DE10063428A1 - Dispersions of nanoparticulate fragrance-containing composite materials - Google Patents

Abstract

The invention relates to aqueous dispersions of nanoparticulate composite materials, the composite materials comprising at least one fragrance and an organic carrier and the particles having an average particle diameter in the range from 1 to 500 nm. The fragrance substances contained in them are released slowly from the composite materials. The composite materials are therefore particularly suitable for long-lasting scenting of substrates, in particular textiles and keratin fibers.

Description

The invention relates to aqueous dispersions of nanoparticulate composite materials, wherein the composite materials at least one fragrance and one organic Include carrier and the particles have an average particle diameter in Have range from 1 to 500 nm. From the composite materials the in the fragrances they contain are released more slowly. The composite materials are suitable for scenting substrates, especially textiles and Keratin fibers.

Fragrances, also called fragrances, have long been used, for example, in Detergents, dishwashing detergents or anti-aging agents as well as in cosmetics Preparations used. They serve less nowadays - as in earlier times - the aim of eliminating unpleasant smells of the substances mentioned in the Preparations cover components, but are in the first place The line is therefore used both for the products themselves and those with the Objects or surfaces treated with agents or with the preparations treated body or part of the body a pleasant and about the Give the treatment a long-lasting fragrance. Furthermore is determined by the fragrance of the product or by the product treated object-transferred fragrance at the consumer also a product Identification reached; the promotional promotion of the fragrance makes of this Product identification use and is used to promote sales. Especially at  Aviva agents make the fragrance a special place in advertising and thus also conceded in the consumer presentation. As a result, there is both at the manufacturers of washing, rinsing, cleaning or finishing agents as well as at the manufacturers of cosmetic preparations need a way, on the one hand Fix odoriferous substances on objects treated with such agents and thus only to allow fragrances to be released during or after treatment can, on the other hand, but also the time for the release of the fragrances to prolong the treatment.

The controlled release of fragrances in a wide variety of preparations of the Detergent, dishwashing, cleaning and personal care sectors, often referred to as "controlled release "or" slow release "is the subject of numerous Publications and patent applications. This reflects that on this technical field the release of fragrances of outstanding Importance is that - for the reasons mentioned above - both the product and also the washing, rinsing, cleaning or finishing agent solution and those with them Medicated objects should be scented intensively and for a long time. In addition to the methods of applying odoriferous substances to carrier materials and these then to coat or encapsulate fragrances or in compounds to be stored in complex form (for example cyclodextrin fragrance complexes), there is the possibility of chemically binding the fragrances to carrier media, whereby the chemical bond is slowly broken and the fragrance is released. This principle is, for example, in the esterification of fragrance alcohols has been realized as described in the publication WO 97/30687. The older patent application DE 198 41 147.2 (Henkel KGaA) discloses esters of Oligosilicic acids with scented alcohols, which have a long-lasting scent of objects (including the human body or parts thereof such as hair) enable. However, it occurs when using the compounds mentioned State of the art in detergents and cleaning agents as well as in cosmetic Preparations problems. So many of the known compounds are in aqueous Detergents and cleaning agents cannot be used because they are already in the product  hydrolyze and the delayed release no longer causes later entry. This is all the more the case as common washing and cleaning agents often have pH Have values that favor the hydrolysis of fragrance esters. Another The disadvantage of proposed solutions in the prior art is that limits the possible incorporation of the controlled release formulations of the Fragrance substances, especially in preparations with a high water content. So there is often instability of the preparations, e.g. B. in the form of Phase separations and sedimentation phenomena. Are still undesirable in many cases, the accompanying substances that come with the controlled release formulations the fragrances are introduced into the preparations, such as B. alcohols as Hydrolysis product of the above-mentioned fragrance esters or cyclodextrins in the case of fragrance-cyclodextrin complexes.

So there was still a need to be technically accessible, inexpensive and to provide a wide range of fragrance forms that are particularly suitable for Use in detergents, cleaning agents, anti-aging agents or cosmetics Preparations are suitable and the objects treated with them last a long time lend lasting fragrance. The object of the invention was also a method for Washing, rinsing, cleaning and finishing as well as for the cosmetic treatment of the Provide body with which a long-lasting fragrance on the washing, rinsing or items to be cleaned or the human body or parts thereof can be.

It has now surprisingly been found that the scent of preparations of various types, for example detergents, dishwashing detergents, Detergents, finishing agents or also of cosmetic preparations lets the objects treated with these preparations be transferred and by them The fragrance is released over a long period of time when the respective preparations a nanoparticulate aqueous dispersion of a composite material from a contain organic carrier and at least one fragrance.  

The invention therefore relates to an aqueous dispersion of a nanoparticulate Composite material, wherein the composite material at least one fragrance and comprises an organic carrier and the particles a medium one Particle diameter in the range from 1 to 500 nm and preferably in the range from 10 up to 200 nm.

The size specifications are to be understood as the diameter in the direction of the largest Linear expansion of the particles. When producing the particles you always get Particles with a size that follows a distribution curve. For experimental The particle size can be determined, for example, by the person skilled in the art Dynamic light scattering method can be applied.

As fragrances, also called fragrances, z. B. Class connections which uses esters, ethers, aldehydes, ketones, alcohols or hydrocarbons become. Fragrances of the ester type are e.g. B. benzyl acetate, Phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethyl benzylcarbinylacetate (DMBCA), phenylethyl acetate, benzyl acetate, ethylmethyl phenylglycinate, allylcyclohexylpropionate, styrallylpropionate, benzyl salicylate, Cyclohexyl salicylate, floramate, melusate and jasmine cyclate. Count among the ethers for example benzyl ethyl ether and ambroxan, to the aldehydes z. B. the linear Alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, Cyclamenaldehyde, Lilial and Bourgeonal, to the ketones z. B. the Jonone, α- Isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, citronellol, Eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, among the Hydrocarbons mainly belong to the terpenes like limonene and pinene.

However, mixtures of different odoriferous substances are preferably used create an appealing fragrance together. Such mixtures will be Also known as perfume oils when they are liquids at room temperature available.  

Natural products can also be used as fragrances or fragrance mixtures vegetable sources are used, e.g. B. pine, citrus, jasmine, patchouli, Rose or ylang-ylang oil. Also suitable are muscatel sage oil, Chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, Juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well Orange blossom oil, neroli oil, orange peel oil and sandalwood oil.

To be perceptible, a fragrance must be volatile, in addition to nature the functional groups and the structure of the chemical compound also the Molar mass plays an important role. Most fragrance substances have molecular weights up to about 300 daltons, while higher molecular weights are an exception. Due to the different volatility of fragrances, the changes Smell of a perfume composed of several fragrances or Fragrance during evaporation, taking the smell impressions in "Top note", "heart or middle note" ("middle note" or "body") and "Base note" ("end note" or "dry out") divided. Because the smell perception too is largely due to the smell intensity, the top note is one Perfume or fragrance not only from volatile compounds, while the Base note for the most part from less volatile, i.e. H. non-stick odorants stands. When composing perfumes, more volatile fragrances can be used For example, be bound to certain fixatives, which makes them too fast Evaporation is prevented. In the following classification of the fragrance substances in "Easily volatile" or "sticky" fragrances is therefore about the odor impression and whether the corresponding fragrance is perceived as a top or heart note nothing is said.

Adhesive odoriferous substances used in the context of the present invention as a fragrance can be used, for example, the essential oils such as angelica root oil, Anise oil, arnica flower oil, basil oil, bay oil, champaca flower oil, noble fir oil, Noble pine cone oil, elemi oil, eucalyptus oil, fennel oil, spruce needle oil, galbanum oil, Geranium oil, ginger grass oil, guaiac wood oil, gurjun balsam oil, helichrysum oil, ho oil,  Ginger oil, iris oil, kajeput oil, calamus oil, chamomile oil, camphor oil, kanaga oil, cardamoms oil, cassia oil, pine needle oil, Kopaïvabalsamöl, coriander oil, spearmint oil, Caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, mandarin oil, Melissa oil, musk grain oil, myrrh oil, clove oil, neroli oil, niaouli oil, olibanum oil, Origanum oil, palmarosa oil, patchuli oil, Peru balsam oil, petitgrain oil, pepper oil, Peppermint oil, allspice oil, pine oil, rose oil, rosemary oil, sandalwood oil, celery oil, Spik oil, star anise oil, turpentine oil, thuja oil, thyme oil, verbena oil, vetiver oil, Juniper berry oil, wormwood oil, wintergreen oil, ylang-ylang oil, hyssop oil, cinnamon oil, Cinnamon leaf oil, lemon oil, lemon oil and cypress oil. But also the higher-boiling or solid fragrances of natural or synthetic origin can be used in the context of the present invention as adhesive odoriferous substances or Fragrance mixtures are used. These connections include the the following compounds and mixtures of these: ambrettolide, Ambroxan, α-amylcinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, Anthranilic acid methyl ester, acetophenone, benzylacetone, benzaldehyde, Ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, Benzyl formate, benzyl valerianate, borneol, bornyl acetate, boisambrene forte, α- Bromostyrene, n-decylaldehyde, n-dodecylaldehyde, eugenol, eugenol methyl ether, euka lyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropin, Heptincarboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether, Hydroxycinnamaldehyde, hydroxycinnamyl alcohol, indole, iron, isoeugenol, isoeugenol methyl ether, isosafrol, jasmon, camphor, karvakrol, karvon, pkresol methyl ether, Coumarin, p-methoxyacetophenone, methyl n-amyl ketone, methyl anthranilic acid methyl ester, p-methylacetophenone, methylchavicol, pmethylquinoline, Methyl-β-naphthyl ketone, methyl-n-nonylacetaldehyde, methyl-nnonyl ketone, muscon, β-naphthol ethyl ether, β-naphthol methyl ether, nerol, n-nonyl aldehyde, nonyl alcohol, n-octylaldehyde, p-oxyacetophenone, pentadecanolide, β-phenylethyl alcohol, Phenylacetaldehyde dimethyacetal, phenylacetic acid, Pulegon, Safrol, Salicyl Acid isoamyl ester, salicylic acid methyl ester, salicylic acid hexyl ester, salicylic acid cyclohexyl ester, Santalol, Sandelice, Skatol, Terpineol, Thymen, Thymol, Troenan,  γ-undelactone, vanilin, veratrum aldehyde, cinnamaldehyde, cimate alcohol, cinnamic acid, cinnamon acidic acid ester, cinnamic acid benzyl ester.

The more volatile fragrances include in particular the lower-boiling ones Fragrance substances of natural or synthetic origin, alone or in mixtures can be used. Examples of more volatile fragrances are Diphenyl oxide, limonene, linalool, linalyl acetate and propionate, melusate, menthol, Menthone, methyl-n-heptenone, pinene, phenylacetaldehyde, terpinylacetate, citral, Citronellal.

According to the invention, a single fragrance or mixtures of different Fragrances are used. Fragrance mixtures are preferred, in particular Perfume oils.

Suitable organic carriers are, for example, in the sense of the invention Waxes, higher fatty alcohols, fatty alcohol alkoxylates, fatty acid amides, quaternary Ammonium compounds and quaternary phosphonium compounds, insofar as these have a melting point of more than 40 ° C and are poorly soluble in water. For the purposes of the invention, poor solubility means a solubility of less than 5% by weight, preferably less than 1% by weight, based on the total weight the solution to understand.

For the purposes of the invention, waxes are natural or synthetic substances understand which kneadable at 20 ° C, hard to brittle hard, coarse to fine crystalline, translucent to opaque, but not glassy, above approx. 40 ° C melt undecomposed and low viscosity just above the melting point and are not stringy. The waxes to be used in the sense of the invention differ from resins, for example, in that they are usually about between and 50 and 90 ° C, in exceptional cases also up to 200 ° C, in the melty, low-viscosity state and practically free of are ash-forming compounds. The waxes are divided into two according to their origin  following three groups: natural waxes vegetable or animal Origin, such as B. candelilla wax, carnauba wax, Japanese wax, Esparto grass wax, cork wax, guaruma wax, rice germ oil wax, Sugar cane wax, ouricury wax, montan wax, beeswax, shellac wax, Walrat, Lanolin (wool wax), Bürzelfett, Ceresin, Ozokerit (Erdwachs), Petrolatum, Paraffin waxes, micro waxes; chemically modified waxes (hard waxes), such as. B. Montanester waxes, Sasol waxes, hydrogenated jojoba waxes or hydrogenated Castor oil and synthetic waxes, such as. B. polyalkylene waxes and Polyethylene glycol.

Among higher fatty alcohols are primary aliphatic alcohols of the formula R-OH understand in the R for an aliphatic, linear or branched Hydrocarbon residue with 14 to 40 carbon atoms and 0, 1, 2 or 3 double bindings stands. Typical examples are myristyl alcohol, cetyl alcohol, Palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, Petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, Arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol, Lignoceryl alcohol, ceryl alcohol, myricyl alcohol, melissyl alcohol and their Mi mixtures. The fatty alcohols can be vegetable, animal or synthetic Be of origin. Synthetic fatty alcohol mixtures which can be used according to the invention z. B. in the high pressure hydrogenation of technical methyl esters based of fats and oils or aldehydes from Roelen's oxosynthesis and as Monomer fraction obtained in the dimerization of unsaturated fatty alcohols. Higher fatty alcohols of vegetable origin are preferred, particularly preferred those with 16 to 18 carbon atoms. Also preferred is cetylstearyl alcohol, which means mixtures of approximately equal parts of cetyl and stearyl alcohol are.

Fatty alcohol alkoxylates suitable according to the invention are addition products of 2 up to 100 moles of ethylene oxide and / or 0 to 20 moles of propylene oxide to linear fatty alcohols with 8 to 22 carbon atoms.  

Quaternary ammonium compounds in the context of the invention are understood to mean, for example, quaternary ammonium compounds of the formulas (I) and (II)

where R and R ^{1 is} an acyclic alkyl radical having 12 to 24 carbon atoms, R ^{2 is} a saturated C ₁ -C ₄ alkyl or hydroxyalkyl radical, R ^{3 is} either R, R ¹ or R ² and COR ⁴ and COR ^{5 are} each stands for an aliphatic acyl radical with 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds and R ^{6 stands} for H or OH, where m, n and o can each independently have the value 1, 2 or 3 and X is either Halide, methosulfate, methophosphate or phosphate ion, and mixtures of these compounds. Compounds which contain alkyl radicals having 16 to 18 carbon atoms are particularly preferred.

Examples of cationic compounds of the formula (I) are Didecyldimethylammonium chloride, ditallow dimethylammonium chloride or Dihexadecylammonium. Examples of compounds of the formula (II) are Methyl-N- (2-hydroxyethyl) -N, N-di (tallow acyl-oxyethyl) ammonium methosulfate, bis- (palmitoyl) ethyl hydroxyethyl methyl ammonium methosulfate or methyl N, N bis (acyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulfate. Are quartered Compounds of formula (II) are used which have unsaturated alkyl chains the acyl groups preferred, the corresponding fatty acids of which have an iodine number between 5 and 25, preferably between 10 and 25 and in particular between  15 and 20 and which have a cis / trans isomer ratio (in% by weight) of 30:70, preferably greater than 50:50 and in particular greater than 70:30.

In addition to the quaternary compounds described above, other known compounds can also be used, such as quaternary imidazolinium compounds of the formula (III)

wherein R ⁷ and R ⁸ each represent a saturated alkyl radical with 12 to 18 carbon atoms, R ^{9 represents} an alkyl radical with 1 to 4 carbon atoms or H and Z represents an NH group or oxygen and A is an anion.

Further suitable quaternary compounds are described by formula (IV)

where R ^{10 represents} a C _1-4 alkyl, alkenyl or hydroxyalkyl group, R ¹¹ and R ¹² each independently represents a C _8-28 alkyl group and p is a number between 0 and 5.

Alkylamidoamines, in particular fatty acid amidoamines such as the one available under the name Tego Amid®S 18  Stearylamidopropyldimethylamine, as well as the so-called "Esterquats", such as those under Methylhydroxyalkyl dialkoyloxy sold under the trademark Stepantex® alkylammonium methosulfates or the products from Dehyquart® known from Cognis Germany GmbH.

Organic carriers which are particularly preferred according to the invention are paraffins and quaternary ammonium compounds.

It is further preferred if the organic carriers melt or Have softening points above 40 ° C and below 100 ° C and are meltable without decomposition.

In the sense of the invention it is understood that the nanoparticulate composite material can also comprise two or more organic carriers.

It has proven to be particularly advantageous that as an organic carrier for the composite material is in many cases a substance suitable in the preferred Forms of application of the composite material, namely as a component of washing, Dishwashing detergents and cleaning agents as well as cosmetic preparations, anyway represents usual ingredient.

For the purposes of the invention, an aqueous dispersion is a dispersion understand the liquid phase of water or a homogeneous mixture of Water with one or more non-aqueous polar solvents, such as for example ethanol, glycerin, ethylene glycol, propylene glycol or N-methyl pyrrolidone exists.

To be able to form a dispersion, it is understood that in the sense of Invention only organic carriers and fragrances with a sufficient low solubility in the liquid phase of the dispersion are suitable. Below is to understand that the composite material of carrier and fragrance mixture in  the liquid phase of the dispersion should be sparingly soluble, under Poor solubility is a solubility of the components of the nanoparticulate Composite materials of less than 5% by weight, preferably less than 1% by weight, based on the total weight of the dispersion to be understood.

The nanoparticulate composite materials according to the invention are preferred encased by at least one surface modifier.

Surface modification agents are understood to mean substances which the surface surfaces of the nanoparticles adhere physically, but preferably not with them react chemically. The individual molecules of the adsorbed on the surface Surface modifiers are essentially free of intermolecular Bonds with each other. Surface modification agents include in particular To understand dispersants. Dispersants are, for example, the person skilled in the art also under the terms emulsifiers, protective colloids, wetting agents and detergents known.

Examples of suitable surface modifiers are emulsifiers of the nonionic surfactant type from at least one of the following groups:

• 1. Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of pro pylene oxide to linear fatty alcohols with 8 to 22 carbon atoms, to fatty acids with 12 to 22 carbon atoms and on alkylphenols with 8 to 15 carbon atoms in the alkyl group;
• 2. C _12/18 fatty acid _monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol;
• 3. Glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated fatty acids with 6 to 22 carbon atoms and their ethylene oxide;
• 4. Alkyl mono- and oligoglycosides with 8 to 22 carbon atoms in the alkyl radical and their ethoxylated analogues;  
• 5. Addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil;
• 6. Polyol and especially polyglycerol esters, such as. B. Polyglycerol polyricino leat, polyglycerol poly-12-hydroxystearate or polyglycerol dimerate. Likewise Mixtures of compounds from several of these sub are suitable substance classes;
• 7. Adducts of 2 to 15 moles of ethylene oxide with castor oil and / or ge hardened castor oil;
• 8. _partial esters based on linear, branched, unsaturated or saturated C _6/22 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. Methyl glucoside, butyl glucoside, lauryl glucoside) and poly glucoside (e.g. cellulose);
• 9. mono-, di- and trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates and their salts;
• 10. wool wax alcohols;
• 11. Polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;
• 12. Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol and / or mixed esters of fatty acids with 6 to 22 carbon atoms, Methyl glucose and polyols, preferably glycerin or polyglycerin as well
• 13. polyalkylene.

The adducts of ethylene oxide and / or propylene oxide with fatty alcohol hole, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or castor oil are known, commercially available liche products. These are mixtures of homologs, the middle ones Degree of alkoxylation the ratio of the amounts of ethylene oxide and / or Propylene oxide and substrate with which the addition reaction is carried out equivalent.  

C _8/18 alkyl mono- and oligoglycosides, their preparation and their use are known from the prior art. They are produced in particular by reacting glucose or oligosaccharides with primary alcohols with 8 to 18 carbon atoms. Regarding the glycoside residue, both monoglycosides in which a cyclic sugar residue is glycosidically bonded to the fatty alcohol and oligomeric glycosides with a degree of oligomerization of up to about 8 are suitable. The degree of oligomerization is a statistical mean value which is based on a homolog distribution customary for such technical products.

Typical examples of anionic surfactants and emulsifiers are soaps, Alkyl benzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, Glycerol ether sulfonates, α-methyl ester sulfonates, sulfofatty acids, alkyl sulfates, Alkyl ether sulfates such as, for example, fatty alcohol ether sulfates, glycerol ether sulfates, Hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, Mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, Sulfotriglyce ride, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, Fatty acid sarcosinates, fatty acid taurides, N-acylamino acids such as Acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially vegetable products based on wheat), and alkyl (ether) - phosphates. If the anionic surfactants contain polyglycol ether chains, this is a conventional, but preferably a narrow, homolog distribution have lung.

Zwitterionic surfactants can also 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-dimethylammonium glycinate, for example the cocoalkyldimethylammonium glycinate, N-acylamino-propyl-N, N-dimethylammonium glycinate, for example the cocoacyl aminopropyldimethylammonium glycinate, and 2-alkyl -3-carboxylmethyl-3-hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. The fatty acid amide derivative known under the CTFA name of Cocamidopropyl Betaine is particularly preferred. Suitable emulsifiers are ampholytic ten side. Ampholytic surfactants are surface-active compounds which, in addition to a C _8/18 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and are capable of forming internal salts , Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylamino butyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are the N-cocoalkylamino propionate, the cocoacylaminoethylaminopropionate and the C _12/18 acyl sarcosine. In addition to the ampholytic emulsifiers, quaternary emulsifiers are also suitable, those of the ester quat type, preferably methyl-quaternized difatty acid triethanol amine ester salts, being particularly preferred.

Protective colloids suitable as surface modifiers are e.g. B. natural water-soluble polymers such as B. gelatin, casein, gum arabic, lysalbine acid, starch, albumin, alginic acid and their alkali and alkaline earth metal salts, water-soluble derivatives of water-insoluble polymeric natural substances such. B. Cellulose ethers such as methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose or modified carboxymethyl cellulose, hydroxyethyl starch or hydroxypropyl Guar, as well as synthetic water-soluble polymers, such as. B. polyvinyl alcohols, Polyvinyl butyrals, polyvinyl pyrrolidones, polyalkylene glycols, polyaspartic acids and Polyacrylates.

Preferred surface modification agents are nonionic surfactants, in particular alkyl polyglycosides in which the alkyl radical is between 12 and 16 Contains carbon atoms, fatty alcohol alkoxylates and fatty acid alkanolamides.  

In the event that the organic carrier is a quaternary compound, come as surface modification agents only non-ionic and / or cationic Substances into consideration, but not anionic such as anionic surfactants. The Selection of those suitable for a particular organic carrier Surface modification agents are possible using simple routine tests.

The amount of surface modifier related to the composite material corresponds at least to the amount that is required to provide a stable dispersion Obtain nanoparticles of the composite material. This minimal amount can can be determined by simple routine tests.

As a rule, this is used for the production of the nanoparticulate composite material Composite material and the surface modifier in a weight ratio of 1:50 to 50: 1, preferably 1: 5 to 10: 1 and in particular 1: 2 to 2: 1 used. Instead of the specified proportions of the surface mode Fication agent can also be used in the same amount, a mixture of two or more Surface modification agents are used.

The dispersions of nanoparticulate composite materials according to the invention can be produced based on the melt emulsification process known, for example, from EP-B1 0 506 197 for the production of nanoparticulate wax dispersions, in a possible variant of the process

• a) a melt of the organic carrier with the at least one Fragrance, optionally in the presence of a surface modifier, will be produced,
• b) this melt in a liquid, preferably water, with which the Melt is immiscible, is dispersed and
• c) the temperature is then below the melting point of the mixture Carrier, fragrance (s) and possibly surface modification agent cooled becomes.

In the preferred embodiment of the manufacturing process, the Fragrance mixture together with the organic carrier material so far warmed until a liquid phase is formed. Then one or more Surface modifiers added and the mixture until a homogeneous liquid phase mixed. If necessary, this is further heated. Then the liquid, water-immiscible mixture is added Stir and water to form a microemulsion, which previously was heated to a temperature above the melting temperature of the Mixture of fragrance mixture, organic carrier material and optionally Surface modifiers lies. The microemulsion then becomes slow cooled until the microemulsified particles solidify, which expediently takes place with stirring, with a stable dispersion of nanoparticulate composite materials is formed.

Another object of the invention is thus a method for producing an aqueous dispersion of a nanoparticulate composite material, the composite material comprising at least one fragrance and an organic carrier and the particles having an average particle diameter in the range from 1 to 500 nm, in which

• a) the molten organic carrier with the fragrance, if appropriate in the presence of a surface modifier, is emulsified in water and  
• b) the emulsion is cooled to a temperature below 40 ° C.

Furthermore, modifications of this method are possible which are the same Way to the desired dispersions. For example, in the first Step of the process from the beginning together with the organic carrier material and the fragrance mixture up to Formation of a homogeneous liquid phase can be heated. In another Variant of the manufacturing process, the heated water can be presented and the liquid phase consisting of a fragrance mixture, organic carrier material and if necessary, surface modification agents are added to the water.

It is understood that each worked at the lowest possible temperatures should be avoided to avoid loss of volatile fragrances. Preferably However, such fragrance mixtures are used in which in the course of Manufacturing process of the composite materials according to the invention not so large Evaporation losses occur that these are in the olfactory profile Make composite materials undesirable. After the However, knowledge of the inventors succeeds according to the teaching of the invention, too converting such fragrance mixtures into composite materials according to the invention, which fragrance components with a boiling point below the maximum Working temperature of the above manufacturing process included. If particularly low-boiling fragrances are to be used, it can be appropriate to lower the melting point of the mixture Fragrance mixture, organic carrier material and optionally Add suitable auxiliary substances to surface modification agents.  

According to the invention, mixtures of water and non-aqueous polar solvents, such as ethanol, glycerol, Ethylene glycol, propylene glycol or N-methylpyrrolidone into consideration, insofar as the nanoparticulate composite materials poorly soluble in these aqueous mixtures are, the term poor solubility as defined above.

The dispersions of the nanoparticulate composite materials are characterized by high storage stability out.

The composite material should, if necessary, together with the Surface modifiers, to be able to, according to the above described manufacturing process stable in water or aqueous mixtures to give dispersible nanoparticles, the mean particle diameter of the Nanoparticles is in the range of 1 to 500 nm. The usable organic Carriers and any additional required Surface modification agents can be found in simple routine tests choose.

The manufacturing process listed is only to be understood as an example and represents not a limitation.

The dispersions according to the invention can contain between 1 and 60% by weight of the nanoparticulate composite materials and / or between 0.1 and 10 wt .-% of Fragrance or fragrance mixture contain, each based on the Total weight of the dispersion.

It has been found that the fragrance release of the in the invention Composite materials present fragrances compared to freely available otherwise identical fragrances are significantly delayed. This means, that the fragrance released from the composite material lasts much longer. What  the fragrance intensity over time, so it goes with the composite materials according to the invention much more uniform. While the Fragrance intensity of the free fragrances is high at the beginning and then quickly drops, the fragrance intensity of the composite material according to the invention is initially Although lower than with the free fragrance, it stays on for a long time a significantly higher level.

It is believed that the fragrances in the invention Composite materials, for example in the form of solid solutions, in small cavities of the carrier included or also partially on the particle surface can be adsorbed. The release of the particles contained inside Fragrance substances can be obtained by diffusion to the surface. However, it is also possible by heating the composite materials beyond their melting point release all the fragrances contained within a very short time and thus an almost sudden release of the associated with the fragrances To cause fragrance. Accordingly, from the composite materials according to the invention the fragrance mixture contained can be released in a controlled manner.

Depending on the fragrance mixture used, the fragrance characteristic of composite material according to the invention with that of the free fragrance mixture match or also deviate. By suitable choice of the mixture contained fragrances and their concentration in the fragrance mixture can However, a person skilled in the art is always responsible for the composite material according to the invention Set the desired fragrance impression.

It has been found that, according to the teaching of the invention, nanoparticulate Have composite materials manufactured that are particularly good on substrates and especially stick to the surfaces of substrates, d. H. a particularly high one Have substantivity. This is especially true for textile fibers and keratin fibers, such as B. human hair, but are under surfaces in the sense of Invention, for example, surfaces of hard substrates such. B.  Ceramic tiles, glass, floors or furniture surfaces or others Understand objects.

So it is with the nanoparticulate composite materials according to the invention possible substrates and especially the surface of substrates a long lend lasting fragrance.

Another object of the present invention is accordingly the use an aqueous dispersion of a nanoparticulate composite material, the Composite material at least one fragrance and an organic carrier and the particles have an average particle diameter in the range from 1 to 500 nm, for scenting a substrate, in particular a textile, one Keratin fiber or a hard surface.

The aqueous dispersions of nanoparticulates according to the invention Composite materials can be stable in formulations, even if they are one contain high water content, incorporate, and can therefore higher Use concentrations of odoriferous substances enable than when using the free ones Fragrances.

The invention further comprises the use of an aqueous dispersion of a nanoparticulate composite material, the composite material at least one Fragrance and an organic carrier and the particles a medium Have particle diameters in the range from 1 to 500 nm, in washing, rinsing, Cleaning and finishing preparations and in cosmetic preparations. It it was found that the task of using washing, rinsing, Cleaning and finishing preparations as well as cosmetic preparations long-lasting fragrance on the objects or treated with these preparations can be transferred to the human body or parts thereof, if dispersions are more nanoparticulate in the respective preparations Composite materials according to the present invention can be used.  

The present invention accordingly furthermore relates to preparations Comprehensive as a detergent in addition to the usual ingredients Detergent preparation, as a detergent in addition to the usual ingredients of a Detergent preparation, as a cleaning agent in addition to the usual components of a Detergent preparation, as a finishing agent in addition to the usual components of a Finishing agent preparation and as a cosmetic agent in addition to the usual ingredients a cosmetic preparation, an aqueous dispersion of a nanoparticulate Composite material, wherein the composite material at least one fragrance and comprises an organic carrier and the particles a medium one Have particle diameters in the range from 1 to 500 nm. preferred Preparations are aqueous preparations.

Liquid detergents, finishing preparations such as Fabric softener and ironing sprays ("spray strength").

Here include washing, rinsing, cleaning and conditioning agents as Active substances such as surfactants (anionic, nonionic, cationic and amphoteric surfactants), builder substances (inorganic and organic Builders), bleaches (such as peroxo bleach and chlorine Bleach), bleach activators, bleach stabilizers, bleach catalysts, enzymes, special polymers (for example those with cobuilder properties), Graying inhibitors, dyes and fragrances (perfumes) without the Ingredients are restricted to these substance groups. Often important ones are Ingredients of these preparations also include washing aids and cleaning aids, for the exemplary and non-limiting optical brighteners, UV Protective substances, so-called soil repellents, i.e. polymers that one Counteract re-soiling of fibers or hard surfaces, as well Silver protection agents are mentioned.

The cosmetic preparations are preferred Embodiment to aqueous preparations, which are particularly for treatment  of keratin fibers, especially human hair, or for the treatment of human skin. For the hair treatment products mentioned these are in particular agents for the treatment of human Head hair. Agents particularly preferred according to the invention include Shampoos and hair care products such as shampoos, conditioners and Hair treatments.

A cosmetic preparation which is likewise preferred according to the invention is a Deodorant spray.

To prepare the above-mentioned preparations, the aqueous dispersion of a nanoparticulate composite material according to the invention, if necessary after prior dilution e.g. B. with water, with the others Recipe components in a manner known per se at a temperature below of the melting point of the composite material mixed or dispersed.

In the preparations described above, the inventive Dispersions used in such an amount that the nanoparticulate Composite material in an amount in the range of 0.01 to 30 wt .-%, preferably an amount in the range of 0.1 to 10 wt .-%, and in particular an amount in Range of 0.5 to 2 wt .-% is included, based on the total weight of the Preparation. In the case of fabric softener, the preferred concentration is of the nanoparticulate composite material in the range of 0.1 to 30 wt .-%, in the case of hair rinses in the range of 0.1 to 20 wt .-%, each based on the Total weight of the preparations.

The invention also relates to a method for scenting a Substrate, in which the surface of the substrate with an olfactory, i.e. H. odorally effective amount of a dispersion according to the invention as above described or brought into contact with a preparation as described above becomes.  

The invention also relates to washing processes, in particular for machine washing Washing laundry, rinsing processes, in particular for machine washing Dishwashing, cleaning processes, in particular for cleaning surfaces or Objects, as well as finishing processes, especially for textiles, in which one Preparations according to the invention applied in respective aqueous liquors and the Treated substrates with the liquors containing the preparations. The Treatment can be done e.g. B. also be done in such a way that the object with the Preparation or the fleet is sprayed.

The invention also relates to a cosmetic treatment method in which a cosmetic preparation according to the invention with the human body or brings some of it into contact and treats it cosmetically.

The following examples are intended to illustrate the present invention without it limit. Unless otherwise stated, all percentages are based on the Total weight of the preparations related.  

Examples

A perfume oil of the following composition was used for Examples 1-6 according to the invention:

Example 1 according to the invention Production of a nanoparticulate dispersion of a Composite material made of paraffin and perfume oil

3 g of perfume oil was dissolved in 100 g of melted paraffin (aliphatic C15 Hydrocarbons) and 100 g Mergital B10 (behenyl alcohol with 10 EO) at 90 ° C solved. Subsequently, 150 g of water preheated to 90 ° C. were added dropwise Formation of an opalescent liquid and it was at 90 ° C for 30 minutes further stirred. A further 150 g of water at 90 ° C. were then added Formation of a milky viscous dispersion, stirring continued at 90 ° C for 5 minutes and then cooled to room temperature. The one determined by means of light scattering Particle size distribution gave particle sizes between 30 and 120 nm with a Maximum at 100 nm.

Example 2 according to the invention Production of a nanoparticulate dispersion of a Composite material made of paraffin and perfume oil

0.5 g of perfume oil was dissolved in 20 g of melted paraffin (aliphatic C15 Hydrocarbons) dissolved at 90 ° C, then 20 g Mergital B 10 with stirring added and stirred for a further 5 minutes. Then 30 g were 90 ° C. slowly added warm water to form an opalescent gel. Then another 29.5 g of water at 90 ° C was quickly added, for about 15 Stirred minutes and finally slowly cooled to RT to form a stable white suspension. This turned into an opalescent with water Dilute the solution. The particle size determination gave one volume-weighted average of 31 nm.  

Example 3 according to the invention Production of a nanoparticulate dispersion of a Composite material made of paraffin and perfume oil

0.5 g of perfume oil was dissolved in 20 g of melted paraffin (aliphatic C15 Hydrocarbons) dissolved at 90 ° C, then 20 g Mergital B 10 with stirring added and stirred for a further 5 minutes. Then 59.5 g of water slowly added dropwise from 90 ° C. to form an opalescent gel. It was stirred for about 15 minutes and finally slowly cooled to RT below Formation of a stable white dispersion. After dilution with water, one gave Particle size determination by means of light scattering a volume-weighted Particle size of 15 nm.

Example 4 according to the invention Production of a nanoparticulate dispersion of a Composite material made of a quaternary ammonium compound and perfume oil

1 g of perfume oil was dissolved in 20 g of Dehyquart AU 56 (Dipalmitoylethyl-hydroxyethyl methyl-ammonium methosulfate) dissolved at 85 ° C. Then 20 g of Plantacare 1200 UP (C12-C16 alkyl polyglycoside) added with stirring and for 5 minutes touched. This mixture was then placed in 55 g of water at 85 ° C. and then heated to 90 ° C. with further stirring and at this temperature for 30 Minutes stirred. After that, the temperature was slowly brought to room temperature lowered. A milky white, creamy, stable dispersion was obtained. The middle Particle size was determined to be 300 nm.

Example 5 according to the invention Production of a nanoparticulate dispersion of a Composite material made of a quaternary ammonium compound and perfume oil

1 g of perfume oil was dissolved in 20 g of Dehyquart AU 56 at 80 ° C. Then 10 g Genapol T 500 (C16-18 fatty alcohol + 50EO) added with stirring and for 5  Minutes stirred. This mixture was then in 69 g of water at 85 ° C. added dropwise and then heated to 90 ° C. with further stirring and at this temperature stirred for 30 minutes. After that, the temperature was slowly brought to room temperature lowered. A creamy dispersion was obtained. The mean particle size was determined with 150 nm.

Comparative Example 6 Production of a nanoparticulate dispersion of a quaternary Ammonium compound with an additional perfume oil content

20 g of Dehyquart AU 56 were added with 3 g of Genapol T 500 while stirring 100 ° C melted. This mixture was then in 76 g of water at 85 ° C. added dropwise and then heated to 90 ° C. with further stirring and at this temperature stirred for 30 minutes. After that, the temperature was slowly brought to room temperature lowered, then 1 g of perfume oil added with stirring and for another 5 Minutes stirred. A low-viscosity dispersion was obtained. The middle Particle size was determined to be 150 nm.

Example 7 Determination of the release kinetics of fragrances

The release kinetics of individual odoriferous substances from the Dispersion according to the invention from Example 5 compared to that conventional prepared dispersion from Comparative Example 6, in which the perfume oil in free Shape, d. H. is not present as part of a composite material. To samples of both dispersions of equal size were placed on filter paper strips applied and then stored at room temperature for 1 hour or 3 hours. After the storage times, the paper strips were placed in a headspace jar and thermostated for 15 minutes at 45 ° C. Those then in the steam room Fragrances Herbavert, Dihydromyrcenol, Tetrahydrolinalool and Isobornylacetat were determined using a GC-MS coupling and spectral comparison using a  Substance library identified and quantified in parallel using an FID. The The numerical values listed in the following table represent relative peak areas and are a measure of the concentration of the respective fragrance.

The results shown show that after 1 or 3 hours the dispersion according to the invention to a much higher concentration Fragrance in the gas space led. This higher concentration in the gas space correlates directly with a correspondingly higher fragrance intensity. From the results is also to be deduced immediately that in the case of Comparative Example 6 Most of the odoriferous substances shown already in the course of the first hour of Attempt had evaporated.

It is particularly important to note that even in the case of the volatile fragrance Herbavert after 1 or 3 hours, the dispersion of the invention to a much higher concentration of fragrance in the headspace, although in this case, the fragrance mixture during the course of the preparation of the dispersion 90 ° C had been heated, while this was not the case in the comparative example.

Claims (27)

1. Aqueous dispersion of a nanoparticulate composite material, the Composite material at least one fragrance and an organic carrier and the particles have an average particle diameter in the range of 1 have up to 500 nm. 2. Dispersion according to claim 1, characterized in that the organic Carrier is selected from the group consisting of waxes, higher fatty alcohols, fatty alcohol alkoxylates, fatty acid amides, quaternary Ammonium compounds and quaternary phosphonium compounds. 3. Dispersion according to claim 2, characterized in that the organic Carrier is a paraffin. 4. Dispersion according to claim 2, characterized in that the organic Carrier is a quaternary ammonium compound. 5. Dispersion according to one of claims 1 to 4, characterized in that the organic carrier undecomposed at a temperature between 40 and 100 ° C is fusible. 6. Dispersion according to one of claims 1 to 5, characterized in that the at least one fragrance is a perfume oil. 7. Dispersion according to one of claims 1 to 6, characterized in that the Particles are enveloped by at least one surface modification agent. 8. Dispersion according to claim 8, characterized in that the at least one Surface modifier is selected from the group that is formed of the non-ionic surfactants.   9. Dispersion according to claim 9, characterized in that the at least one Surface modification agent an alkyl polyglycoside and / or Is fatty alcohol alkoxylate. 10. Dispersion according to one of claims 1 to 9, characterized in that it contains between 1 and 60% by weight of the nanoparticulate composite material, based on the total weight of the dispersion. 11. Dispersion according to one of claims 1 to 9, characterized in that it contains between 0.1 and 10% by weight of the fragrance or mixture of fragrances, based on the total weight of the dispersion. 12. A method for producing a dispersion according to any one of claims 1 to 11, in which

• a) the molten organic carrier with the fragrance, optionally in the presence of a surface modifier, is emulsified in water and
• b) the emulsion is cooled to a temperature below 40 ° C.

13. Use of a dispersion according to one of claims 1 to 11 for controlled release of at least one fragrance. 14. Use of a dispersion according to one of claims 1 to 11 for scenting of a substrate. 15. Use according to claim 14, characterized in that the substrate Textile, a keratin fiber or a hard surface.   16. Preparation, comprising in addition to the usual ingredients Detergent preparation is a dispersion according to one of claims 1 to 11. 17. Preparation, comprising in addition to the usual ingredients Detergent preparation is a dispersion according to one of claims 1 to 11. 18. Preparation, comprising in addition to the usual ingredients Detergent preparation is a dispersion according to one of claims 1 to 11. 19. Preparation, comprising in addition to the usual ingredients A softening agent preparation is a dispersion according to any one of claims 1 to 11th 20. Preparation comprising in addition to the usual components of a cosmetic Preparation of a dispersion according to one of claims 1 to 11. 21. Preparation according to one of claims 16 to 20, characterized in that the nanoparticulate composite material in the preparation in an amount in Range of 0.01 to 30% by weight, preferably an amount in the range of 0.1 up to 10% by weight, and in particular an amount in the range from 0.5 to 2% by weight is included, based on the total weight of the preparation. 22. A method for scenting a substrate, in which the surface of the Substrate with an olfactory effective amount of a dispersion after a of claims 1 to 11 or a preparation according to one of claims 16 to 20 is brought into contact. 23. Washing process, in particular machine washing process, wherein one applies a preparation according to claim 16 to the wash liquor and that Treated laundry with it.   24. Rinsing method, in particular method for automatic dishwashing, in which one applies a preparation according to claim 17 to the washing liquor and that Treated wash ware with it. 25. Cleaning method for cleaning surfaces or objects, in which one applied a preparation according to claim 18 in the cleaning liquor and the Treated surfaces or objects with it. 26. A finishing process for textiles, wherein a preparation according to claim 19 in applied the washing liquor or finishing liquor and treated the textiles with it. 27. Cosmetic treatment method, in which a preparation according to Claim 20 in contact with the human body or a part thereof brings and treated it so cosmetically.