et al.) Of 1968; the application as a physiological coolant is in DE 4226043 A1 (H & R) claims.

For the purposes of the invention, preferably, the menthol compounds Menthyl Lactate (FEMA GRAS 3748 = Frescolat ^® ML) and in particular the Menthone glyceryl acetal (FEMA GRAS 3807) or Menthone glyceryl ketal (FEMA GRAS 3808), which is marketed under the name Frescolat ^® MGA are ,

The former structure is obtained by esterification of lactic acid with menthol, the latter by acetalization of menthone with glycerol (cf. DE 2608226 A1 , MR). Also included in this group of compounds is 3- (1-menthoxy) -1,2, propanediol, also known as Cooling Agent 10 (FEMA GRAS 3784, cf. US 6,328,982 , TIC), and the 3- (1-menthoxy) -2-methyl-1,2-propanediol (FEMA GRAS 3849), which has an additional methyl group.

The preparation of 3- (l-menthoxy) -1,2, propanediol takes place, for example, starting from menthol according to the following scheme (see. US 4,459,425 , Takagaso):

Alternative routes in which menthol is reacted with epichlorohydrin in the first stage is called in US 6,407,293 and US 6,515,188 (Takagaso). The following is an overview of the preferred menthol compounds that are characterized by a CO bond:

Very particularly advantageous in these materials menthones glyceryl acetal / ketal and the Menthyl Lactate and Menthol Ethylene Glycol carbonates or menthol Propylene Glycol Carbonatw have proven that the Applicant under the names Frescolat ^® MGA, Frescolat ^® ML, Frecolat ^® MGC and Frescolat ^® MPC sells.

In the 1970s, menthol compounds were first developed which have a C-C bond in the 3-position and of which a number of representatives in accordance with the invention can also be used. These substances are generally referred to as WS types. Base is a menthol derivative in which the hydroxyl is replaced by a carboxyl group (WS-1). All other WS types are derived from this structure, such as, for example, the preferred species WS-3, WS-4, WS-5, WS-12, WS-14 and WS-30. The two following graphs show the synthetic routes:

The esters derived from WS-1 are described, for example, in US Pat US 4,157,384 , the corresponding N-substituted amides in J. Soc. Cosmet. Chem. Pp. 185-200 (1978) described.

flavorings

The flavoring agents which form component (b2) are selected from the group consisting of anethole, acetanisole, acetaldehyde, acetylmethylcarbinol, acetylpyrazine-2, acetylpyridine-2, acetylthiazoline-2, acetylthiazole-2, allylcapronate, amylcinnamaldehyde-alpha , Anisaldehyde-para, anisalcohol, dimethylisopropyldithiazine, benzaldehyde, benzylacetate, borneol-1, butyric acid, butylacetate, butylidene-phthalate-3, caproic acid, carvacrol, carvone-1, carvone-d, carvomenthone, carvylacetate-cis, caryophyllene, cineole-1,8 , Cineol-1,4, cinnamylacetate, citral, citronellal, citronellol, citronellylacetate, cuminaldehyde, cyclopentadecanolide, damascon-alpha, damascon-beta, damascenon-alpha, damascenon-beta, decalactone delta, decalactone-gamma, dehydromenthofurolactone, dihydromenthofurolactone, diethylpyrazine 2,3, dihydroanethol, dihydrocarvone, dihydrocoumarin, dihydroionone-beta, dimethylanthranilate, dimethylsulfide, dimethylpyrazine, sotolone, diphenyloxide, divanillin, decadienal-2,4, dodecalactone-delta, dode calactone-gamma, acetic acid, ethyl acetate, ethyl butyrate, ethyl methyl butyrate-2, ethyl capronate, ethyl caprylate, ethyl cinnamate, ethyl isobutyrate, ethyl vanillin, ethyl lactate, ethyl maltol, ethyl methyl thiopropionate, ethyl phenol-4, ethyl isovalerate, eugenol, fenchol, furanol, filbertone, frambinone, frambinone methyl ether, furfuryl thiol, Undecatriene, geraniol, geranyl acetate, geranyl isobutyrate, guaiacol, heliotropin, heptanone-2, heptenal-Z-4, hexalactone-gamma, heptalactone-gamma, hexenol-Z-3, hexenol-E-2, hexanol, hexylacetate, hexenylacetate-Z; 3, hexenylacetate-E-2, hexylcinnamaldehyde-alpha, hexenylcapronate-Z-3, hotrienol, indole, iron-alpha, ionon-alpha, ionone-beta, isoamylacetate, isoamylbutyrate, isoamylisovaranate, isobutylacetate, isobutylthiazole, isobutyraldehyde, isovaleraldehyde, isoeugenol, Isomenthone, isopropylmethoxypyrazine, isobutylmethoxypyrazine, isopropylmethylpyrazine-2,4, isopulegol, jasmine lactone, jasmon cis, camphor, ketoisophorone, cresol, limonene-d, linalool-1, linalool-d, linalyl acetate, Linalooloxide, maltol, methylcyclopentenolone, L-menthone, D-menthone, 1-menthol, D-menthol, neo-menthol, L-menthyl acetate, D menthyl acetate, massoilactone, melonal, menthenthiol-1,8, epithiomentan-1,8, thiomenthanone 8,3, menthofurolactone, menthadienylacetate, methoxymethylpyrazine-2,3, methylanthranilate, methylsalicylate, thymol, methylbutyrate, methylbutylacetate-2, methylcinnamate, methylfuranthiol-2,3, methyltetrahydrofuranethiol-2,3, methyljasmonate, methyldihydrojasmonate, methylthiobutyrate, methylthiohexylacetate-1, 3, Methylthiohexanol-1,3, Methional, Myrtenal, Naringin, Neral, Nerol, Nerylacetate, Nonalactone-gamma, Nonalactone-delta, Nonenal-E-2, Nonenal-Z-6, Nonenol-Z-6, Nootkatone, Dihydronootkaton, Octenol-1,3, Octalactone-gamma, Octalactone-delta, Pelitorin, Pentenone-1,3, Pentylacetate, Phenylacetaldehyde, Phenylethylalcohol, Phenylethylacetate, Piperitanate, Prenylthiol, Prenylthioacetate, Roseoxid, Rubenamine, Rubescenamine, Sabinehydrate, Skatol, Styrolylacetate, Terpineol, Terpinenol-4, thiohexano l-1,3, thiohexylacetate-1,3, thiopentanone-4,4,2, trimethylpyrazine, undecalacton-gamma and delta, decadienal-2,4, nonadienal-2,4, nonadienal-2,6, undecadienal-2, 4, vanillin, vinyl guaiacol, whiskey lactone, cinnamaldehyde, cinnamyl alcohol, diallyl disulfide, allyl isothiocyanate, hexanal, E-2-hexenal, octanal, decanal, tridecatrienal, 12-methyltridecanal, pinene-alpha, pinene-beta, piperitone and mixtures thereof.

In a further preferred embodiment of the invention, the preparations may contain as component (c) cosmetic additives which are selected from the group formed by Surfactants, oil bodies, emulsifiers, pearlescent waxes, bodying agents, thickeners, superfatting agents, stabilizers, polymers, silicone compounds, fats, waxes, lecithins, phospholipids, UV protection factors, moisturizers, biogenic agents, antioxidants, deodorants, antiperspirants, antidandruff agents, film formers, swelling agents, insect repellents , Self-tanning, tyrosine (depigmentation), hydrotropes, solubilizers, preservatives, perfume oils and dyes and their mixtures. Such preparations, especially if they are present as emulsions, are distinguished by improved storage stability.

The preparations according to the invention may contain components (a) and (b) in a weight ratio of 0.1: 99 to 99.9: 1, in particular 10:90 to 90:10, more preferably 25:75 to 75:25 and particularly preferably 40: 60 to 60:40 included. The components (a + b) and (c) may be contained in the weight ratio 0.01: 99.9 to 2:98, preferably 0.5: 99.5 to 1.5: 98.5 and in particular about 1:99.

INDUSTRIAL APPLICABILITY

COSMETIC AND / OR PHARMACEUTICAL PREPARATIONS

• (a) das Amid der Formel (I),
• (b) Menthol und/oder Mentholverbindungen der Formeln (II), (III) und/oder (IV) oder Aromastoffe, sowie
• (c) einen für kosmetische Anwendungen zugelassenen Träger.

Another object of the present invention relates to cosmetic preparations containing

• (a) the amide of the formula (I),
• (b) menthol and / or menthol compounds of the formulas (II), (III) and / or (IV) or flavorings, and
• (c) a carrier approved for cosmetic applications.

The cosmetic products are preferably skin care products, hair care products, personal care products, sunscreens and oral and dental care products. Particularly preferred are those preparations which are present as emulsions, microemulsions or PIT emulsions.

• (a) das Amid der Formel (I),
• (b) Menthol und/oder Mentholverbindungen der Formeln (II), (III) und/oder (IV) oder Aromastoffe sowie
• (c) einen für pharmazeutische Anwendungen zugelassenen Träger

zur Behandlung von Erkältungszuständen, wobei das Kennzeichen der Erfindung darin besteht, dass eine therapeutische Verwendung erfolgt.Another object of the present invention relates to pharmaceutical preparations containing

• (a) the amide of the formula (I),
• (b) menthol and / or menthol compounds of the formulas (II), (III) and / or (IV) or flavorings, and
• (c) a carrier approved for pharmaceutical applications

for the treatment of cold conditions, wherein the hallmark of the invention is that a therapeutic use is made.

The pharmaceutical products are preferably lozenges, cold drops, cold suds, cold ointments and cold sprays.

The cosmetic or pharmaceutical carriers may preferably be selected from the group formed by water, alcohols having 2 to 6 carbon atoms, polyols having 1 to 10 carbon atoms and 2 to 4 hydroxyl groups and oil bodies. Particularly preferred are, in addition to water, ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, glycerol, trimethylolpropane, pentaerythritol and esters of linear or branched, saturated and especially unsaturated fatty acids having 6 to 22 and preferably 8 to 18 carbon atoms with alcohols having 1 to 6 carbon atoms.

The cosmetic and / or pharmaceutical preparations according to the invention may contain components (a) and (b) in a weight ratio of 0.1: 99 to 99.9: 1, in particular 10:90 to 90:10, more preferably 25:75 to 75:25 and more preferably 40:60 to 60:40. The components (a + b) and (c) may be contained in the weight ratio 0.01: 99.9 to 2:98, preferably 0.5: 99.5 to 1.5: 98.5 and in particular about 1:99. The total content of the components (a + b) in the end products can be between 1 and 5,000, preferably 10 to 4,000 and in particular 100 to 1,000 ppm.

The cosmetic and / or pharmaceutical compositions according to the invention may contain further typical auxiliaries and additives, such as, for example, mild surfactants, oil bodies, emulsifiers, pearlescent waxes, consistency regulators, thickeners, superfatting agents, stabilizers, polymers, silicone compounds, fats, waxes, lecithins, phospholipids, UV stabilizers. Sunscreens, humectants, biogenic agents, antioxidants, deodorants, antiperspirants, antidandruff agents, film formers, swelling agents, insect repellents, tansy inhibitors, tyrosine inhibitors (depigmenting agents), hydrotropes, solubilizers, preservatives, perfume oils, dyes and the like.

surfactants

Surfactants which may be present are anionic, nonionic, cationic and / or amphoteric or zwitterionic surfactants, the proportion of which in the compositions is usually from about 1 to 70, preferably from 5 to 50, and in particular from 10 to 30,% by weight. Typical examples of anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, alkyl ether sulfates, glycerol ether sulfates, fatty acid ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates , Mono- and dialkylsulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acyl amino acids such as acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially wheat-based vegetable products) and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, these may 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 ethers, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers, optionally partially oxidized alk (en) yloligoglycosides or glucuronic acid derivatives, fatty acid N-alkylglucamides, protein hydrolysates (especially wheat-based vegetable products). , Polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution. Typical examples of cationic surfactants are quaternary ammonium compounds such as dimethyl distearyl ammonium chloride, and ester quats, especially quaternized fatty acid trialkanolamine ester salts. Typical examples of amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. The surfactants mentioned are exclusively known compounds. Typical examples of particularly suitable mild, d. H. particularly skin-compatible surfactants are fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and / or dialkyl sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, α-olefinsulfonates, ether carboxylic acids, alkyl oligoglucosides, fatty acid glucamides, alkylamidobetaines, amphoacetals and / or protein fatty acid condensates, the latter preferably based on wheat proteins.

oil body

Examples of oil bodies are Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C ₆ -C ₂₂ fatty acids with linear or branched C ₆ -C ₂₂ fatty alcohols or esters of branched C ₆ -C ₁₃ carboxylic acids with linear or branched C ₆ -C ₂₂ fatty alcohols, such as. B. myristyl myristate, myristyl palmitate, myristyl stearate, Myristylisostearat, myristyl, Myristylbehenat, Myristylerucat, cetyl myristate, cetyl palmitate, cetyl stearate, Cetylisostearat, cetyl oleate, cetyl behenate, Cetylerucat, Stearylmyristat, stearyl palmitate, stearyl stearate, Stearylisostearat, stearyl oleate, stearyl behenate, Stearylerucat, isostearyl, isostearyl palmitate, Isostearylstearat, isostearyl isostearate, Isostearyloleat, isostearyl behenate, Isostearyloleat, oleyl, oleyl palmitate, oleyl stearate, oleyl isostearate, oleate, Oleylbehenat, oleyl, behenyl myristate, behenyl, behenyl, Behenylisostearat, behenyl oleate, behenyl, erucyl, erucyl, erucyl, erucyl, erucyl, erucyl, erucyl behenate and erucyl. In addition, esters, esters of C ₁₈ -C are linear C ₆ -C ₂₂ fatty acids with branched alcohols, especially 2-ethylhexanol ₃₈ alkylhydroxycarboxylic with linear or branched C ₆ -C ₂₂ fatty alcohols, more especially Dioctyl Malate, esters of linear and / or branched fatty acids with polyhydric alcohols (such as propylene glycol, dimerdiol or trimer triol) and / or Guerbet alcohols, triglycerides based on C ₆ -C ₁₀ fatty acids, liquid mono- / di- / triglyceride mixtures based on C ₆ - C ₁₈ 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 -C ₁₂ 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 and branched C ₆ -C ₂₂ fatty alcohol carbonates, such as. B. Dicaprylyl carbonates (Cetiol ^® CC) Guerbetcarbonate based on fatty alcohols having 6 to 18, preferably 8 to 10 C atoms, esters of benzoic acid with linear and / or branched C ₆ -C ₂₂ alcohols (eg Finsolv ^® TN), linear or branched, symmetrical or asymmetrical dialkyl ethers having 6 to 22 carbon atoms per alkyl group, such as. B. dicaprylyl ethers (Cetiol ^® OE), ring-opening products of epoxidized fatty acid esters with polyols, silicone oils (Cyclomethicone, silicon methicone types, etc.) and / or aliphatic or naphthenic hydrocarbons, such as. As squalane, squalene or dialkylcyclohexanes into consideration.

emulsifiers

• • Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C-Atomen, an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe sowie Alkylamine mit 8 bis 22 Kohlenstoffatomen im Alkylrest;
• • Alkyl- und/oder Alkenyloligoglykoside mit 8 bis 22 Kohlenstoffatomen im Alk(en)ylrest und deren ethoxylierte Analoga;
• • Anlagerungsprodukte von 1 bis 15 Mol Ethylenoxid an Ricinusöl und/oder gehärtetes Ricinusöl;
• • Anlagerungsprodukte von 15 bis 60 Mol Ethylenoxid an Ricinusöl und/oder gehärtetes Ricinusöl;
• • Partialester von Glycerin und/oder Sorbitan mit ungesättigten, linearen oder gesättigten, verzweigten Fettsäuren mit 12 bis 22 Kohlenstoffatomen und/oder Hydroxycarbonsäuren mit 3 bis 18 Kohlenstoffatomen sowie deren Addukte mit 1 bis 30 Mol Ethylenoxid;
• • Partialester von Polyglycerin (durchschnittlicher Eigenkondensationsgrad 2 bis 8), Polyethylenglycol (Molekulargewicht 400 bis 5000), Trimethylolpropan, Pentaerythrit, Zuckeralkoholen (z. B. Sorbit), Alkylglucosiden (z. B. Methylglucosid, Butylglucosid, Laurylglucosid) sowie Polyglucosiden (z. B. Cellulose) mit gesättigten und/oder ungesättigten, linearen oder verzweigten Fettsäuren mit 12 bis 22 Kohlenstoffatomen und/oder Hydroxycarbonsäuren mit 3 bis 18 Kohlenstoffatomen sowie deren Addukte mit 1 bis 30 Mol Ethylenoxid;
• • Mischester aus Pentaerythrit, Fettsäuren, Citronensäure und Fettalkohol und/oder Mischester von Fettsäuren mit 6 bis 22 Kohlenstoffatomen, Methylglucose und Polyolen, vorzugsweise Glycerin oder Polyglycerin.
• • Mono-, Di- und Trialkylphosphate sowie Mono-, Di- und/oder Tri-PEG-alkylphosphate und deren Salze;
• • Wollwachsalkohole;
• • Polysiloxan-Polyalkyl-Polyether-Copolymere bzw. entsprechende Derivate;
• • Block-Copolymere z. B. Polyethylenglycol-30 Dipolyhydroxystearate;
• • Polymeremulgatoren, z. B. Pemulen-Typen (TR-1, TR-2) von Goodrich oder Cosmedia^® SP von Cognis;
• • Polyalkylenglycole sowie
• • Glycerincarbonat.

Examples of suitable emulsifiers are nonionic surfactants from at least one of the following groups:

• Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms, to alkylphenols having 8 to 15 carbon atoms in the alkyl group and Alkylamines having 8 to 22 carbon atoms in the alkyl radical;
• • alkyl and / or alkenyl oligoglycosides having 8 to 22 carbon atoms in the alk (en) yl radical and their ethoxylated analogs;
• Adducts of 1 to 15 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;
• Adducts of 15 to 60 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;
• Partial esters of glycerol and / or sorbitan with unsaturated, linear or saturated, branched fatty acids having 12 to 22 carbon atoms and / or hydroxycarboxylic acids having 3 to 18 carbon atoms and their adducts with 1 to 30 moles of ethylene oxide;
• Partial esters of polyglycerol (average intrinsic degree of condensation 2 to 8), polyethylene glycol (molecular weight 400 to 5000), trimethylolpropane, pentaerythritol, sugar alcohols (eg sorbitol), alkylglucosides (eg methylglucoside, butylglucoside, laurylglucoside) and polyglucosides (e.g. Cellulose) with saturated and / or unsaturated, linear or branched fatty acids containing 12 to 22 carbon atoms and / or hydroxycarboxylic acids containing 3 to 18 carbon atoms and adducts thereof with 1 to 30 moles of ethylene oxide;
• Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol and / or mixed esters of fatty acids having 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol or polyglycerol.
• Mono-, di- and trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates and their salts;
• • wool wax alcohols;
• Polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;
• Block copolymers z. For example, polyethylene glycol-30 dipolyhydroxystearates;
• • Polymer emulsifiers, eg. B. Pemulen grades (TR-1, TR-2) from Goodrich or Cosmedia SP ^® Cognis;
• • Polyalkylene glycols as well
• • Glycerine carbonate.

In the following, particularly suitable emulsifiers are explained in more detail:

(a) Alkoxylates

The addition products of ethylene oxide and / or of propylene oxide onto fatty alcohols, fatty acids, alkylphenols or castor oil are known, commercially available products. These are mixtures of homologues whose average degree of alkoxylation corresponds to the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate, with which the addition reaction is carried out corresponds. C _12/18 fatty acid _mono- and diesters of addition products of ethylene oxide with glycerol are known as refatting agents for cosmetic preparations.

(a) alkyl and / or alkenyl oligoglycosides

Alkyl and / or alkenyl oligoglycosides, their preparation and their use are known from the prior art. They are prepared in particular by reacting glucose or oligosaccharides with primary alcohols having 8 to 18 carbon atoms. With regard to the glycoside radical, both monoglycosides in which a cyclic sugar residue is glycosidically linked to the fatty alcohol and oligomeric glycosides having a degree of oligomerization of preferably approximately 8 are suitable. The degree of oligomerization is a statistical mean, which is based on a homolog distribution typical for such technical products.

(b) partial glycerides

Typical examples of suitable partial glycerides are hydroxystearic hydroxystearic acid diglyceride, isostearic acid, Isostearinsäurediglycerid monoglyceride, oleic acid diglyceride, Ricinolsäuremoglycerid, Ricinolsäurediglycerid, Linolsäuremonoglycerid, Linolsäurediglycerid, Linolensäuremonoglycerid, Linolensäurediglycerid, Erucasäuremonoglycerid, Erucasäurediglycerid, Weinsäuremonoglycerid, Weinsäurediglycerid, Citronensäuremonoglycerid, Citronendiglycerid, Äpfelsäuremonoglycerid, Apfelsäurediglycerid and technical mixtures thereof, which are still subordinate to the manufacturing process may contain small amounts of triglyceride. Also suitable are addition products of 1 to 30, preferably 5 to 10 moles of ethylene oxide to said Partialglyceride.

(c) sorbitan esters

As sorbitan sorbitan, sorbitan sesquiisostearate, Sorbitan, sorbitan triisostearate, sorbitan monooleate, sorbitan, sorbitan, Sorbitanmonoerucat, Sorbitansesquierucat, Sorbitandierucat, Sorbitantrierucat, Sorbitanmonoricinoleat, Sorbitansesquiricinoleat, Sorbitandiricinoleat, Sorbitantriricinoleat, Sorbitanmonohydroxystearat, Sorbitansesquihydroxystearat, Sorbitandihydroxystearat, Sorbitantrihydroxystearat, Sorbitanmonotartrat, Sorbitansesqui tartrate, Sorbitanditartrat come , Sorbitan tritartrate, sorbitan monocitrate, sorbitan siccitrate, sorbitan di-citrate, sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate, sorbitan dimaleate, sorbitan trimaleate, and technical mixtures thereof. Also suitable are addition products of 1 to 30, preferably 5 to 10 moles of ethylene oxide to said sorbitan esters.

(d) polyglycerol ester

Typical examples of suitable polyglycerol esters are Polyglyceryl-2 Dipolyhydroxystearate (Dehymuls ^® PGPH), Polyglycerin-3-Diisostearate (Lameform ^® TGI), Polyglyceryl-4 Isostearate (Isolan ^® GI 34), Polyglyceryl-3 Oleate, Diisostearoyl Polyglyceryl-3 Diisostearate (Isolan ® PDI), Polyglyceryl-3 methylglucose Distearate (Tego Care ® 450), Polyglyceryl-3 Beeswax (Cera Bellina ^®), Polyglyceryl-4 Caprate (polyglycerol Caprate T2010 / 90), Polyglyceryl-3 Cetyl ether (Chimexane ^® NL), Polyglyceryl -3 Distearate (Cremophor ^® GS 32) and Polyglyceryl polyricinoleates (Admul ^® WOL 1403) polyglyceryl dimerates Isostearate and mixtures thereof. Examples of other suitable polyol esters are the mono-, di- and triesters of trimethylolpropane or pentaerythritol with lauric acid, coconut fatty acid, tallow fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like, which are optionally reacted with from 1 to 30 mol of ethylene oxide.

(e) anionic emulsifiers

Typical anionic emulsifiers are aliphatic fatty acids having 12 to 22 carbon atoms, such as palmitic acid, stearic acid or behenic acid, and dicarboxylic acids having 12 to 22 carbon atoms, such as azelaic acid or sebacic acid.

(f) Amphoteric and cationic emulsifiers

Furthermore, zwitterionic surfactants can be used as emulsifiers. Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammoniumglycinate, for example Kokosalkyldimethylammoniumglycinat, N-acylaminopropyl-N, N-dimethylammoniumglycinate, for example Kokosacylaminopropyldimethyl-ammoniumglycinat, and 2-alkyl-3-carboxylmethyl-3 -hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and cocoacylaminoethylhydroxyethylcarboxymethylglycinate. Particularly preferred is the fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine. Also suitable emulsifiers are ampholytic surfactants. Ampholytic surfactants are understood as meaning those surface-active compounds which, apart from a C _8/18 -alkyl or acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO ₃ H group and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C _12/18 acylsarcosine. Finally, cationic surfactants are also suitable as emulsifiers, those of the esterquat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, being particularly preferred.

Fats and waxes

Typical examples of fats are glycerides, ie solid or liquid vegetable or animal products, which consist essentially of mixed glycerol esters of higher fatty acids, waxes include natural waxes such. Candelilla wax, carnauba wax, Japan wax, Esparto grass wax, Cork wax, guaruma wax, rice germ oil wax, sugarcane wax, ouricury wax, montan wax, beeswax, shellac wax, spermaceti, lanolin (wool wax), crepe fat, ceresin, ozokerite (groundwax), petrolatum, paraffin waxes, microwaxes; chemically modified waxes (hard waxes), such as. As montan ester waxes, Sasol waxes, hydrogenated jojoba waxes and synthetic waxes such. As polyalkylene waxes and polyethylene glycol waxes in question. In addition to the fats come as additives and fat-like substances such as lecithins and phospholipids in question. By the term lecithin, those skilled in the art will understand those glycerophospholipids which are formed from fatty acids, glycerol, phosphoric acid and choline by esterification. Lecithins are therefore often referred to in the art as Phosphatidylcholine (PC). Examples of natural lecithins include the cephalins, which are also referred to as phosphatidic acids and derivatives of 1,2-diacyl-sn-glycerol-3-phosphoric acids. On the other hand, phospholipids are usually understood as meaning mono- and preferably diesters of phosphoric acid with glycerol (glycerol phosphates), which are generally regarded as fats. In addition, sphingosines or sphingolipids are also suitable.

pearlescent

Suitable pearlescing waxes are, for example: alkylene glycol esters, especially ethylene glycol distearate; Fatty acid alkanolamides, especially coconut fatty acid diethanolamide; Partial glycerides, especially stearic acid monoglyceride; Esters of polybasic, optionally hydroxy-substituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; Fatty substances, such as fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which in total have at least 24 carbon atoms, especially lauron and distearyl ether; Fatty acids such as stearic acid, hydroxystearic acid or behenic acid, ring-opening products of olefin epoxides having 12 to 22 carbon atoms with fatty alcohols having 12 to 22 carbon atoms and / or polyols having 2 to 15 carbon atoms and 2 to 10 hydroxyl groups and mixtures thereof.

Consistency and thickener

As consistency factors are primarily fatty alcohols or hydroxy fatty alcohols having 12 to 22 and preferably 16 to 18 carbon atoms and in addition partial glycerides, fatty acids or hydroxy fatty acids into consideration. Preference is given to a combination of these substances with alkyl oligoglucosides and / or fatty acid N-methylglucamides of the same chain length and / or polyglycerol poly-12-hydroxystearates. Suitable thickeners are, for example, Aerosil types (hydrophilic silicic acids), polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl and hydroxypropyl cellulose, and also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, (. eg Carbopol ^® and Pemulen grades from Goodrich; Synthalens ^® from Sigma; Keltrol grades from Kelco; Sepigel grades from Seppic; Salcare grades from Allied Colloids), polyacrylamides, polymers, polyvinyl alcohol and polyvinyl pyrrolidone. Be particularly effective bentonites such. B. Bentone ^® Gel VS-5PC (Rheox), which is a mixture of cyclopentasiloxane, disteardimonium hectorite and propylene carbonate. Also suitable are surfactants, such as, for example, ethoxylated fatty acid glycerides, esters of fatty acids with polyols, for example pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with narrow homolog distribution or alkyl oligoglucosides and also electrolytes, such as common salt and ammonium chloride.

superfatting

As superfatting agents, substances such as lanolin and lecithin as well as polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides can be used, the latter also serving as foam stabilizers.

stabilizers

As stabilizers metal salts of fatty acids, such as. For example, magnesium, aluminum and / or zinc stearate or ricinoleate can be used.

polymers

Suitable cationic polymers are, for example, cationic cellulose derivatives, such as. Example, a quaternized hydroxyethylcellulose obtainable under the name Polymer JR 400 ^® from Amerchol, cationic starch, copolymers of diallyl ammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers, such. As Luviquat ^® (BASF), condensation products of polyglycols and amines, quaternized collagen polypeptides, for example lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat® ^® L / Grunau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers such. B. Amodimethicone, copolymers of adipic acid and Dimethylaminohydroxypropyldiethylentriamin (Cartaretine ^® / Sandoz), copolymers of acrylic acid with dimethyl-diallyl ammonium chloride (Merquat ^® 550 / Chemviron), polyaminopolyamides and their crosslinked water-soluble polymers, cationic chitin derivatives such as quaternized chitosan, optionally microcrystalline distributed, condensation products of dihaloalkylene, such as. B. dibromobutane with bis-dialkylamines, such as. B. bis-dimethylamino-1,3-propane, cationic guar gum, such as. ^Jaguar® CBS, ^Jaguar® C-17, ^Jaguar® C-16 from Celanese, quaternized ammonium salt polymers, e.g. B. Mirapol ^® A-15, Mirapol ^® AD-1, Mirapol ^® AZ-1 from Miranol.

Examples of anionic, zwitterionic, amphoteric and nonionic polymers are vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and their esters, uncrosslinked polyols crosslinked with polyols, acrylamidopropyltrimethylammonium chloride / acrylate -Copolymers, octylacrylamide / methyl methacrylate / tert.Butylaminoethylmethacrylat / 2-hydroxypropyl methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymers, vinylpyrrolidone / dimethylaminoethyl methacrylate / vinylcaprolactam terpolymers and optionally derivatized cellulose ethers and silicones in question.

silicone compounds

Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones and amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or alkyl-modified silicone compounds which may be both liquid and resin-form at room temperature. Also suitable are simethicones, which are mixtures of dimethicones having an average chain length of from 200 to 300 dimethylsiloxane units and hydrogenated silicates.

UV protection factors

• • 3-Benzylidencampher bzw. 3-Benzylidennorcampher und dessen Derivate, z. B. 3-(4-Methylbenzyliden)campher beschrieben;
• • 4-Aminobenzoesäurederivate, vorzugsweise 4-(Dimethylamino)benzoesäure-2-ethylhexylester, 4-(Dimethylamino)benzoesäure-2-octylester und 4-(Dimethylamino)benzoesäureamylester;
• • Ester der Zimtsäure, vorzugsweise 4-Methoxyzimtsäure-2-ethylhexylester, 4-Methoxyzimtsäurepropylester, 4-Methoxyzimtsäureisoamylester 2-Cyano-3,3-phenylzimtsäure-2-ethylhexylester (Octocrylene);
• • Ester der Salicylsäure, vorzugsweise Salicylsäure-2-ethylhexylester, Salicylsäure-4-isopropylbenzylester, Salicylsäurehomomenthylester;
• • Derivate des Benzophenons, vorzugsweise 2-Hydroxy-4-methoxybenzophenon, 2-Hydroxy-4-methoxy-4'-methylbenzophenon, 2,2'-Dihydroxy-4-methoxybenzophenon;
• • Ester der Benzalmalonsäure, vorzugsweise 4-Methoxybenzmalonsäuredi-2-ethylhexylester;
• • Triazinderivate, wie z. B. 2,4,6-Trianilino-(p-carbo-2'-ethyl-1'-hexyloxy)-1,3,5-triazin und Octyl Triazon oder Dioctyl Butamido Triazone (Uvasorb^® HEB);
• • Propan-1,3-dione, wie z. B. 1-(4-tert.Butylphenyl)-3-(4'methoxyphenyl)propan-1,3-dion;
• • Ketotricyclo(5.2.1.0)decan-Derivate.

Under UV sun protection factors are, for example, at room temperature, liquid or crystalline organic substances present (sunscreen) to understand that are able to absorb ultraviolet rays and the absorbed energy in the form of longer-wave radiation, eg. B. to give off heat again. Usually, the UV sunscreen factors are present in amounts of 0.1 to 5 and preferably 0.2 to 1 wt .-%. UVB filters can be oil-soluble or water-soluble. As oil-soluble substances z. To name, for example:

• • 3-Benzylidencampher or 3-Benzylidennorcampher and its derivatives, eg. B. 3- (4-methylbenzylidene) camphor;
• 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and 4- (dimethylamino) benzoic acid ester;
• Esters of cinnamic acid, preferably 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isoamyl ester 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene);
• Esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomenthyl salicylate;
• Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone;
• Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate;
• Triazine derivatives, such as. For example, 2,4,6-trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine and Octyl Triazone or Dioctyl Butamido Triazone (Uvasorb HEB ^®);
• • Propane-1,3-dione, such as B. 1- (4-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione;
• • Ketotricyclo (5.2.1.0) decane derivatives.

• • 2-Phenylbenzimidazol-5-sulfonsäure und deren Alkali-, Erdalkali-, Ammonium-, Alkylammonium-, Alkanolammonium- und Glucammoniumsalze;
• • 1H-Benzimidazole-4,6-Disulfonic Acid, 2,2'-(1,4-Phenylene)Bis-, Disodium Salt (Neo Heliopan^® AP)
• • Sulfonsäurederivate von Benzophenonen, vorzugsweise 2-Hydroxy-4-methoxybenzophenon-5-sulfonsäure und ihre Salze;
• • Sulfonsäurederivate des 3-Benzylidencamphers, wie z. B. 4-(2-Oxo-3-bornylidenmethyl)benzolsulfonsäure und 2-Methyl-5-(2-oxo-3-bornyliden)sulfonsäure und deren Salze.

Suitable water-soluble substances are:

• 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts;
• • 1H-Benzimidazole-4,6-disulfonic acid, 2,2 '- (1,4-phenylene) bis-, disodium salt (Neo Heliopan AP ^®)
• Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts;
• Sulfonic acid derivatives of 3-Benzylidencamphers, such as. B. 4- (2-oxo-3-bomylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and salts thereof.

As a typical UV-A filter in particular derivatives of benzoylmethane are suitable, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl -4'methoxydibenzoylmethane Hexyl (Parsol ^® 1789), 2- (4-diethylamino-2-hydroxybenzoyl) -benzoic acid (Uvinul A Plus ^®), 1-phenyl-3- (4'-isopropylphenyl) -propane-1,3-dione as well as enamine compounds , Of course, the UV-A and UV-B filters can also be used in mixtures. Particularly favorable combinations consist of the derivatives of benzoylmethane, z. B. 4-tert-butyl-4'-methoxydibenzoylmethane (Parsol ^® 1789) and 2-cyano-3,3-phenylcinnamate-2-ethyl-hexyl ester (octocrylene) in combination with esters of cinnamic acid, preferably 4-methoxycinnamic acid-2 ethylhexyl ester and / or 4-methoxycinnamic acid propyl ester and / or 4-methoxycinnamic acid isoamyl ester. Advantageously, such combinations with water-soluble filters such. B. 2-phenylbenzimidazole-5-sulfonic acid and their alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium combined.

In addition to the soluble substances mentioned, insoluble photoprotective pigments, namely finely dispersed metal oxides or salts, are also suitable for this purpose. Examples of suitable metal oxides are in particular zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof. As salts silicates (talc), barium sulfate or zinc stearate can be used. The oxides and salts are used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics. 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. They may have a spherical shape, but it is also possible to use those particles which have an ellipsoidal or otherwise deviating shape from the spherical shape. The pigments can also be surface-treated, ie hydrophilized or hydrophobized. Typical examples are coated titanium dioxides, such as. Example, titanium dioxide T 805 (Degussa) or Eusolex ^® T2000, Eusolex ^® T, Eusolex ^® T-ECO, Eusolex ^® TS, Eusolex ^® T-Aqua, Eusolex ^® T-45D (all Merck), Uvinul TiO ₂ (BASF). Suitable hydrophobic coating agents are in particular silicones and in particular trialkoxyoctylsilanes or simethicones. In sunscreens, so-called micro- or nanopigments are preferably used. Preferably, micronized zinc oxide such as. B. Z-COTE ^® or Z-COTE HP1 ^® used.

Humectants

Humectants serve to further optimize the sensory properties of the composition and to regulate the moisture of the skin. At the same time, the low-temperature stability of the preparations according to the invention, in particular in the case of emulsions, is increased. The humectants are usually contained in an amount of 0.1 to 15 wt .-%, preferably 1 to 10 wt .-%, and especially 5 to 10 wt .-%.

According to the invention are suitable u. a. Amino acids, pyrrolidonecarboxylic acid, lactic acid and its salts, lactitol, urea and urea derivatives, uric acid, glucosamine, creatinine, cleavage products of collagen, chitosan or chitosan salts / derivatives, and in particular polyols and polyol derivatives (eg glycerol, diglycerol, triglycerol, ethylene glycol, Propylene glycol, butylene glycol, erythritol, 1,2,6-hexanetriol, polyethylene glycols such as PEG-4, PEG-6, PEG-7, PEG-8, PEG-9, PEG-10, PEG-12, PEG-14, PEG- 16, PEG-18, PEG-20), sugars and sugar derivatives (including fructose, glucose, maltose, maltitol, mannitol, inositol, sorbitol, sorbitanlsilanediol, sucrose, trehalose, xylose, xylitol, glucuronic acid and their salts), ethoxylated sorbitol (sorbeth -6, sorbeth-20, sorbeth-30, sorbeth-40), honey and hardened honey, hardened starch hydrolysates and mixtures of hardened wheat protein and PEG-20 acetate copolymer. Preferably suitable as humectants according to the invention are glycerol, diglycerol, triglycerol and butylene glycol.

Biogenic agents and antioxidants

Examples of biogenic active substances include tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, (deoxy) ribonucleic acid and their fragmentation products, β-glucans, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts, such as B. Prunusextrakt, Bambaranussextrakt and vitamin complexes to understand.

Antioxidants interrupt the photochemical reaction chain, which is triggered when UV radiation penetrates the skin. Typical examples thereof are amino acids (eg glycine, 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, chlorogenic acid and its derivatives, lipoic acid and its derivatives (eg dihydrolipoic acid), aurothioglucose , Propylthiouracil and other thiols (eg thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, Oleyl, γ-linoleyl, cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate, Distearyl thiodipropionate, thiodipropionic acid and its derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (eg buthionine sulfoximines, homocysteinesulfoximine, bithine sulfones, penta, hexa, heptathionine sulfoximine) in very low tolerated dosages (eg. Pmol to μmol / kg), furthermore (metal) chelators (eg α-hydroxyfatty 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 B. ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (eg, vitamin E acetate), vitamin A and derivatives (vitamin A palmitate), and benzylic benzylic benzoate, Ruti acid and its derivatives, α-glycosylrutin, ferulic acid, furfurylideneglucitol, carnosine, butylhydroxytoluene, butylhydroxyanisole, nordihydroguaiacetic acid, nordihydroguiaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, superoxide dismutase, zinc and its derivatives (e.g. ZnO, ZnSO ₄ ) selenium and its derivatives (eg selenium methionine), stilbenes and their derivatives (eg stilbene oxide, trans-stilbene oxide) and the derivatives suitable according to the invention (salts, esters, ethers, sugars, Nucleotides, nucleosides, peptides and lipids) of said active substances.

Deodorants and germ repellents

Cosmetic deodorants (deodorants) counteract, cover or eliminate body odors. Body odors are caused by the action of skin bacteria on apocrine sweat, forming unpleasant-smelling degradation products. Accordingly, deodorants contain active ingredients which act as anti-sprouting agents, enzyme inhibitors, odor absorbers or odor maskers.

(a) Germ-inhibiting agents

As germ-inhibiting agents are basically all effective against Gram-positive bacteria substances such. B. 4-hydroxybenzoic acid and its salts and esters, N- (4-chlorophenyl) -N '- (3,4-dichlorophenyl) urea, 2,4,4'-trichloro-2'-hydroxy-diphenyl ether (triclosan), 4-chloro-3,5-dimethyl-phenol, 2,2'-methylenebis (6-bromo-4-chlorophenol), 3-methyl-4- (1-methylethyl) -phenol, 2-benzyl-4 chlorophenol, 3- (4-chlorophenoxy) -1,2-propanediol, 3-iodo-2-propynyl butylcarbamate, chlorhexidine, 3,4,4'-trichlorocarbanilide (TTC), antibacterial fragrances, thymol, thyme oil, eugenol, clove oil, menthol , Mint oil, farnesol, phenoxyethanol, glycerol monocaprinate, glycerol monocaprylate, glycerol monolaurate (GML), diglycerol monocaprinate (DMC), salicylic acid N-alkylamides such as. Salicylic acid n-octylamide or salicylic acid n-decylamide.

(b) enzyme inhibitors

For example, esterase inhibitors are suitable as enzyme inhibitors. These are preferably trialkyl such as trimethyl citrate, tripropyl, triisopropyl, tributyl citrate and especially triethyl citrate (Hydagen® ^® CAT). The substances inhibit the enzyme activity and thereby reduce odors. Further substances which are suitable as esterase inhibitors are sterol sulfates or phosphates, such as, for example, lanosterol, cholesterol, campesterol, stigmasterol and sitosterol sulfate or phosphate, dicarboxylic acids and their esters, for example glutaric acid, glutaric acid monoethyl ester, glutaric acid diethyl ester, adipic acid, Adipic acid monoethyl ester, diethyl adipate, malonic acid and diethyl malonate, hydroxycarboxylic acids and their esters such as citric acid, malic acid, tartaric acid or diethyl tartrate, and zinc glycinate.

(c) Odor Absorber

Suitable odor absorbers are substances that absorb and largely retain odor-forming compounds. They reduce the partial pressure of the individual components and thus also reduce their propagation speed. It is important that perfumes must remain undisturbed. Odor absorbers have no activity against bacteria. They contain, for example, as a main component of a complex zinc salt of ricinoleic acid or special, largely odorless fragrances, which are known in the art as "fixatives", such. B. Extracts of Labdanum or Styrax or certain Abietinsäurederivate. Odor maskers are fragrances or perfume oils which, in addition to their function as odor maskers, give the deodorants their respective scent. Examples of perfume oils are mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers, stems and leaves, fruits, fruit peel, roots, woods, herbs and grasses, needles and twigs, as well as resins and balsams. Furthermore, animal raw materials come into question, such as civet and Castoreum. Typical synthetic fragrance compounds are products of the ester, ether, Aldehydes, ketones, alcohols and hydrocarbons. Fragrance compounds of the ester type are e.g. Benzyl acetate, p-tert-butylcyclohexyl acetate, linalyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether to the aldehydes z. B. the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones z. The alcohols include anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons include mainly the terpenes and balsams. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Also essential oils of lower volatility, which are mostly used as aroma components, are suitable as perfume oils, eg. B. sage oil, camomile oil, clove oil, lemon balm oil, mint oil, cinnamon oil, lime blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labdanum oil and lavandin oil. Preferably, bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol, benzylacetone, cyclamen aldehyde, linalool, Boisambrene Forte, Ambroxan, indole, hedione, Sandelice, citron oil, tangerine oil, orange oil, Allylamylglycolat, Cyclovertal, Lavandinöl, Muskateller Sage oil, β-damascone, geranium oil Bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, fixolide NP, evernyl, iraldeine gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilate, irotyl and floramate alone or in mixtures.

(d) antiperspirants

• • adstringierende Wirkstoffe,
• • Ölkomponenten,
• • nichtionische Emulgatoren,
• • Coemulgatoren,
• • Konsistenzgeber,
• • Hilfsstoffe wie z. B. Verdicker oder Komplexierungsmittel und/oder
• • nichtwässrige Lösungsmittel wie z. B. Ethanol, Propylenglykol und/oder Glycerin.

Antiperspirants (antiperspirants) reduce the formation of sweat by influencing the activity of eccrine sweat glands and thus counteract underarm wetness and body odor. Aqueous or anhydrous formulations of antiperspirants typically contain the following ingredients:

• Astringent agents,
• • oil components,
• Nonionic emulsifiers,
• Coemulsifiers,
• • bodybuilder,
• • auxiliaries such as B. thickener or complexing agent and / or
• • non-aqueous solvents such. As ethanol, propylene glycol and / or glycerol.

• • entzündungshemmende, hautschützende oder wohlriechende ätherische Öle,
• • synthetische hautschützende Wirkstoffe und/oder
• • öllösliche Parfümöle.

Salts of aluminum, zirconium or zinc are especially suitable as astringent antiperspirant active ingredients. Such suitable antiperspirant active ingredients are, for. For example, aluminum chloride, aluminum chlorohydrate, aluminum dichlorohydrate, aluminum sesquichlorohydrate and their complex compounds z. With propylene glycol-1,2. Aluminum hydroxyallotate, aluminum chloride tartrate, aluminum-zirconium trichlorohydrate, aluminum zirconium tetrachlorohydrate, aluminum zirconium pentachlorohydrate and their complex compounds e.g. With amino acids such as glycine. In addition, antiperspirants may contain customary oil-soluble and water-soluble adjuvants in smaller amounts. Such oil-soluble aids may, for. For example:

• • anti-inflammatory, skin-protecting or fragrant essential oils,
• • synthetic skin-protecting agents and / or
• • oil-soluble perfume oils.

Usual water-soluble additives are z. As preservatives, water-soluble fragrances, pH adjuster, z. B. buffer mixtures, water-soluble thickeners, eg. B. water-soluble natural or synthetic polymers such. As xanthan gum, hydroxyethyl cellulose, polyvinylpyrrolidone or high molecular weight polyethylene oxides.

film formers

Typical film formers are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives, collagen, hyaluronic acid or salts thereof and similar compounds.

Antidandruff agents

Suitable antidandruff active ingredients are piroctone amine come oil (1-hydroxy-4-methyl-6- (2,4,4-trimythylpentyl) -2- (1H) -pyridinonmonoethanolaminsalz) Baypival ^® (Climbazole), ketoconazole ^®, (4-acetyl-1 - {- 4- [2- (1H-imidazol-1-ylmethyl) -1,3-dioxylan-c-4-ylmethoxyphenyl} piperazine, ketoconazole, elubiol, selenium disulfide, sulfur colloid, Sulfur polyethyleneglycol sorbitan monooleate, sulfur trizinol polyethoxylate, black tea distillates, salicylic acid (or in combination with hexachlorophene), undecylenic acid Monoethanolamide sulfosuccinate Na salt, Lamepon® ^® UD (protein undecylenic acid), zinc pyrithione, magnesium pyrithione Aluminiumpyrithion and / dipyrithione magnesium sulfate.

swelling agent

Suitable swelling agents for aqueous phases are montmorillonites, clay minerals, pemulen and alkyl-modified carbopol types (Goodrich). Other suitable polymers or swelling agents can the overview of R. Lochhead in Cosm. Toil. 108, 95 (1993) be removed.

insect repellents

Suitable insect repellents are N, N-diethyl-m-toluamide, 1,2-pentanediol or ethyl butylacetylaminopropionate. As a self-tanner dihydroxyacetone is suitable. As Tyrosinhinbitoren that prevent the formation of melanin and find application in depigmenting, for example, arbutin, ferulic acid, kojic acid, coumaric acid and ascorbic acid (vitamin C) come into question.

Ingredients for oral and dental care products

Toothpastes or toothpastes are generally understood to be gelatinous or pasty preparations of water, thickeners, humectants, abrasives or cleaning articles, surfactants, sweeteners, flavorings, deodorizing active ingredients and active ingredients for oral and dental diseases. In the toothpastes according to the invention all the usual cleaning body, such as. As chalk, dicalcium phosphate, insoluble sodium metaphosphate, aluminum silicates, calcium pyrophosphate, finely divided resins, silicas, alumina and alumina trihydrate are used.

Preferably suitable cleaning bodies for the toothpastes according to the invention are, above all, finely divided xerogel silicas, hydrogel silicic acids, precipitated silicas, alumina trihydrate and finely divided alpha alumina or mixtures of these cleansers in amounts of from 15 to 40% by weight of the toothpaste. The humectants are mainly low molecular weight polyethylene glycols, glycerol, sorbitol or mixtures of these products in amounts up to 50 wt .-% in question. Among the known thickeners are the thickening, finely divided gel silicas and hydrocolloids, such as. As carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl guar, hydroxyethyl starch, polyvinyl pyrrolidone, high molecular weight polyethylene glycol, vegetable gums such as tragacanth, agar-agar, Irish moss, gum arabic, xantham gum, and carboxyvinyl polymers (eg. Carbopol ^® grades) is suitable. In addition to the mixtures of menthofuran and menthol compounds, the oral and dental care products may contain, in particular, surface-active substances, preferably anionic and nonionic foamy surfactants, such as the substances mentioned above, but especially alkyl ether sulfate salts, alkyl polyglucosides and mixtures thereof.

• • Konservierungsmittel und antimikrobielle Stoffe wie z. B. p-Hydroxybenzösäuremethyl-, -ethyl- oder -propylester, Natriumsorbat, Natriumbenzoat, Bromchlorophen, Phenylsalicylsäureester, Thymol und dergleichen;
• • Antizahnsteinwirkstoffe, z. B. Organophosphate wie 1-Hydroxyethan-1.1-diphosphonsäure, 1-Phosphonpropan-1,2,3-tricarbonsäure und andere, die z. B. aus US 3,488,419 , DE 2224430 A1 und DE 2343196 A1 bekannt sind;
• • andere karieshemmende Stoffe wie z. B. Natriumfluorid, Natriummonofluorphosphat, Zinnfluorid;
• • Süssungsmittel, wie z. B. Saccharin-Natrium, Natrium-Cyclamat, Sucrose, Lactose, Maltose, Fructose oder Apartam^®, (L-Aspartyl-L-phenylalanin-methylester), Stivia-extrakte oder deren süßenden Bestandteile, insbesondere Ribeaudioside;
• • Zusätzliche Aromen wie z. B. Eukalyptusöl, Anisöl, Fenchelöl, Kümmelöl, Methylacetat, Zimtaldehyd, Anethol, Vanillin, Thymol sowie Mischungen dieser und anderer natürlicher und synthetischer Aromen;
• • Pigmente wie z. B. Titandioxid;
• • Farbstoffe;
• • Puffersubstanzen wie z. B. primäre, sekundäre oder tertiäre Alkaliphosphate oder Citronensäure/Natriumcitrat;
• • wundheilende und entzündungshemmende Stoffe wie z. B. Allantoin, Harnstoff, Azulen, Kamillenwirkstoffe und Acetylsalicylsäurederivate.

Other common toothpaste additives are:

• Preservatives and antimicrobials such. P-hydroxybenzoic acid methyl, ethyl or propyl ester, sodium sorbate, sodium benzoate, bromochlorophene, phenylsalicylic acid ester, thymol and the like;
• • anticalculus ingredients, e.g. B. organophosphates such as 1-hydroxyethane-1,1-diphosphonic acid, 1-phosphonopropane-1,2,3-tricarboxylic acid and others, the z. B. off US 3,488,419 . DE 2224430 A1 and DE 2343196 A1 are known;
• • other caries-inhibiting substances such. Sodium fluoride, sodium monofluorophosphate, stannous fluoride;
• • Sweeteners, such as B. saccharin sodium, sodium cyclamate, sucrose, lactose, maltose, fructose or Apartam ^®, (L-aspartyl-L-phenylalanine-methylester), Stivia extracts or their sweetening components, in particular Ribeaudioside;
• • Additional flavors such. Eucalyptus oil, aniseed oil, fennel oil, caraway oil, methyl acetate, cinnamaldehyde, anethole, vanillin, thymol, and mixtures of these and other natural and synthetic flavors;
• • pigments such as For example, titanium dioxide;
• • dyes;
• • Buffer substances such. Primary, secondary or tertiary alkali phosphates or citric acid / sodium citrate;
• • wound healing and anti-inflammatory substances such. Allantoin, urea, azulene, chamomile agents and acetylsalicylic acid derivatives.

A preferred embodiment of the cosmetic preparations are toothpastes in the form of an aqueous, pasty dispersion containing polishing agents, humectants, viscosity regulators and optionally contain further customary components, and the mixture of menthofuran and menthol compounds in amounts of 0.5 to 2 wt .-%.

In mouthwashes, a combination with aqueous-alcoholic solutions of various grades of essential oils, emulsifiers, astringent and toning drug extracts, anti-calculus, anti-bacterial additives and flavoring agents is readily possible. A further preferred embodiment of the invention is a mouthwash in the form of an aqueous or aqueous-alcoholic solution containing the mixture of menthofuran and menthol compounds in amounts of from 0.5 to 2% by weight. In mouthwashes that are diluted before use, sufficient effects can be obtained with higher concentrations, according to the intended dilution ratio.

hydrotropes

• • Glycerin;
• • Alkylenglycole, wie beispielsweise Ethylenglycol, Diethylenglycol, Propylenglycol, Butylenglycol, Hexylenglycol sowie Polyethylenglycole mit einem durchschnittlichen Molekulargewicht von 100 bis 1.000 Dalton;
• • technische Oligoglyceringemische mit einem Eigenkondensationsgrad von 1,5 bis 10 wie etwa technische Diglyceringemische mit einem Diglyceringehalt von 40 bis 50 Gew.-%;
• • Methyolverbindungen, wie insbesondere Trimethylolethan, Trimethylolpropan, Trimethylolbutan, Pentaerythrit und Dipentaerythrit;
• • Niedrigalkylglucoside, insbesondere solche mit 1 bis 8 Kohlenstoffen im Alkylrest, wie beispielsweise Methyl- und Butylglucosid;
• • Zuckeralkohole mit 5 bis 12 Kohlenstoffatomen, wie beispielsweise Sorbit oder Mannit,
• • Zucker mit 5 bis 12 Kohlenstoffatomen, wie beispielsweise Glucose oder Saccharose;
• • Aminozucker, wie beispielsweise Glucamin;
• • Dialkoholamine, wie Diethanolamin oder 2-Amino-1,3-propandiol.

To improve the flow behavior, it is also possible to use hydrotropes, such as, for example, ethanol, isopropyl alcohol, or polyols; These substances largely correspond to the initially described carriers. Polyols contemplated herein preferably have from 2 to 15 carbon atoms and at least two hydroxyl groups. The polyols may contain other functional groups, in particular amino groups, or be modified with nitrogen. Typical examples are

• • glycerin;
• Alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol, and polyethylene glycols having an average molecular weight of 100 to 1,000 daltons;
• Technical Oligoglyceringemische with an intrinsic degree of condensation of 1.5 to 10 such as technical Diglyceringemische with a diglycerol content of 40 to 50 wt .-%;
• Methyolverbindungen, in particular trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;
• Lower alkyl glucosides, especially those having 1 to 8 carbons in the alkyl radical, such as, for example, methyl and butyl glucoside;
• Sugar alcohols having 5 to 12 carbon atoms, such as sorbitol or mannitol,
• • sugars having 5 to 12 carbon atoms, such as glucose or sucrose;
• • amino sugars, such as glucamine;
• Dialcohols, such as diethanolamine or 2-amino-1,3-propanediol.

preservative

Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid and the silver ^complexes known under the name Surfacine® and the further classes of compounds listed in Appendix 6, Parts A and B of the Cosmetics Regulation.

Perfume oils and flavors

As perfume oils are called mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers (lily, lavender, roses, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (aniseed, coriander, caraway, juniper), fruit peel (bergamot, lemon, Oranges), roots (macis, angelica, celery, cardamom, costus, iris, calmus), wood (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme), Needles and twigs (spruce, fir, pine, pines), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Furthermore, animal raw materials come into question, such as civet and Castoreum. Typical synthetic fragrance compounds are ester type products, ethers, aldehydes, ketones, alcohols and hydrocarbons. Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethylacetate, linalylbenzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate. The ethers include, for example, benzyl ethyl ether to the aldehydes z. B. the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones z. The alcohols include anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons include mainly the terpenes and balsams. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Also essential oils of lower volatility, which are mostly used as aroma components, are suitable as perfume oils, eg. B. sage oil, camomile oil, clove oil, lemon balm oil, mint oil, cinnamon oil, lime blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labolanum oil and lavandin oil. Preferably, bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol, benzylacetone, cyclamen aldehyde, linalool, Boisambrene Forte, Ambroxan, indole, hedione, Sandelice, citron oil, tangerine oil, orange oil, Allylamylglycolat, Cyclovertal, Lavandinöl, Muskateller Sage oil, β-damascone, geranium oil Bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, fixolide NP, evernyl, iraldeine gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilllat, irotyl and floramate alone or in mixtures.

Suitable flavors are, for example, peppermint oil, spearmint oil, aniseed oil, star aniseed oil, caraway oil, eucalyptus oil, fennel oil, citron oil, wintergreen oil, clove oil, menthol and the like.

dyes

Dyes which may be used are the substances suitable and approved for cosmetic purposes, as described, for example, in the publication "Cosmetic colorants" of the Dye Commission of the Deutsche Forschungsgemeinschaft, Verlag Chemie, Weinheim, 1984, pp. 81-106 are compiled. Examples are Kochillerot A (CI 16255), Patent Blue V (CI 42051), Indigotin (CI 73015), Chlorophyllin (CI 75810), Quinoline Yellow (CI 47005), Titanium Dioxide (CI 77891), Indanthrene Blue RS (CI 69800) and Krapplack (CI 58000). As a luminescent dye and luminol may be included. These dyes are usually used in concentrations of 0.001 to 0.1 wt .-%, based on the total mixture.

The total amount of auxiliaries and additives may be 1 to 50, preferably 5 to 40 wt .-% - based on the means - amount. The preparation of the agent can be carried out by conventional cold or hot processes; It is preferable to work according to the phase inversion temperature method.

FOOD PREPARATIONS

• (a) das Amid der Formel (I),
• (b) Menthol und/oder Mentholverbindungen der Formeln (II), (III) und/oder (IV) oder Aromastoffe sowie
• (c) einen für Nahrungsmittelzwecke zugelassenen Träger.

Another object of the invention relates to food preparations containing

• (a) the amide of the formula (I),
• (b) menthol and / or menthol compounds of the formulas (II), (III) and / or (IV) or flavorings, and
• (c) a carrier authorized for food purposes.

The carriers may be selected from the group formed by water, ethanol and glycerol.

The food preparations are preferably beverages, dairy products, baked goods, and in particular chewing gum and candy.

The preparations according to the invention may contain components (a) and (b) in a weight ratio of 0.1: 99 to 99.9: 1, in particular 10:90 to 90:10, more preferably 25:75 to 75:25 and particularly preferably 40: 60 to 60:40 included. The components (a + b) and (c) may be contained in the weight ratio 0.01: 99.9 to 2:98, preferably 0.5: 99.5 to 1.5: 98.5 and in particular about 1:99. The total content of the components (a + b) in the end products can be between 1 and 5,000, preferably 10 to 4,000 and in particular 100 to 1,000 ppm.

CHEWING GUMS

The preferred food preparations containing the blends of the amides and menthol or menthol compounds as flavoring agents are chewing gums. These products typically contain a water-insoluble and a water-soluble component.

Water-insoluble base

The water-insoluble base, which is also referred to as "gum base", usually comprises natural or synthetic elastomers, resins, fats and oils, plasticizers, fillers, dyes and optionally waxes. The proportion of the base in the total composition is usually from 5 to 95, preferably 10 to 50 and in particular 20 to 35 wt .-% of. In a typical embodiment of the invention, the base is comprised of 20 to 60% by weight of synthetic elastomers, 0 to 30% by weight of natural elastomers, 5 to 55% by weight of plasticizers, 4 to 35% by weight of fillers and minor amounts of additives such as dyes, antioxidants and the like, with the proviso that they are at most in small amounts soluble in water.

Suitable synthetic elastomers include, for example, polyisobutylenes having average molecular weights (by GPC) of 10,000 to 100,000 and preferably 50,000 to 80,000, isobutylene-isoprene copolymers ("butyl elastomers"), styrene-butadiene copolymers (styrene: butadiene ratio e.g. 1: 3 to 3: 1), polyvinyl acetates having average molecular weights (by GPC) of 2,000 to 90,000, and preferably 10,000 to 65,000, polyisoprenes, polyethylene, vinyl acetate-vinyl laurate copolymers, and mixtures thereof. Examples of suitable natural elastomers are rubbers such as smoked or liquid latex or guayules and natural rubbers such as Jelutong, Lechi caspi, Perillo, Sorva, Massaranduba balata, Massaranduba chocolate, Nispero, Rosindinba, Chicle, Gutta hang 1kang and mixtures thereof. The selection of synthetic and natural elastomers and their mixing ratios depend essentially on whether bubbles are to be produced with the chewing gum ("bubble gums") or not. Elastomer blends containing Jelutong, Chicle, Sorva and Massaranduba are preferably used.

In most cases, the elastomers are found to be too hard or too deformable in processing, so it has been found to be advantageous to use special plasticizers, which, of course, in particular also have to meet all requirements for approval as food additives. In this regard, especially esters of resin acids are suitable, for example esters of lower aliphatic alcohols or polyols with completely or partially cured, monomeric or oligomeric resin acids. In particular, the methyl, glycerol or Pentareythritester and mixtures thereof are used for this purpose. Alternatively, terpene resins are also suitable, which can be derived from alpha-pinene, beta-pinene, delta-limonene or mixtures thereof.

Suitable fillers or texturing agents are magnesium or calcium carbonate, ground pumice, silicates, especially magnesium or aluminum silicates, clays, aluminum oxides. Talc, titanium dioxide, mono-, di- and tricalcium phosphate as well as cellulose polymers.

Suitable emulsifiers are tallow, hardened tallow, hardened or partially hydrogenated vegetable oils, cocoa butter, partial glycerides, lecithin, triacetin and saturated or unsaturated fatty acids having 6 to 22 and preferably 12 to 18 carbon atoms and mixtures thereof.

Examples of suitable dyes and whitening agents are the FD and C types, plant and fruit extracts and titanium dioxide permitted for coloring foods.

The base stocks may contain waxes or be wax-free; Examples of wax-free compositions can be found inter alia in the patent specification US 5,286,500 , the contents of which are hereby expressly incorporated by reference.

Water soluble ingredients

In addition to the water-insoluble gum base, chewing gum preparations regularly contain a water-soluble portion formed, for example, from softeners, sweeteners, fillers, flavors, flavor enhancers, emulsifiers, colorants, acidulants, antioxidants and the like, provided that the ingredients have at least sufficient water solubility , Depending on the water solubility of the specific representatives, individual constituents may accordingly belong to both the water-insoluble and the water-soluble phase. However, it is also possible to use combinations of, for example, a water-soluble and a water-insoluble emulsifier, the individual representatives then being in different phases. Usually, the water-insoluble content accounts for 5 to 95 and preferably 20 to 80 wt .-% of the preparation.

Water-soluble softeners or plasticizers are added to the chewing gum compositions to improve chewability and chewing sensation and are typically present in the blends in amounts of from 0.5 to 15 percent by weight. Typical examples are glycerol, lecithin and aqueous solutions of sorbitol, hardened starch hydrolysates or corn syrup.

Suitable sweeteners are both sugar-containing and sugar-free compounds which are used in amounts of 5 to 95, preferably 20 to 80 and in particular 30 to 60 wt .-% based on the chewing gum composition. Typical saccharide sweeteners are sucrose, dextrose, maltose, dextrin, dried invert sugar, fructose, levulose, galactose, corn syrup and mixtures thereof. Suitable sugar substitutes are sorbitol, mannitol, xylitol, hardened starch hydrolysates, maltitol and mixtures thereof. Also suitable as additives are so-called HIAS ("High Intensity Articifical Sweeteners"), for example sucralose, aspartame, acesulfame salts, alitame, saccharin and saccharin salts, cyclamic acid and their salts, glycyrrhizines, dihydrochalcones, thaumatin, monellin and the like, alone or in admixtures. Particularly effective are the hydrophobic HIAS, the subject of the international patent application WO 2002 091849 A1 (Wrigleys) and Stevia extracts and their active ingredients, in particular ribeaudioside A are. The amount used of these substances depends primarily on their performance and is typically in the range of 0.02 to 8 wt .-%.

Fillers such as, for example, polydextrose, raftilose, rafitilin, fructooligosaccharides (NutraFlora), palatinose oligosaccharides, guar gum hydrolysates (Sun Fiber) and dextrins are particularly suitable for the production of low-calorie chewing gums.

The range of other flavors is virtually unlimited and uncritical of the essence of the invention. Usually, the total content of all flavorings is 0.1 to 15 and preferably 0.2 to 5 wt .-% based on the chewing gum composition. Suitable further flavoring agents are, for example, essential oils, synthetic flavors and the like, such as aniseed oil, star aniseed oil, caraway oil, eucalyptus oil, fennel oil, lemon oil, wintergreen oil, clove oil, and the like, which are also used, for example, in oral and dental care products.

The chewing gums may further contain adjuvants and additives which are suitable for example for dental care, especially for controlling plaque and gingivitis, such as. Chlorhexidine, CPC or Trichlosan. In addition, pH regulators (eg, buffer or urea), anti-caries (eg, phosphates or fluorides), biogenic agents (antibodies, enzymes, caffeine, plant extracts) may be included as long as these substances are approved for food, and do not interact in an undesirable manner.

CAPSULES

The preparations of the specific amides and menthol or the menthol compounds alone or else the ready-made cosmetic, pharmaceutical and food preparations can also be present in encapsulated form. In addition to conventional macrocapsules based on gelatin, especially so-called micro- or nanocapsules come into consideration. These are understood by the expert spherical aggregates having a diameter in the range of about 0.0001 to about 5 and preferably 0.005 to 0.5 mm, which contain at least one solid or liquid core, which is enclosed by at least one continuous shell. More specifically, it is finely dispersed liquid or solid phases coated with film-forming polymers, in the preparation of which the polymers precipitate on the material to be enveloped after emulsification and coacervation or interfacial polymerization. According to another method, molten waxes are taken up in a matrix ("microsponge"), which may additionally be enveloped as microparticles with film-forming polymers. According to a third method, particles are coated alternately with polyelectrolytes of different charge ("layer-by-layer" method). The microscopic capsules can be dried like powder. Besides mononuclear microcapsules, multinuclear aggregates, also called microspheres, are known, which contain two or more cores distributed in the continuous shell material. Mono- or polynuclear microcapsules can also be enclosed by an additional second, third, etc., sheath. The shell may be made of natural, semi-synthetic or synthetic materials. Of course, wrapping materials are gum arabic, agar-agar, agarose, maltodextrins, alginic acid or its salts, eg. For example, sodium or calcium alginate, fats and fatty acids, cetyl alcohol, collagen, chitosan, lecithins, gelatin, albumin, shellac, polysaccharides such as starch or dextran, polypeptides, protein hydrolysates, sucrose and waxes. Semisynthetic shell materials include chemically modified celluloses, especially cellulose esters and ethers, eg. As cellulose acetate, ethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose and carboxymethyl cellulose, and starch derivatives, in particular starch ethers and esters. Synthetic envelope materials are, for example, polymers such as polyacrylates, polyamides, polyvinyl alcohol or polyvinylpyrrolidone. Examples of microcapsules of the prior art are the following commercial products (in parentheses is the shell material): Hallcrest Microcapsules (gelatin, gum arabic), Coletica Thalaspheres (marine collagen), Lipotec Millicapseln (alginic acid, agar-agar), Induchem Unispheres (lactose , microcrystalline cellulose, hydroxypropylmethylcellulose); Unicerin C30 (lactose, microcrystalline cellulose, hydroxypropylmethylcellulose), Kobo Glycospheres (modified starch, fatty acid esters, phospholipids), Softspheres (modified agar-agar) and Kuhs Probiol Nanospheres (phospholipids) as well as Primaspheres and Primasponges (chitosan, alginates) and Primasys (phospholipids) , Particularly interesting for the encapsulation of preparations for cosmetic applications are coacervates of cationic polymers, in particular of chitosan, with anionic polymers, especially alginates. Corresponding methods are for example in the publications WO 2001 001926 . WO 2001 001927 . WO 2001 001928 and WO 2001 001929 (Cognis).

gelling agent

Microcapsules often contain the active ingredients dissolved or dispersed in a gel phase. As gelling agents, preference is given to those substances which exhibit the property of forming gels in aqueous solution at temperatures above 40 ° C. Typical examples are heteropolysaccharides and proteins. Preferred thermogelling heteropolysaccharides are agaroses which, in the form of the agar agar to be obtained from red algae, may also be present together with up to 30% by weight of non-gel-forming agaropectins. The main constituent of the agaroses are linear polysaccharides of D-galactose and 3,6-anhydro-L-galactose, which are linked alternately to β-1,3- and β-1,4-glycosidic compounds. The heteropolysaccharides preferably have a molecular weight in the range of 110,000 to 160,000 and are both colorless and tasteless. Pectins, xanthans (including xanthan gum) as well as their mixtures come into consideration as alternatives. Furthermore, preference is given to those types which still form gels in 1% strength by weight aqueous solution which do not melt below 80 ° C. and solidify again above 40 ° C. From the group of thermogeling proteins are exemplified the different types of gelatin.

cationic polymers

Suitable cationic polymers are, for example, cationic cellulose derivatives, such as. Example, a quaternized hydroxyethylcellulose obtainable under the name Polymer JR 400 ^® from Amerchol, cationic starch, copolymers of diallyl ammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers, such. As Luviquat ^® (BASF), condensation products of polyglycols and amines, quaternized collagen polypeptides such as, for example, Lauryldimonium Hydroxypropyl Hydrolyzed Collagen (Lamequat® ^® L / Grunau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers such. B. Amodimethicone, copolymers of adipic acid and Dimethylaminohydroxypropyldiethylentriamin (Cartaretine ^® / Sandoz), copolymers of acrylic acid with dimethyldiallylammonium chloride (Merquat ^® 550 / Chemviron), polyaminopolyamides and their crosslinked water-soluble polymers, cationic chitin derivatives such as quaternized chitosan, optionally microcrystalline distributed, condensation products of dihaloalkylene , such as B. dibromobutane with bis-dialkylamines, such as. B. bis-dimethylamino-1,3-propane, cationic guar gum, such as. ^Jaguar® CBS, ^Jaguar® C-17, ^Jaguar® C-16 from Celanese, quaternized ammonium salt polymers, e.g. B. Mirapol ^® A-15, Mirapol ^® AD-1, Mirapol ^® AZ-1 from Miranol. Preferably, chitosan is used as the encapsulating material. Chitosans are biopolymers and are counted among the group of hydrocolloids. Chemically, they are partially deacetylated chitins of different molecular weight containing the following - idealized - monomer unit:

Unlike most hydrocolloids, which are negatively charged at biological pH levels, chitosans are cationic biopolymers under these conditions. The positively charged chitosans can interact with oppositely charged surfaces and are therefore used in cosmetic hair and body care products as well as pharmaceuticals Preparations used. For the production of chitosans is based on chitin, preferably the shell remains of crustaceans, which are available as cheap raw materials in large quantities. The chitin is thereby in a procedure, the first of Hackmann et al. has been described, usually initially deproteinized by the addition of bases, demineralized by the addition of mineral acids and finally deacetylated by the addition of strong bases, wherein the molecular weights may be distributed over a broad spectrum. Preference is given to using those types having an average molecular weight of 10,000 to 500,000 or 800,000 to 1,200,000 daltons and / or a Brookfield viscosity (1% strength by weight in glycolic acid) below 5000 mPas, a degree of deacetylation in the range from 80 to 88% and having an ash content of less than 0.3% by weight. For reasons of better solubility in water, the chitosans are generally used in the form of their salts, preferably as glycolates.

anionic polymers

The anionic polymers have the task of forming with the cationic membranes. Salts of alginic acid are preferably suitable for this purpose. Alginic acid is a mixture of carboxyl-containing polysaccharides with the following idealized monomer unit:

The average molecular weight of the alginic acids or alginates is in the range of 150,000 to 250,000. In this case, salts of alginic acid are understood as meaning both their complete and their partial neutralization products, in particular the alkali metal salts and, preferably, the sodium alginate ("algin") and the ammonium and alkaline earth salts; mixed alginates, such as, for example, are particularly preferred. As sodium / magnesium or sodium / calcium alginates. In an alternative embodiment of the invention, however, come for this purpose, anionic chitosan derivatives such. As carboxylation and especially Succinylierungsprodukte in question. Alternatively, poly (meth) acrylates having average molecular weights in the range of 5,000 to 50,000 daltons and the various carboxymethylcelluloses come into question. Instead of the anionic polymers, it is also possible to use anionic surfactants or low molecular weight inorganic salts, for example pyrophosphates, for the formation of the enveloping membrane.

encapsulation

For the preparation of the microcapsules is usually prepared from 1 to 10, preferably 2 to 5 wt .-% aqueous solution of the gelling agent, preferably the agar agar ago and heated them under reflux. In the boiling heat, preferably at 80 to 100 ° C, a second aqueous solution is added, which contains the cationic polymer, preferably the chitosan in amounts of 0.1 to 2, preferably 0.25 to 0.5 wt .-% and the active ingredients in amounts of 0.1 to 25 and in particular 0.25 to 10 wt .-%; this mixture is called a matrix. The loading of the microcapsules with active ingredients can therefore also amount to 0.1 to 25% by weight, based on the capsule weight. If desired, water-insoluble constituents, for example inorganic pigments, can also be added at this time to adjust the viscosity, these being added as a rule in the form of aqueous or aqueous / alcoholic dispersions. To emulsify or disperse the active ingredients, it may also be useful to add emulsifiers and / or solubilizers to the matrix. After the preparation of the matrix of gelling agent, cationic polymer and active ingredients, the matrix can optionally be very finely dispersed in an oil phase under high shear in order to produce the smallest possible particles in the subsequent encapsulation. It has proved to be particularly advantageous to heat the matrix to temperatures in the range of 40 to 60 ° C, while the oil phase is cooled to 10 to 20 ° C. In the last, now again obligatory step then the actual encapsulation takes place, d. H. the formation of the enveloping membrane by contacting the cationic polymer in the matrix with the anionic polymers. For this purpose, it is recommended that the optionally dispersed in the oil phase matrix at a temperature in the range of 40 to 100, preferably 50 to 60 ° C with an aqueous, about 1 to 50 and preferably 10 to 15 wt .-% aqueous solution of the anion polymer to treat and, if necessary, at the same time or subsequently to remove the oil phase. The resulting aqueous preparations generally have a microcapsule content in the range of 1 to 10 wt .-%. In some cases, it may be advantageous if the solution of the polymers contains other ingredients, such as emulsifiers or preservatives. After filtration, microcapsules are obtained, which on average have a diameter in the range of preferably about 0.01 to 1 mm. It is recommended to sift the capsules to ensure the most even size distribution possible. The microcapsules thus obtained may have any shape in the production-related framework, but they are preferably approximately spherical. Alternatively, one can also use the anionic polymers for the preparation of the matrix and perform the encapsulation with the cationic polymers, especially the chitosans.

Alternatively, the encapsulation can also be carried out using cationic polymers exclusively, taking advantage of their property of coagulating at pH values above the pKa value.

In a second alternative method, an O / W emulsion is initially prepared for producing the microcapsules according to the invention, which contains an effective amount of emulsifier in addition to the oil body, water and the active ingredients. To prepare the matrix, this preparation is mixed with vigorous stirring with an appropriate amount of an aqueous anionic polymer solution. The membrane formation takes place by adding the chitosan solution. The entire process preferably takes place in the weakly acidic range at pH = 3 to 4. If necessary, the pH is adjusted by adding mineral acid. After membrane formation, the pH is raised to 5 to 6, for example by adding triethanolamine or another base. This results in an increase in the viscosity, the addition of further thickening agents, such as. As polysaccharides, especially xanthan gum, guar-guar, agar-agar, alginates and Tyloses, carboxymethylcellulose and hydroxyethylcellulose, high molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, polyacrylamides and the like can still be supported. Finally, the microcapsules are separated from the aqueous phase, for example by decantation, filtration or centrifugation.

In a third alternative method, the formation of the microcapsules is carried out around a preferably solid, for example, crystalline core by coating it in layers with oppositely charged polyelectrolytes. In this connection, see the European patent EP 1064088 B1 (Max Planck Society).

USE OF PREPARATIONS

• (a) das Amid der Formel (I) und
• (b) Menthol und/oder Mentholverbindungen der Formeln (II), (III) und/oder (IV) oder Aromastoffe

zur Herstellung von kosmetischen Zubereitungen, pharmazeutischen Zubereitungen sowie Nahrungsmittelzubereitungen, wobei der Gesamtgehalt der Komponenten (a + b) in den Endprodukten vorzugsweise zwischen 1 und 5.000, vorzugsweise 10 bis 4.000 und insbesondere 100 bis 1.000 ppm liegt.Finally, the invention further relates to the use of mixtures containing

• (a) the amide of formula (I) and
• (b) menthol and / or menthol compounds of the formulas (II), (III) and / or (IV) or flavorings

for the preparation of cosmetic preparations, pharmaceutical preparations and food preparations, wherein the total content of the components (a + b) in the end products is preferably between 1 and 5,000, preferably 10 to 4,000 and in particular 100 to 1,000 ppm.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• WO 2012061698 A2 [0003]
• US 3111127 [0011]
• US 5725865 [0011]
• US 5843466 [0011]
• WO 2003043431 [0012]
• EP 1332772 A1 [0012]
• US Pat. No. 3,419,543 [0014]
• DE 4226043 A1 [0014]
• DE 2608226 A1 [0016]
• US 6328982 [0016]
• US 4459425 [0017]
• US 6407293 [0018]
• US 6515188 [0018]
• US 4,157,384 [0021]
• US 3488419 [0072]
• DE 2224430 Al [0072]
• DE 2343196 A1 [0072]
• US 5286500 [0092]
• WO 2002091849 A1 [0095]
• WO 2001001926 [0099]
• WO 2001001927 [0099]
• WO 2001001928 [0099]
• WO 2001001929 [0099]
• EP 1064088 B1 [0108]

Cited non-patent literature

• J. Soc. Cosmet. Chem. Pp. 185-200 (1978) [0021]
• R. Lochhead in Cosm. Toil. 108, 95 (1993) [0068]
• "Cosmetic Colorants" of the Dye Commission of the Deutsche Forschungsgemeinschaft, Verlag Chemie, Weinheim, 1984, pp. 81-106 [0079]
• Hackmann et al. [0102]

Claims (13)

Preparations containing (a) 2- (p-tolyloxy) -N- (1H-pyrazol-5-yl) -N - ((thiophen-2-yl) methyl) -acetamide corresponding to the following formula (I)

and their salts, and (b1) menthol and / or menthol compounds of the formulas (II), (III) and / or (IV)

in which X represents -OY or -COZ and Y represents the following groups: (i) a linear or branched alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms or an allyl radical; (ii) a hydroxy or dihydroxyalkyl radical having 1 to 6 carbon atoms; (iii) a residue -OCR ¹ ; (iv) a residue -OCO (M) OH; (v) a residue -OCO-S; (vi) a radical -OC (CH ₂ ) _n COR ² where M is a linear or branched alkyl and / or alkenyl radical having 1 to 10 carbon atoms; S is a carbohydrate moiety having from 5 to 12 carbon atoms; n is 0 or numbers from 1 to 6; R ¹ is a linear or branched alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms or an allyl radical; R ^{2 is} a hydroxyl radical or a radical NR ³ R ⁴ ; R ³ and R ⁴ independently of one another represent hydrogen or a linear or branched alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, while Z represents the following groups: (vii) a radical NR ⁵ R ⁶ or (viii) a radical NHR ⁷ wherein R ⁵ and R ^{6 are} independently hydrogen or a linear or branched alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, a phenyl radical or an alkoxyphenyl radical having 1 to 6 carbon atoms in the alkoxy radical R ^{7 is} a radical - (CH ₂ ) _n COOR ⁸ R ^{8 is} a linear or branched alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms and n is 0 or numbers from 1 to 10 or (b2) flavoring agents. Preparations according to claim 1, characterized in that they contain as component (b) menthol compounds selected from the group consisting of menthol methyl ether, menthone glyceryl acetal (FEMA GRAS 3807), menthone glyceryl ketal (FEMA GRAS 3808) , Menthyl lactate (FEMA GRAS 3748), menthol ethylene glycol carbonates (FEMA GRAS 3805), menthol propylene glycol carbonates (FEMA GRAS 3806), menthyl N -ethyloxamate, monomethyl succinate (FEMA GRAS 3810), monomenthyl glutamate (FEMA GRAS 4006), menthoxy-1, 2-propanediol (FEMA GRAS 3784), menthoxy-2-methyl-1,2-propanediol (FEMA GRAS 3849) and the menthane carboxylic acid esters and amides WS-3, WS-4, WS-5, WS-12, WS-14 and WS-30 and their mixtures. Preparations according to claims 1 and / or 2, characterized in that they contain a cosmetic additive (component c) which is selected from the group consisting of surfactants, oil bodies, emulsifiers, pearlescent waxes, bodying agents, thickeners, superfatting agents, stabilizers , Polymers, silicone compounds, fats, waxes, lecithins, phospholipids, UV protection factors, moisturizers, biogenic agents, antioxidants, deodorants, antiperspirants, antidandruff agents, film formers, swelling agents, insect repellents, self-tanning agents, tyrosine inhibitors (depigmentation agents), hydrotropes, solubilizers, preservatives, perfume oils and dyes and their mixtures. Preparations according to at least one of claims 1 to 3, characterized in that they contain the components (a) and (b) in a weight ratio of 0.1: 99 to 99.9: 1. Preparations according to at least one of claims 1 to 4, characterized in that they contain the components (a + b) and (c) in a weight ratio of 0.01: 99.9 to 2:98. Cosmetic preparations containing (a) the amide of the formula (I), (b) menthol and / or menthol compounds of the formulas (II), (III) and / or (IV) or flavorings, and (c) a carrier approved for cosmetic applications. Cosmetic preparations according to claim 6, characterized in that the carrier is selected from the group formed by water, alcohols having 2 to 6 carbon atoms, polyols having 1 to 10 carbon atoms and 2 to 4 hydroxyl groups and oil bodies. Cosmetic preparations according to claims 6 and / or 7, characterized in that they are products selected from the group consisting of skin care agents, hair care products, personal care products, sunscreens and oral and dental care products. Pharmaceutical preparations containing (a) the amide of the formula (I), (b) menthol and / or menthol compounds of the formulas (II), (III) and / or (IV) or flavoring agents and (c) a carrier approved for pharmaceutical applications for the treatment of cold conditions, characterized in that a therapeutic use is made. Pharmaceutical compositions according to claim 9, characterized in that the carrier is selected from the group formed by water, alcohols having 2 to 6 carbon atoms, polyols having 1 to 10 carbon atoms and 2 to 4 hydroxyl groups and oil bodies. Pharmaceutical compositions according to claims 9 and / or 10, characterized in that they are products selected from the group consisting of sucking pastilles, cold drops, cold suds, cold ointments and cold sprays. Food preparations containing (a) the amide of the formula (I), (b) menthol and / or menthol compounds of the formulas (II), (III) and / or (IV) or flavorings, and (c) a carrier authorized for food purposes. Use of mixtures comprising (a) the amide of the formula (I) and (b) menthol and / or menthol compounds of the formulas (II), (III) and / or (IV) or flavorings for the preparation of cosmetic preparations, pharmaceutical preparations and food preparations.