WO2002050230A1

WO2002050230A1 - Dispersions of nanoparticulate fragrance-containing composite materials

Info

Publication number: WO2002050230A1
Application number: PCT/EP2001/014639
Authority: WO
Inventors: Marcel Roth; Christian Kropf; Christine Schröder
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2000-12-20
Filing date: 2001-12-13
Publication date: 2002-06-27
Also published as: EP1349911A1; DE10063428A1; AU2002219178A1

Abstract

The invention relates to aqueous dispersions of nanoparticulate composite materials, comprising at least one fragrance and an organic support and the particles comprise a mean particle diameter in the range of 1 to 500 nm. The fragrances contained in the composite materials are slowly released. The composite materials are thus preferably suitable for long-term perfuming of substrates, in particular textiles and keratin fibres.

Description

Dispersions of nanoparticulate fragrance-containing composite materials

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 suitable for scenting substrates, especially textiles and keratin fibers.

Fragrance substances, also known as fragrances, have long been used, for example, in washing, rinsing, cleaning or conditioning agents, as well as in cosmetic preparations. Nowadays, they serve less - as in earlier times - to mask unpleasant smells of the components contained in the above-mentioned agents or preparations, but are primarily used to treat both the products themselves and the objects or agents treated with the agents To give surfaces or the body or part of the body treated with the preparations a pleasant and long-lasting fragrance beyond the treatment. In addition, product identification is also achieved by the consumer via the fragrance of the product or the fragrance transmitted by the product to the object being treated; the promotional promotion of the fragrance makes use of this product identification and is used to promote sales. The fragrance note is given a special place in advertising, and thus also in consumer presentation, especially for avivage products. As a result, there is a need both for the manufacturers of detergents, dishwashing detergents or cleaning agents and also for the manufacturers of cosmetic preparations for a way of fixing fragrance substances on objects treated with such agents on the one hand and thus making it possible to do so at or after can be released during the treatment, but on the other hand also extend the time for the release of the fragrances after the treatment. The controlled release of fragrances in a wide variety of preparations in the detergent, dishwashing, cleaning and personal care sector, 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 is of outstanding importance, because - for the reasons mentioned above - both the product, as well as the washing, rinsing, cleaning or finishing agent solution and the objects treated with these agents are intensely and long-lasting fragranced In addition to the methods of applying odoriferous substances to carrier materials and then coating them or encapsulating them or encapsulating them in complex form (for example cyclodextrin odorant complexes), there is the possibility of chemically binding the odoriferous substances to carrier media, the chemical binding being slow split and the Riec material is released. This principle has been implemented, for example, in the esterification of fragrance alcohols, as described in WO 97/30687. The older patent application DE 198 41 147.2 (Henkel KGaA) discloses esters of oligosilicic acids with scented alcohols, which enable objects (including the human body or parts thereof such as hair) to be scented for a long time. However, problems arise when using the compounds of the prior art mentioned in detergents and cleaning agents and also in cosmetic preparations. For example, many of the known compounds cannot be used in aqueous washing and cleaning agents, since they already hydrolyze in the product and the delayed release does not subsequently occur as a result. This is all the more the case since conventional washing and cleaning agents often have pH values which promote the hydrolysis of fragrance esters. Another disadvantage of proposed solutions of the prior art is the fact that the controlled-release formulations of the fragrance substances can often be incorporated only to a limited extent, in particular in preparations with a high water content. This often leads to instability of the preparations, e.g. B. in the form of phase separations and sedimentation. Also undesirable in many cases are the accompanying substances which are introduced into the preparations with the controlled-release formulations of the fragrance substances, such as. B. alcohols as the hydrolysis product of the above-mentioned fragrance esters or cyclodextrins in the case of fragrance-cyclodextrin complexes.

There was therefore still a need to provide technically accessible, inexpensive and widely usable fragrance forms which are particularly suitable for use in detergents, cleaners or conditioners or cosmetic preparations and give the objects treated with them a long-lasting fragrance. The object of the invention was also to provide methods for washing, rinsing, cleaning and finishing as well as for cosmetic treatment of the body, with which a long-lasting fragrance can be applied to the items to be washed, washed or cleaned or to the human body or parts thereof.

Surprisingly, it has now been found that the scent of preparations of the most varied types, for example detergents, dishwashing detergents, cleaning agents, finishing agents or also cosmetic preparations, can be transferred to the objects treated with these preparations and the scent is released over a longer period of time , if the respective preparations contain a nanoparticulate aqueous dispersion of a composite material composed of an organic carrier and at least one fragrance.

The invention therefore relates to 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 and preferably in the range from 10 to 200 nm.

The size specifications are to be understood as the diameter in the direction of the greatest longitudinal expansion of the particles. When producing the particles, particles are always obtained with a size that follows a distribution curve. For example, the method of dynamic light scattering known to the person skilled in the art can be used for the experimental determination of the particle size. As fragrances, also called fragrances, z. B. Compounds from the class of esters, ethers, aldehydes, ketones, alcohols or hydrocarbons can be used. Fragrances of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate (DMBCA), phenylethyl acetate, benzyl acetate, ethyl methylphenylglycinate, allylcyclohexylpropylate, cyclosilate, methyllateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylamylacylateylateylamylateylateylateylamylacylate, stylalylateylateylateylamylacylate, stylalylateylateylate, methylateylateolate, benzylate, The ethers include, for example, benzylethyl ether and ambroxan, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxy acetaldehyde, cyclamenaldehyde, lilial and bourgeonal, the ketones, for example, the jonones, α-isomethylionone and methyl cedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene.

However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Such mixtures are also referred to as perfume oils if they are present as liquids at room temperature.

Natural products from plant sources can also be used as fragrances or fragrance mixtures, 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 as orange blossom oil, neroli oil, orange peel oil and sandalwood oil.

In order to be perceptible, a fragrance must be volatile, whereby in addition to the nature of the functional groups and the structure of the chemical compound, the molar mass also plays an important role. Most fragrances have molecular weights of up to around 300 daltons, while higher molecular weights are an exception. Due to the different volatility of fragrances, the smell of a perfume or fragrance composed of several fragrances changes during evaporation, whereby the Odor impressions are divided into "top note", "heart or middle note"("middlenote" or "body") and "base note"("endnote" or "dry out"). Since the smell is largely based on the intensity of the smell, the top note of a perfume or fragrance does not consist solely of volatile compounds, while the base note largely consists of less volatile, ie non-stick fragrances. When composing perfumes, more volatile fragrances can be bound to certain fixatives, for example, which prevents them from evaporating too quickly. In the subsequent classification of the fragrances into "more volatile" or "adherent" fragrances, nothing is said about the odor impression and whether the corresponding fragrance is perceived as a top or heart note.

Adhesive fragrances that can be used as a fragrance in the context of the present invention are, for example, the essential oils such as angelica root oil, aniseed oil, basil oil, bay oil, champaca blossom oil, noble pine cone oil, elemi oil, eucalyptus oil, fennel oil, spruce oil, gum oil oil, gum oil oil, gum oil oil Helichrysumöl, Ho oil, ginger oil, iris oil, cajeput oil, calamus oil, camomile oil, camphor oil Kanagaöl, cardamom oil, cassia oil, pine needle oil, Kopaϊvabalsamöl coriander oil, spearmint oil, caraway oil, Kuminöl, lavender oil, lemongrass oil lime oil, mandarin oil, melissa oil, Moschuskömeröl, 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, Stemanis oil, Turpentine oil, Thuja oil, Thyme oil, Verbena oil, Verbena oil derbeer oil, wormwood oil, wintergreen oil YlangYlang oil, hyssop oil, cinnamon oil, cinnamon leaf oil, lemon oil, lemon oil and cypress oil. However, the higher-boiling or solid odorants of natural or synthetic origin can also be used as adhesive odorants or odorant mixtures in the context of the present invention. These compounds include the compounds mentioned below 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, ce-bromostyrene, n-decylaldehyde, n-dodecylaldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, geranyl acetate, fenchyl acetate, fenchyl acetate, fenchyl acetate, fenchyl acetate, fenchyl acetate, fenchyl acetate, fenchyl acetate, fenchyl acetate, fenchyl acetate, fenchyl acetate, fenchyl acetate, fenchyl acetate, fenchyl acetate, fenchyl acetate, fenchyl acetate, fenchyl acetate, fenchyl acetate, fenchyl acetate, fenchyl acetate, fenchyl acetate, fenchyl acetate, fenchyl acetate, fenchyl acetate, fenchyl acetate, fenchyl acetate, fenchyl acetate, fenchyl acetate, fenchyl acetate, fenchonyl heptyl acetate, , Heptaldehyde, hydroquinone-dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamyl alcohol, indole, Iran, isoeugenol, isoeugenol methyl ether, isosafrol, jasmon, camphor, karvakrol, carvone, pKresol methyl ether, coumarin, p-methoxyacetophenone, methyl-n-amyl-methyl-phenyl-methyl-acetyl-methyl-methyl-acetyl-methyl-methacrylate , pMethylquinoline, methyl-ß-naphthyl ketone, methyl-n-nonylacetaldehyde, methyl-nnonyl ketone, muscon, ß-naphthol ethyl ether, ß-naphthol methyl ether, nerol, n-nonyl aldehyde, nonyl alcohol, n-octyl aldehyde, p-oxy-acetekanolidone, p -Phenylethyl alcohol, phenyl acetaldehyde dimethyl acetal, phenylacetic acid, Pulegon, Safrol, salicylic acid isoamyl ester, salicyls Acid methyl ester, salicylic acid hexyl ester, salicylic acid cyclohexyl ester, Santalol, Sandelice, Skatol, Terpineol, Thymen, Thymol, Troenan, γ-undelactone, Vanilin, Veratrumaldehyde, Cinnamaldehyde, Zimatalkohol, Cinnamic acid, Cinnamic acid ethyl ester.

The more volatile fragrances include in particular the lower-boiling fragrances of natural or synthetic origin, which can be used alone or in mixtures. 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 can be used. Fragrance mixtures, in particular perfume oils, are preferred.

Suitable organic carriers in the context of the invention are, for example, 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 of the solution.

In the context of the invention, waxes are understood to mean natural or synthetic substances which are kneadable at 20 ° C., solid to brittle hard, coarse to fine crystalline, translucent to opaque, but not glassy, melt undecomposed above approx. 40 ° C. and are already are slightly viscous and not stringy just above the melting point. The waxes to be used for the purposes of the invention differ, for example, from resins in that they generally pass between about 50 and 90 ° C., in exceptional cases even up to 200 ° C., into the molten, low-viscosity state and are practically free from ash-forming compounds are. The waxes are divided into the following three groups according to their origin: natural waxes of plant or animal origin, such as 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, walnut, lanolin (wool wax), pretzel fat, ceresin, ozokerite (earth wax), petrolatum, paraffin waxes, microfax waxes chemically modified waxes (hard waxes), e.g. Montanester waxes, Sasol waxes, hydrogenated jojoba waxes or hydrogenated castor oil as well as synthetic waxes, e.g. Polyalkylene waxes and polyethylene glycol waxes.

Higher fatty alcohols are to be understood as primary aliphatic alcohols of the formula R-OH, in which R represents an aliphatic, linear or branched hydrocarbon radical having 14 to 40 carbon atoms and 0, 1, 2 or 3 double bonds. 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 mixtures thereof. The fatty alcohols can be vegetable, animal or synthetic Be of origin. Synthetic fatty alcohol mixtures which can be used according to the invention are, for. B. in the high pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols. Higher fatty alcohols of vegetable origin are preferred, particularly preferably those with 16 to 18 carbon atoms. Also preferred is cetylstearyl alcohol, which means mixtures of approximately equal parts of cetyl and stearyl alcohol.

Fatty alcohol alkoxylates suitable according to the invention are addition products of 2 to 100 moles of ethylene oxide and / or 0 to 20 moles of propylene oxide with 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)

R ² CH ₃ l + l +

R - N - R ³ X ^" R ⁴ OC-O- (CH ₂ ) _m - N - (CH ₂ ) _n -O-COR ⁵ X ~

R ¹ R ⁶ - (CH ₂ ) ₀

(0 (N)

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 or R ² and COR ⁴ and COR ^{5 are} each is an aliphatic acyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds and R ^{6 is} H or OH, where m, n and o can each independently have the value 1, 2 or 3 and X is either a halide -, Methosulfat-, 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. If quaternized compounds of formula (II) are used which have unsaturated alkyl chains, preference is given to the acyl groups whose corresponding fatty acids 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 group with 12 to 18 carbon atoms, R ^{9 represents} an alkyl group 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)

10

(R) ₃ N - (CH ₂ ) _P - CH - OOCR 11

CH ₂ - OOCR 12

(IV) wherein R ⁰ represents a C _{_1-4} alkyl, alkenyl or hydroxyalkyl group, R ¹¹ and R ¹² are each independently selected a C. ₈ _{28 represents} alkyl group and p is a number between 0 and 5.

It is also possible to use alkylamidoamines, in particular fatty acid amidoamines such as the stearylamidopropyldimethylamine available under the name Tego Amid ^® S 18, and the so-called "esterquats", such as the methylhydroxyalkyldialkoyloxyalkylammonium methosulfates sold under the trademark Stepantex ^® or the products from Cog known under Dehyquart ^® Germany ,

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

It is further preferred if the organic carrier substances have melting or 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 in many cases a substance is suitable as the organic carrier for the composite material which, in the preferred forms of use of the composite material, namely as a constituent of detergents, dishwashing detergents and cleaning agents and cosmetic preparations, is in any case a common ingredient represents.

For the purposes of the invention, an aqueous dispersion is understood to mean a dispersion whose liquid phase consists of water or a homogeneous mixture of water with one or more non-aqueous polar solvents, such as, for example, ethanol, glycerol, ethylene glycol, propylene glycol or N-methylpyrrolidone. In order to be able to form a dispersion, it goes without saying that only organic carriers and fragrances with a sufficiently low solubility in the liquid phase of the dispersion are suitable for the purposes of the invention. This is to be understood to mean that the composite material composed of carrier and fragrance mixture should be sparingly soluble in the liquid phase of the dispersion, with solubility of the constituents of the nanoparticulate composite materials being less than 5% by weight, preferably less than 1% by weight. , based on the total weight of the dispersion, should be understood.

The nanoparticulate composite materials according to the invention are preferably encased by at least one surface modification agent.

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

Suitable surface modifiers are, for example, emulsifiers of the nonionic surfactant type from at least one of the following groups:

(1) Adducts of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms and with alkylphenols with 8 to 15 C atoms in the alkyl group;

(2) Ci _{2 /} ι ₈ fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol; (3) glycerol monoesters and diesters and sorbitan monoesters and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and their ethylene oxide addition products;

(4) alkyl mono- and oligoglycosides with 8 to 22 carbon atoms in the alkyl radical and their ethoxylated analogs;

(5) adducts of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil;

(6) polyol and especially polyglycerol esters such as e.g. Polyglycerol polyricino leat, polyglycerol poly-12-hydroxystearate or polyglycerol dimerate. Mixtures of compounds from several of these classes of substances are also suitable;

(7) adducts of 2 to 15 moles of ethylene oxide with castor oil and / or 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 glycerin, polyglycerin, pentaerythritol, dipentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. methyl glucoside, butyl glucoside Lauryl glucoside) and polyglucosides (eg cellulose);

(9) mono-, di- and trialkyl phosphates as well as 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 glycerol or polyglycerol and

(13) Polyalkylene glycols.

The adducts of ethylene oxide and / or of propylene oxide with fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or with castor oil are known, commercially available products. These are mixtures of homologs, the middle of which 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 corresponds.

Cβ _/ is 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, alkylbenzenesulfonates, alkanesulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether, α-methyl ester sulfonates, sulfofatty acids, alkyl sulfates, alkyl ether sulfates, such as fatty alcohol ether sulfates, Glycerol ether, Hydroxymischethersulfate, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates , Mono- and dialkyl-sulfosuccinates, mono- and dialkyl-sulfosuccinamates, sulfotetriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acylamino acids such as, for example, acylglutamates and acylasucate based products, ), and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.

Zwitterionic surfactants can also be used as emulsifiers. Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyldimethylammonium. glycinate, N-acylamino-propyl-N, N-dimethylammonium glycinate, for example the cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxylmethyl-3-hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethyl carbox. The fatty acid amide derivative known under the CTFA name of Cocamidopropyl Betaine is particularly preferred. Suitable emulsifiers are ampholytic surfactants. Ampholytic surfactants are surface-active compounds which, apart from a _{C8 /} ι ₈ alkyl or - acyl group, contain at least one free amino group and at least one - containing COOH or -SO ₃ H group and are capable of forming inner salts , Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid, each with approximately 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and Ci _{2 /} ιs-acylsarcosine. In addition to the ampholytic emulsifiers, quaternary emulsifiers are also suitable, those of the esterquat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, being particularly preferred.

Protective colloids suitable as surface modifiers are e.g. natural water-soluble polymers such as B. gelatin, casein, gum arabic, lysalbic 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, and 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 contains between 12 and 16 carbon atoms, fatty alcohol alkoxylates and fatty acid alkanolamides. In the event that the organic carrier is a quaternary compound, only nonionic and / or cationic substances come into consideration as surface modification agents, but not anionic ones such as anionic surfactants. The selection of the surface modification agents suitable for a specific organic carrier is possible by means of simple routine tests.

The amount of the surface modifier with respect to the composite material corresponds at least to the amount required to obtain a stable dispersion of nanoparticles of the composite material. This minimum amount can be determined by simple routine tests.

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

The dispersions of nanoparticulate composite materials according to the invention can be based on what is known, for example, from EP-B1 0 506 197 for the production of nanoparticulate wax dispersions

Melt emulsification processes are made by using a possible variant of the process

(a) a melt of the organic carrier is produced with the at least one fragrance, optionally in the presence of a surface modifier,

(b) this melt is dispersed in a liquid, preferably water, with which the melt is not miscible, and (c) the temperature is then cooled below the melting point of the mixture of carrier substance, fragrance substance (s) and optionally surface modification agent.

In the preferred embodiment of the production process, the fragrance mixture is first heated together with the organic carrier material until a liquid phase is formed. Then one or more surface modifiers are added and the mixture is mixed until a homogeneous liquid phase is formed. If necessary, this is further heated. Subsequently, water is added to the liquid, water-immiscible mixture with stirring and with the formation of a microemulsion, which water has previously been heated to a temperature which is above the melting temperature of the mixture of fragrance mixture, organic carrier material and optionally surface modifiers. The microemulsion is then slowly cooled until the microemulsified particles solidify, which is expediently carried out with stirring, a stable dispersion of the nanoparticulate composite materials being formed.

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

Furthermore, modifications of this method are possible which lead to the desired dispersions in the same way. For example, in the first step of the process, the surface modification agent (s) can be heated from the beginning together with the organic carrier material and the fragrance mixture until a homogeneous liquid phase is formed become. In a further variant of the production process, the heated water can be initially introduced and the liquid phase composed of a fragrance mixture, organic carrier material and optionally surface modification agents can be added to the water.

It is understood that work should be carried out at the lowest possible temperatures in order to avoid losses of volatile fragrances. However, preference is given to using fragrance mixtures in which no such evaporation losses occur in the course of the manufacturing process of the composite materials according to the invention that they are undesirably noticeable in the odor profile of the composite materials. According to the inventors' knowledge, however, according to the teaching of the invention, it is also possible to convert those fragrance mixtures into composite materials according to the invention which contain fragrance components with a boiling point below the maximum working temperature of the above-mentioned production process. If particularly low-boiling fragrances are to be used, it may be expedient to add suitable auxiliaries to lower the melting point of the mixture of fragrance mixture, organic carrier material and, if appropriate, surface modification agents.

Instead of water, mixtures of water and non-aqueous polar solvents, such as, for example, ethanol, glycerol, ethylene glycol, propylene glycol or N-methylpyrrolidone, are also suitable according to the invention, provided that the nanoparticulate composite materials are sparingly soluble in these aqueous mixtures, the term sparingly soluble as defined above is.

The dispersions of the nanoparticulate composite materials produced by the process according to the invention are distinguished by a high storage stability.

The composite material should, if appropriate together with the surface modifying agent, be able according to the above production processes described in water or aqueous mixtures to give stable dispersible nanoparticles, the mean particle diameter of the nanoparticles being in the range from 1 to 500 nm. The usable organic carriers and the additional surface modification agents that may be required can be selected by simple routine tests.

The manufacturing process listed is only to be understood as an example and does not constitute a restriction.

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% by weight of the fragrance or fragrance mixture, in each case based on the total weight of the dispersion.

It has been found that the fragrance release of the fragrances present in the composite materials according to the invention is significantly delayed compared to the otherwise identical fragrances present. This means that the fragrance released from the composite material lasts much longer. As far as the fragrance intensity is concerned over the course of time, this is much more uniform with the composite materials according to the invention. While the fragrance intensity of the freely available fragrance substances is initially high and then rapidly drops, the fragrance intensity of the composite material according to the invention is initially lower than that of the free fragrance substance, but then remains at a significantly elevated level over a longer period of time.

It is assumed that the odoriferous substances in the composite materials according to the invention can be present, for example, in the form of solid solutions, enclosed in small cavities in the carrier material or even partially adsorbed on the particle surface. The fragrance contained in the interior of the particles can be released by diffusion to the surface. However, it is also possible to heat the composite materials beyond their melting point within a very short period of time release fragrances contained and thus to cause an almost sudden release of the fragrance associated with the fragrances. The fragrance mixture contained can accordingly be released in a controlled manner from the composite materials according to the invention.

Depending on the fragrance mixture used, the fragrance characteristic of the composite material according to the invention can match or even deviate from that of the free fragrance mixture. By a suitable choice of the fragrances contained in the mixture and their concentration in the fragrance mixture, however, the person skilled in the art can always set the desired fragrance impression for the composite material according to the invention.

It has been found that, according to the teaching of the invention, nanoparticulate composite materials can be produced which adhere particularly well to substrates and in particular to the surfaces of substrates. H. have a particularly high substantivity. This is particularly true for textile fibers and keratin fibers, such as. B. human hair, but among surfaces within the meaning of the invention, for example, surfaces of hard substrates such. B. ceramic tiles, glass, floors or furniture surfaces or other objects to understand.

It is thus possible with the nanoparticulate composite materials according to the invention to give substrates and in particular the surface of substrates a long-lasting fragrance.

Another object of the present invention is accordingly the use of 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, for scenting a substrate, in particular one Textile, a keratin fiber or a hard surface. The aqueous dispersions of nanoparticulate composite materials according to the invention can be stably incorporated into formulations, even if they contain a high proportion of water, and can thus enable higher concentrations of fragrances to be used than when the free fragrances are used.

The invention further comprises the use of 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 washing, rinsing, cleaning and finishing preparations as well as in cosmetic preparations. It has been found that the task of transferring a long-lasting fragrance to the objects treated with these preparations or to the human body or parts thereof through the use of washing, rinsing, cleaning and finishing preparations as well as cosmetic preparations, can be solved if dispersions of nanoparticulate composite materials according to the present invention are used in the respective preparations.

Accordingly, the present invention further provides preparations comprising detergent in addition to the usual constituents of a detergent preparation, detergent in addition to the usual constituents of a detergent preparation, cleaning agent in addition to the usual constituents of a detergent preparation, finishing agent in addition to the usual constituents of a detergent preparation and cosmetic agent in addition to the usual constituents of a cosmetic preparation, 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. Preferred preparations are aqueous preparations.

Liquid detergents, finishing preparations such as fabric softeners and ironing sprays (“spray strength”) are also preferred. Here, washing, rinsing, cleaning and finishing agent preparations comprise as active substances substances such as surfactants (anionic, non-ionic, cationic and amphoteric surfactants), builder substances (inorganic and organic builder substances), bleaching agents (such as, for example, peroxo bleaching agents and chlorine bleaching agents). , Bleach activators, bleach stabilizers, bleach catalysts, enzymes, special polymers (for example those with cobuilder properties), graying inhibitors, dyes and fragrances (perfumes), without the ingredients being restricted to these substance groups. Frequently important ingredients of these preparations are also washing aids and cleaning aids, for which exemplary and non-limiting optical brighteners, UV protection substances, so-called soil repellents, i.e. polymers which counteract re-soiling of fibers or hard surfaces, and silver protection agents.

In a preferred embodiment, the cosmetic preparations are aqueous preparations which are particularly suitable for the treatment of keratin fibers, in particular human hair, or for the treatment of human skin. The hair treatment agents mentioned are in particular agents for treating human hair. The particularly preferred agents according to the invention include hair washing and hair care products such as hair shampoos, hair rinses and hair treatments.

A cosmetic preparation that is also 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 is preferably used, if appropriate after prior dilution, for. B. with water, mixed or dispersed with the other recipe components in a conventional manner at a temperature below the melting point of the composite material. In the preparations described above, the dispersions according to the invention are used in such an amount that the nanoparticulate composite material in an amount in the range from 0.01 to 30% by weight, preferably in an amount in the range from 0.1 to 10% by weight. , and in particular an amount in the range from 0.5 to 2% by weight, based on the total weight of the preparation. In the case of fabric softeners, the preferred use concentration of the nanoparticulate composite material is in the range from 0.1 to 30% by weight, in the case of hair conditioners in the range from 0.1 to 20% by weight, in each case 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 is coated with an olfactory, ie. H. odorally effective amount of a dispersion according to the invention as described above or a preparation as described above is brought into contact.

The invention also relates to washing processes, in particular for machine washing of laundry, washing processes, in particular for machine dishwashing, cleaning processes, in particular for cleaning surfaces or objects, and also finishing processes, in particular for textiles, in which preparations according to the invention are applied to respective aqueous liquors and treated the 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 is sprayed with the preparation or the liquor.

The invention also relates to a cosmetic treatment method in which a cosmetic preparation according to the invention is brought into contact with the human body or a part thereof and is treated cosmetically in this way.

The following examples are intended to illustrate the present invention without restricting it. Unless otherwise stated, all percentages are based on the total weight of the preparations. 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 from paraffin and perfume oil

3 g of perfume oil were dissolved in 100 g of melted paraffin (aliphatic C15 hydrocarbons) and 100 g of Mergital B10 (behenyl alcohol with 10 EO) at 90 ° C. Then 150 g of water preheated to 90 ° C. were added dropwise to form an opalescent liquid, and stirring was continued at 90 ° C. for 30 minutes. A further 150 g of water at 90 ° C. were then added to form a milky, viscous dispersion, the mixture was stirred at 90 ° C. for 5 minutes and then cooled to room temperature. The particle size distribution determined by means of light scattering 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 from paraffin and perfume oil

0.5 g of perfume oil was dissolved in 20 g of melted paraffin (aliphatic C15 hydrocarbons) at 90 ° C., then 20 g of Mergital B 10 were added with stirring and the mixture was stirred for a further 5 minutes. Then 30 g of 90 ° C warm water were slowly added dropwise to form an opalescent gel. A further 29.5 g of water at 90 ° C. were then added rapidly, the mixture was stirred for about 15 minutes and finally slowly cooled to RT to form a stable white suspension. This could be diluted with water to an opalescent solution. The particle size determination gave a volume-weighted average of 31 nm. Example 3 according to the invention: Production of a nanoparticulate dispersion of a composite material from paraffin and perfume oil

0.5 g of perfume oil was dissolved in 20 g of melted paraffin (aliphatic C15 hydrocarbons) at 90 ° C., then 20 g of Mergital B 10 were added with stirring and the mixture was stirred for a further 5 minutes. 59.5 g of water at 90 ° C. were then slowly added dropwise to form an opalescent gel. The mixture was stirred for about 15 minutes and finally slowly cooled to RT to form a stable white dispersion. After dilution with water, a particle size determination using light scattering gave a volume-weighted particle size of 15 nm.

Example 4 according to the invention: Production of a nanoparticulate dispersion of a composite material from 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) at 85 ° C. Then 20 g of Plantacare 1200 UP (C12-C16 alkyl polyglycoside) were added with stirring and stirred for 5 minutes. This mixture was then poured into 55 g of water at 85 ° C. and then heated to 90 ° C. with further stirring and stirred at this temperature for 30 minutes. The temperature was then slowly lowered to room temperature. A milky white, creamy, stable dispersion was obtained. The average particle size was determined to be 300 nm.

Example 5 according to the invention: Production of a nanoparticulate dispersion of a composite material from 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 of Genapol T 500 (C16-18 fatty alcohol + 50EO) were added with stirring and stirred for 5 minutes. This mixture was then added dropwise to 69 g of water at 85.degree. C. and then heated to 90.degree. C. with further stirring and at this temperature Temperature stirred for 30 minutes. The temperature was then slowly lowered to room temperature. A creamy dispersion was obtained. The average particle size was determined to be 150 nm.

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

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

Example 7: Determination of the release kinetics of fragrances

In a model experiment, the release kinetics of individual odoriferous substances from the dispersion according to the invention from example 5 were compared to the conventionally produced dispersion from comparative example 6, in which the perfume oil is in free form, ie not as part of a composite material. For this purpose, samples of both dispersions of the same size were applied to filter paper strips and these were then stored at room temperature for 1 hour or 3 hours. After the storage times, the paper strips were placed in a headspace vessel and thermostatted at 45 ° C. for 15 minutes. The fragrances Herbavert, Dihydromyrcenol, Tetrahydrolinalool and Isobornylacetat then in the steam room were identified by means of a GC-MS coupling and spectrum comparison using a substance library, and quantified in parallel using an FID. The numerical values listed in the following table represent relative Peak areas represent 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 in all cases led to a significantly higher concentration of fragrance in the gas space. This higher concentration in the gas space correlates directly with a correspondingly higher fragrance intensity. It can also be derived directly from the results that, in the case of comparative example 6, the majority of the fragrance substances shown had already evaporated in the course of the first hour of the experiment.

It should be particularly noted that even in the case of the volatile fragrance Herbavert after 1 or 3 hours the dispersion according to the invention led to a significantly higher concentration of fragrance in the gas space, although in this case the fragrance mixture heated to 90 ° C. during the course of the preparation of the dispersion had been, while this was not the case in the comparative example.

Claims

claims:

1. 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.

2. Dispersion according to claim 1, characterized in that the organic carrier is selected from the group formed by 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 is meltable without decomposition at a temperature between 40 and 100 ° C.

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 modifier.

8. Dispersion according to claim 8, characterized in that the at least one surface modifier is selected from the group formed by the nonionic surfactants.

9. Dispersion according to claim 9, characterized in that the at least one surface modifier is an alkyl polyglycoside and / or a fatty alcohol alkoxylate.

10. Dispersion according to one of claims 1 to 9, characterized in that it contains between 1 and 60 wt .-% 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 wt .-% of the fragrance or fragrance mixture, 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

(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 the controlled release of at least one fragrance.

14. Use of a dispersion according to one of claims 1 to 11 for scenting a substrate.

15. Use according to claim 14, characterized in that the substrate is a textile, a keratin fiber or a hard surface.

16. A preparation comprising, in addition to the usual constituents of a detergent preparation, a dispersion as claimed in one of claims 1 to 11.

17. Preparation comprising, in addition to the usual constituents of a detergent preparation, a dispersion according to one of claims 1 to 11. '

18. Preparation comprising, in addition to the usual constituents of a cleaning agent preparation, a dispersion according to one of claims 1 to 11.

19. A preparation comprising, in addition to the usual constituents of a finishing agent preparation, a dispersion as claimed in one of claims 1 to 11.

20. Preparation comprising, in addition to the usual constituents of a cosmetic preparation, a dispersion as claimed in 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 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 the range of 0.5 to 2 wt .-%, based on the total weight of the preparation.

22. A method for scenting a substrate, in which the surface of the substrate is brought into contact with an olfactory effective amount of a dispersion according to one of claims 1 to 11 or a preparation according to one of claims 16 to 20.

23. Washing method, in particular method for machine washing, in which a preparation according to claim 16 is applied to the wash liquor and the laundry is treated with it.

24. Rinsing method, in particular method for automatic dishwashing, in which a preparation according to claim 17 is applied to the washing liquor and the items to be washed are thus treated.

25. Cleaning method for cleaning surfaces or objects, wherein a preparation according to claim 18 is applied to the cleaning liquor and the surfaces or objects are treated with it.

26.Avivageverfahren for textiles, wherein one applies a preparation according to claim 19 in the washing liquor or finishing liquor and the textiles are treated with it.

27. A cosmetic treatment method in which a preparation according to claim 20 is brought into contact with the human body or a part thereof and is thus treated cosmetically.