EP2963103A1 - pH-sensitive nanocapsules - Google Patents

Abstract

The present invention relates to a process for the preparation of pH-sensitive nanocapsules by means of a miniemulsion process, which process comprises (i) preparing a preemulsion of a mixture of (a) 2.5 to 19.0% by weight of at least one monoethylenically unsaturated C 3 -5-carboxylic acid monomer; (b) from 71.0 to 97.5% by weight of at least one monoethylenically unsaturated C "3-5" carboxylic acid C "1-10" alkyl ester monomer; and (c) from 0.0% to 10.0% by weight of at least one monomer bearing at least two ethylenically unsaturated groups, wherein the monomers are selected such that the copolymer obtainable from the monomer mixture has a theoretical glass transition temperature calculated analogously to the Fox equation T g of 95 ° C or more, in an aqueous solution containing a stabilizer, (ii) a homogenization step to produce a miniemulsion, and (iii) a polymerization step. The invention further relates to a method for encapsulating substances in such nanocapsules, the nanocapsules prepared by the described method, their use, and agents containing these nanocapsules.

Description

The present invention relates to a process for preparing pH-sensitive nanocapsules by a high shear process, the process comprising preparing a preemulsion of a mixture of ethylenically unsaturated monomers in an aqueous solution, a homogenizing step to produce a miniemulsion, and a polymerization step. The invention further relates to a method for encapsulating substances in such nanocapsules, the nanocapsules prepared by the described method, their use and means containing these nanocapsules.

Fragrance molecules are volatile substances used in a variety of fields, such as detergents, cosmetics and sanitary articles, soaps and many others. The high volatility of these substances has led to a variety of strategies for the controlled release of such fragrances have been developed and are commercially available. In general, these fragrance release systems can be divided into two main groups. On the one hand in systems that represent a physical barrier, e.g. a polymer matrix; and secondly, chemical systems that provide the fragrances as less volatile precursor compounds that are chemically cleaved in use and release the fragrance.

As systems based on a physical barrier, microcapsules are already well established in the art. In the field of detergents and cleaners in particular melamine-formaldehyde capsules are used. Microcapsules have a size of 1 to 1000 microns and are usually opened mechanically by breaking, releasing the contents. This is disadvantageous, because the release kinetics are difficult to control. The size of the capsules also causes them to tend to coagulate or sediment in use.

Nanocapsules are an alternative to the known microcapsules. However, due to their size in the range of only 50 to 500 nm, these capsules can not be mechanically opened by rupture, but must be formulated to open in response to particular signals or environmental conditions , Such conditions include temperature changes, light irradiation, change in redox conditions and pH, and many more. However, it is difficult to achieve a high encapsulation efficiency with nanocapsules, which is due to the small size and the fact that the thin shell of the nanocapsules can only very limited serve as a diffusion barrier. It is therefore an object of the present invention to provide nanocapsules which overcome the existing disadvantages and provide high encapsulation efficiency with high colloidal stability. Furthermore, the nanocapsules should allow the controlled release of the substances encapsulated therein.

The present invention solves this problem by containing the nanocapsules in one step by means of a combined emulsion / miniemulsion polymerization approach of a monomer mixture containing pH-sensitive monomers, crosslinking monomers and other monomers in such a manner and amount as to provide them copolymer obtainable has a calculated by the Fox equation theoretical glass transition temperature greater than 95 ° C, and optionally a hydrophobic substance or substance mixture to be encapsulated are prepared. The nanocapsules obtainable in this way have a core-shell morphology, with the polymer built up from the monomers forming the shell and the substance to be encapsulated the core.

The nanocapsules thus obtainable are pH sensitive, i. The content of the nanocapsules can be released controlled by increasing the pH. Furthermore, the nanocapsules are characterized by a very high encapsulation efficiency and a high colloidal stability.

1. (i) Emulgieren einer Monomermischung in eine kontinuierliche wässrige Phase, insbesondere Wasser, die mindestens einen Stabilisator, insbesondere mindestens ein Tensid, umfasst, um eine Präemulsion zu bilden, wobei die Monomermischung bezogen auf das Gesamtgewicht der Monomermischung umfasst:
   1. (a) 2,5 bis 19,0 Gew.-%, insbesondere 5,0 bis 10,0 Gew.-%, mindestens eines einfach ethylenisch ungesättigten C_3-5-Carbonsäure-Monomers;
   2. (b) 71,0 bis 97,5 Gew.-%, insbesondere 80,0 bis 90,0 Gew.-%, mindestens eines einfach ethylenisch ungesättigten C_3-5-Carbonsäure-C_1-10-Alkylester-Monomers;
   3. (c) 0,0 bis 10,0 Gew.-%, insbesondere 0,5 bis 7 Gew.-%, mindestens eines Monomers, das mindestens zwei ethylenisch ungesättigte Gruppen trägt, vorzugsweise eines Divinylbenzols oder eines Di- oder Triesters eines C₂-C₁₀ Polyols mit ethylenisch ungesättigten C₃-C₅-Carbonsäuren, insbesondere eines Di- oder Triesters eines C₂-C₁₀ Alkandiols oder -triols mit ethylenisch ungesättigten C₃-C₅-Carbonsäuren,
   wobei die Monomere derart gewählt sind, dass das aus der Monomermischung erhältliche Copolymer eine analog zur Fox-Gleichung berechnete, theoretische Glasübergangstemperatur T_g von 95°C oder mehr, insbesondere 100°C oder mehr, noch bevorzugter 105°C oder und mehr, aufweist;
2. (ii) Homogenisieren der Präemulsion, um stabilisierte Miniemulsionströpfchen zu bilden, die die Monomermischung enthalten;
3. (iii) Polymerisieren der Monomere in den Miniemulsionströpfchen, um pH-sensitive Nanokapseln zu erhalten.

In a first aspect, the invention relates to a method for producing pH-sensitive nanocapsules, the method comprising:

1. (i) emulsifying a monomer mixture into a continuous aqueous phase, in particular water, which comprises at least one stabilizer, in particular at least one surfactant, to form a preemulsion, the monomer mixture comprising, based on the total weight of the monomer mixture:
   1. (a) 2.5 to 19.0% by weight, especially 5.0 to 10.0% by weight, of at least one monoethylenically unsaturated C _3-5 carboxylic acid monomer;
   2. (b) 71.0 to 97.5% by weight, especially 80.0 to 90.0% by weight, of at least one monoethylenically unsaturated C "_3-5" carboxylic acid C "_1-10" alkyl ester monomer;
   3. (c) 0.0 to 10.0 wt .-%, particularly 0.5 to 7 wt .-% of at least one monomer carrying at least two ethylenically unsaturated groups, preferably a divinyl benzene or di- or triester of a C ₂ -C ₁₀ polyol with ethylenically unsaturated C ₃ -C ₅ -carboxylic acids, in particular a di- or triester of a C ₂ -C ₁₀ -alkanediol or -triol with ethylenically unsaturated C ₃ -C ₅ -carboxylic acids,
   wherein the monomers are selected such that the copolymer obtainable from the monomer mixture has a theoretical value calculated analogously to the Fox equation Glass transition temperature T _g of 95 ° C or more, especially 100 ° C or more, more preferably 105 ° C or more;
2. (ii) homogenizing the preemulsion to form stabilized miniemulsion droplets containing the monomer mixture;
3. (iii) polymerizing the monomers in the miniemulsion droplets to obtain pH-sensitive nanocapsules.

1. (i) Emulgieren der mindestens einen hydrophoben Verbindung und einer Monomermischung in eine kontinuierliche wässrige Phase, insbesondere Wasser, die mindestens einen Stabilisator, insbesondere mindestens ein Tensid, umfasst, um eine Präemulsion zu bilden, wobei die Monomermischung bezogen auf das Gesamtgewicht der Monomermischung umfasst:
   1. (a) 2,5 bis 19,0 Gew.-%, insbesondere 5,0 bis 10,0 Gew.-%, mindestens eines einfach ethylenisch ungesättigten C_3-5-Carbonsäure-Monomers;
   2. (b) 71,0 bis 97,5 Gew.-%, insbesondere 80,0 bis 90,0 Gew.-%, mindestens eines einfach ethylenisch ungesättigten C_3-5-Carbonsäure-C_1-10-Alkylester-Monomers;
   3. (c) 0,0 bis 10,0 Gew.-%, insbesondere 0,5 bis 7 Gew.-%, mindestens eines Monomers, das mindestens zwei ethylenisch ungesättigte Gruppen trägt, vorzugsweise eines Divinylbenzols oder eines Di- oder Triesters eines C₂-C₁₀ Polyols mit ethylenisch ungesättigten C₃-C₅-Carbonsäuren, insbesondere eines Di- oder Triesters eines C₂-C₁₀ Alkandiols oder -triols mit ethylenisch ungesättigten C₃-C₅-Carbonsäuren,
      wobei die Monomere derart gewählt sind, dass das aus der Monomermischung erhältliche Polymer eine analog zur Fox-Gleichung berechnete Glasübergangstemperatur T_g von 95°C oder mehr, insbesondere 100°C oder mehr, noch bevorzugter 105°C oder und mehr, aufweist;
2. (ii) Homogenisieren der Präemulsion, um stabilisierte Miniemulsionströpfchen zu bilden, die die Monomermischung enthalten;
3. (iii) Polymerisieren der Monomere in den Miniemulsionströpfchen, um pH-sensitive Nanokapseln, die die mindestens eine hydrophobe Verbindung einschließen, zu erhalten.

A second aspect relates to a method for encapsulating at least one hydrophobic compound in pH-sensitive nanocapsules, the method comprising:

1. (i) emulsifying the at least one hydrophobic compound and a monomer mixture into a continuous aqueous phase, in particular water comprising at least one stabilizer, in particular at least one surfactant, to form a preemulsion, the monomer mixture comprising, based on the total weight of the monomer mixture:
   1. (a) 2.5 to 19.0% by weight, especially 5.0 to 10.0% by weight, of at least one monoethylenically unsaturated C _3-5 carboxylic acid monomer;
   2. (b) 71.0 to 97.5% by weight, especially 80.0 to 90.0% by weight, of at least one monoethylenically unsaturated C "_3-5" carboxylic acid C "_1-10" alkyl ester monomer;
   3. (c) 0.0 to 10.0 wt .-%, particularly 0.5 to 7 wt .-% of at least one monomer carrying at least two ethylenically unsaturated groups, preferably a divinyl benzene or di- or triester of a C ₂ -C ₁₀ polyol with ethylenically unsaturated C ₃ -C ₅ -carboxylic acids, in particular a di- or triester of a C ₂ -C ₁₀ -alkanediol or -triol with ethylenically unsaturated C ₃ -C ₅ -carboxylic acids,
      wherein the monomers are selected such that the polymer obtainable from the monomer mixture has a glass transition temperature T _g of 95 ° C or more, in particular 100 ° C or more, more preferably 105 ° C or more, calculated in accordance with the Fox equation;
2. (ii) homogenizing the preemulsion to form stabilized miniemulsion droplets containing the monomer mixture;
3. (iii) polymerizing the monomers in the miniemulsion droplets to obtain pH-sensitive nanocapsules including the at least one hydrophobic compound.

A further aspect is directed to the nanocapsules obtainable by the methods described above and their use for the encapsulation of fragrances.

Yet another aspect relates to agents and compositions containing the nanocapsules of the invention.

"At least one" as used herein means 1 or more, ie 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. With regard to an ingredient, the indication refers to the type of ingredient and not on the absolute number of molecules. Thus, "at least one fragrance" means, for example, at least one type of fragrance, ie, one type of fragrance or a mixture of several different riches may be used. The term "weight information" refers to all compounds of the specified type which are contained in the composition / mixture, ie that the composition does not contain any further compounds of this type beyond the stated amount of the corresponding compounds.

All percentages given in connection with the compositions described herein, unless explicitly stated otherwise, relate to% by weight, in each case based on the mixture in question.

"Approximately" as used herein in reference to numerical references refers to ± 10%, preferably ± 5% of the numerical value to which the claim refers. Thus, "about 70 ° C" means 70 ± 7, preferably 70 ± 3.5 ° C.

"Miniemulsion" as used herein refers to an oil-in-water (O / W) emulsion in which the emulsified phase is in the form of droplets or particles, preferably of approximately spherical shape, in the continuous water phase. The droplets / particles preferably have an average size, with an approximately spherical shape an average diameter, in the size range of 30 to 5000 nm, preferably 30 to 1000 nm, in particular 50 to 500 nm, particularly preferably 100 to 300 nm. The averaged above Values refer to the z-average ("z-average") from dynamic light scattering according to ISO 22412: 2008.

The combined emulsion / miniemulsion polymerization technique described herein simplifies the synthesis of the pH-sensitive nanocapsules by causing nucleation to occur substantially in the droplets, thus permitting the introduction of highly hydrophobic compounds. Because of the relatively larger amounts of water-soluble (meth) acrylic acid, such systems can not be considered classic miniemulsion systems, but rather are a combination of emulsion and miniemulsion polymerization that combines the advantages of both techniques.

"Glass transition temperature" or " _Tg " as used herein refers to the temperature at which a given polymer transitions from a solidified glassy state to a rubbery state and awakens polymer segment mobility. It is related to the stiffness and free volume of a polymer and can be experimentally determined by known methods such as Dynamic Mechanical Thermal Analysis (DMTA) or Differential Scanning Calorimetry (DSC). Both methods are in the art known. It should be noted that different glass transition temperatures for an identical polymer system can be obtained, depending on the measurement method and the measurement conditions used or the thermal history of the polymer sample. In fact, the indication of a defined temperature already has a certain inaccuracy, since the glass transition typically takes place within a temperature range. In addition, glass transition temperatures of nanocapsules are experimentally difficult to access and not every determination method is suitable. The glass transition temperatures reported herein are therefore calculated theoretically analogous to the Fox equation unless otherwise indicated. In the following, the correspondingly calculated values of the glass transition temperature are sometimes referred to as "estimated".

The Fox equation (cf. TG Fox, Bull. Phys. Soc. 1 (1956) p. 123 ) states that the reciprocal glass transition temperature of a copolymer can be calculated using the proportions by weight of the comonomers used and the glass transition temperatures of the corresponding homopolymers of the comonomers: $$\frac{1}{T_G}={\displaystyle \underset{i=1}{\overset{n}{\Sigma }}}\frac{w_i}{T_{G.i}}$$

In the general equation, n represents the number of runs via the monomers used, w _i the mass fraction of the particular monomer i (in% by weight) and T _{g, i} the respective glass transition temperature of the homopolymer from the respective monomers i in K (Kelvin).

The values for the glass transition temperatures of the corresponding homopolymers can also be taken from relevant reference works (cf. J. Brandrup, EH Immergut, EA Grulke, "Polymer Handbook", 4th edition, Wiley, 2003 ). For some selected monomers, the corresponding glass transition temperatures of the homopolymers used in the calculation or relevant are listed below: methyl acrylate (MA), T _g = 10 ° C .; Methyl methacrylate (MMA), T _g = 105 ° C; Ethyl acrylate (EA), T _g = -24 ° C; Ethyl methacrylate (EMA), T _g = 65 ° C; n-butyl acrylate (BA), T _g = -54 ° C; n-butyl methacrylate (BMA), T _g = 20 ° C; n-hexyl acrylate (HA), T _g = 57 ° C; n- hexyl methacrylate (HMA), T _g = -5 ° C; Styrene (S), T _g = 100 ° C; Cyclohexyl acrylate (CHA), _Tg = 19 ° C; Cyclohexyl methacrylate (CHMA), T _g = 92 ° C; 2-ethylhexyl acrylate (EHA), T _g = -50 ° C; 2-ethylhexyl methacrylate (EHMA), T _g = -10 ° C; Isobornyl acrylate (IBOA), T _g = 94 ° C; Isobornyl methacrylate (IBOMA), T _g = 110 ° C; Acrylic acid (AA), T _g = 105 ° C; Methacrylic acid (MAA), T _g = 228 ° C.

It should be noted that in the present case when using polyvinylically or ethylenically unsaturated, radically polymerizable monomers (so-called "branching" or "crosslinker") these are not included in the calculation of the glass transition temperature. The values calculated by means of the listed equation as described above are therefore referred to herein as "theoretically calculated analogous to the Fox equation" or "estimated".

The terms "perfume" and "perfume" are used interchangeably herein and refer, in particular, to those which have a fragrance that people find pleasing.

The method described herein is based on a polymerization-induced phase separation determined by the interaction with water and in which a hydrophobic compound is entrapped in a slightly less hydrophobic polymer shell. The formation of nanocapsules by phase separation is based on the poor solubility of a polymer in a solution. Here, the organic liquid to be included serves as a solvent for the monomers, whereas after the polymerization, it can no longer function as a solvent for the polymer.

In the methods described herein, the compound or compound mixture to be encapsulated is preferably a compound that is liquid at room temperature and normal pressure. "Liquid", as used in this context, includes all substances which are flowable under the conditions mentioned. In such embodiments, the monomers of the monomer mixture are predominantly hydrophobic enough to be soluble in the compound to be encapsulated. In various embodiments, the monomer mixture can therefore be used as a solution of the monomers in at least one hydrophobic compound. Alternatively, the compound to be encapsulated may also be a solid which is soluble in the monomers or other constituents of the monomer mixture. The other constituents may be, for example, further compounds to be encapsulated or adjuvants. In this case, the monomers are then used as solvents for the compound to be encapsulated. Although not preferred according to the invention, the compound to be encapsulated and the monomers may also be dissolved in an organic, water-immiscible solvent and the resulting solution emulsified in step (i) in the continuous phase.

In order for the hydrophobic compound to be effectively encapsulated, it is necessary that the compound be sufficiently hydrophobic so that it does not interact with the polymer formed from the monomers such that it excessively swells and thereby becomes more permeable to the compound. It is therefore preferred that the at least one hydrophobic Compound has a Hansen parameter δ _t of less than 20, in particular less than 19; and / or has a Hansen parameter δ _h of less than 10, in particular less than 6.

The Hansen parameter is a widely used parameter in polymer chemistry for comparing the solubility or miscibility of various substances. This parameter was developed by Charles Hansen to predict the solubility of one material in another. The cohesive energy of a liquid is considered, which can be divided into at least three different forces: (a) dispersion forces between the molecules δ _d, (b) dipolar intermolecular forces between the molecules δ _p and (c) hydrogen bonds between the molecules δ _h. These three parameters can be combined into a parameter δ _t according to the formula δ _t ² = δ _d ² + δ _p ² + δ _h ² . The more similar the Hansen parameter of different materials, the better they are miscible.

It is further preferred that the hydrophobic compound does not show a strong interfering side reaction in radical polymerization (e.g., by radical scavengers such as phenols) or with the monomers (e.g., no Michael reaction). The hydrophobic compound is therefore preferably inert under the conditions used in relation to the monomers and the reactants used in the polymerization.

In various embodiments, the hydrophobic compound is a hydrophobic perfume or a hydrophobic perfume mixture selected from synthetic, semi-synthetic or natural perfumes or perfume mixtures.

Natural perfume mixtures as available from vegetable sources include, but are not limited to, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil. Also suitable are Muskateller sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil and orange blossom oil, neroli oil, orange peel oil and sandalwood oil. Other suitable perfume mixtures are essential oils such as angelica root oil, aniseed oil, arnica blossom oil, basil oil, bay oil, champa blossom oil, fir oil, pinecone oil, elemi oil, eucalyptus oil, fennel oil, pine needle oil, galbanum oil, geranium oil, ginger grass oil, guaiac wood oil, gurdy balm oil, helichrysum oil, ho oil, ginger oil, iris oil , Cajuput oil, calamus oil, camomile oil, camphor oil, kanga oil, cardamom oil, cassia oil, pine oil, copaiba balsam, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, tangerine oil, lemon balm oil, musk kernel oil, myrrh oil, clove oil, neroli oil, niaouli oil, olibanum oil, oregano oil , Palmarosa oil, Patchouli oil, Peruvian balsam oil, Petitgrain oil, Pepper oil, Peppermint oil, Pimento oil, Pine oil, Rose oil, Rosemary oil, Sandalwood oil, Celery oil, Spik oil, Star aniseed 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 oil, citronella oil, lemon oil and cypress oil.

Also suitable are the various fragrance aldehydes, such as, for example, adoxal (2,6,10-trimethyl-9-undecenal), anisaldehyde (4-methoxybenzaldehyde), cymal (3- (4-isopropylphenyl) -2-methylpropanal), ethylvanillin, florhydral ( 3- (3-isopropylphenyl) butanal]), helional (3- (3,4-methylenedioxyphenyl) -2-methylpropanal), heliotropin, hydroxycitronellal, lauraldehyde, lyral (3- and 4- (4-hydroxy-4-methylpentyl) 3-cyclohexene-1-carboxaldehyde), methylnonylacetaldehyde, Lilial (3- (4-tert-butylphenyl) -2-methylpropanal), phenylacetaldehyde, undecylenealdehyde, vanillin, 2,6,10-trimethyl-9-undecenal, 3-dodecene -1-al, alpha-n-amylcinnamaldehyde, melonal (2,6-dimethyl-5-heptenal), 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde (triplalite), 4-methoxybenzaldehyde, benzaldehyde, 3- ( 4-tert-butylphenyl) -propanal, 2-methyl-3- (para-methoxyphenyl) propanal, 2-methyl-4- (2,6,6-timethyl-2 (1) -cyclohexen-1-yl) butanal, 3-phenyl-2-propenal, cis- / trans-3,7-dimethyl-2,6-octadiene-1-al, 3,7-dimethyl-6-octene-1-al, [(3,7-dimethyl -6-octenyl ) oxy] acetaldehyde, 4-isopropylbenzylaldehyde, 1,2,3,4,5,6,7,8-octahydro-8,8-dimethyl-2-naphthaldehyde, 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde , 2-methyl-3- (isopropylphenyl) propanal, 1-decanal, 2,6-dimethyl-5-heptenal, 4- (tricyclo [5.2.1.0 (2,6)] decylidene-8) -butanal, octahydro 4,7-methane-1H-indenecarboxaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, para-ethyl-alpha, alpha-dimethylhydrocinnamaldehyde, alpha-methyl-3,4- (methylenedioxy) -hydrocinnamaldehyde, 3,4-methylenedioxybenzaldehyde, alpha n-hexylcinnamaldehyde, m-cymene-7-carboxaldehyde, alpha-methylphenylacetaldehyde, 7-hydroxy-3,7-dimethyloctanal, undecenyl, 2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde, 4- (4 Methyl 3-pentenyl) -3-cyclohexene carboxaldehyde, 1-dodecanal, 2,4-dimethylcyclohexene-3-carboxaldehyde, 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde, 7-methoxy-3 , 7-dimethyloctan-1-al, 2-methylundecanal, 2-methyldecanal, 1-nonanal, 1-octanal, 2,6,10-trimethyl-5,9-undecadienal, 2-methyl-3- (4-tert-butyl) butyl) propanal, dihydrocinnamaldehyde, 1-methyl-4- (4- methyl-3-pentenyl) -3-cyclohexene-1-carboxaldehyde, 5- or 6-methoxy-hexahydro-4,7-methanindane-1 or 2-carboxaldehyde, 3,7-dimethyloctan-1-al, 1-undecanal, 10-undecene-1-al, 4-hydroxy-3-methoxybenzaldehyde, 1-methyl-3- (4-methylpentyl) -3-cyclohexenecarboxaldehyde, 7-hydroxy-3,7-dimethyl-octanal, trans-4-decenal, 2,6-nonadienal, para-tolylacetaldehyde, 4-methylphenylacetaldehyde, 2-methyl-4- (2,6,6-trimethyl-1-cyclohexen-1-yl) -2-butenal, ortho-methoxycinnamaldehyde, 3,5, 6-trimethyl-3-cyclohexene carboxaldehyde, 3,7-dimethyl-2-methylene-6-octenal, phenoxyacetaldehyde, 5,9-dimethyl-4,8-decadienal, peonyaldehyde (6,10-dimethyl-3-oxa-5, 9-undecadiene-1-al), hexahydro-4,7-methanindane-1-carboxaldehyde, 2-methyloctanal, alpha-methyl-4- (1-methylethyl) benzene-acetaldehyde, 6,6-dimethyl-2-norpinen-2 propionaldehyde, para-methylphenoxyacetaldehyde, 2-methyl-3-phenyl-2-propen-1-al, 3,5,5-trimethylhexanal, hexahydro-8,8-dimethyl-2-naphthaldehyde, 3-propylbicyclo [2.2.1] -hept-5-en-2-carbaldehyde, 9-decenal, 3-methyl-5-phenyl 1-pentanal, methylnonylacetaldehyde, hexanal, trans-2-hexenal and mixtures thereof.

Preferred aldehydes include, without limitation, lilial, helional, anisaldehyde, cyclamen aldehyde, triplal, melonal, methyl undecanal, undecanal, nonanal and octanal.

Suitable perfume ketones include, but are not limited to, methyl-betanaphthyl ketone, muskindanone (1,2,3,5,6,7-hexahydro-1,1,2,3,3-pentamethyl-4H-inden-4-one ), Talalum (6-acetyl-1,1,2,4,4,7-hexamethyltetralin), alpha-damascone, beta-damascone, delta-damascone, iso-damascone, damascenone, methyldihydrojasmonate, menthone, carvone, camphor, koavon (3,4,5,6,6-pentamethylhept-3-en-2-one), fenchone, alpha-ionone, beta-ionone, gamma-methyllonone, fleuramon (2-heptylcyclopentanone), dihydrojasmon, cis-jasmone, 1 - (1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl-2-naphthalenyl) ethan-1-one and isomers thereof, methyl cetrenyl ketone, acetophenone, methyl acetophenone, para-methoxyacetophenone, methyl betanaphthyl ketone, benzylacetone, benzophenone, para-hydroxyphenylbutanone, celery ketone (3-methyl-5-propyl-2-cyclohexenone), 6-isopropyldeca-hydro-2-naphthone, dimethyloctenone, frescomenthe (2-butane -2-ylcyclohexan-1-one), 4- (1-ethoxyvinyl) -3,3,5,5-tetramethylcyclohexanone, methylheptenone, 2- (2- (4-methyl-3-cy clohexen-1-yl) propyl) cyclopentanone, 1- (p-menthene-6 (2) yl) -1-propanone, 4- (4-hydroxy-3-methoxyphenyl) -2-butanone, 2-acetyl 3,3-dimethylnorbornane, 6,7-dihydro-1,1,2,3,3-pentamethyl-4 (5H) in-danone, 4-damascol, dulcinyl (4- (1,3-benzodioxol-5-yl ) butan-2-one), hexalon (1- (2,6,6-trimethyl-2-cyclohexene-1-yl) -1,6-heptadien-3-one), isocyclone E (2-acetonaphthone-1, 2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl), methyl nonyl ketone, methylcyclocitron, methyl lavender ketone, orivone (4-tert-amylcyclohexanone), 4-tert-butylcyclohexanone, dolphone ( 2-pentylcyclopentanone), Muscon (CAS 541-91-3), neobutenone (1- (5,5-dimethyl-1-cyclohexenyl) pent-4-en-1-one), Plicaton (CAS 41724-19-0) , Veloutone (2,2,5-trimethyl-5-pentylcyclopentan-1-one), 2,4,4,7-tetramethyl-oct-6-en-3-one, tetrameran (6,10-dimethylundecene-2-one) on) and mixtures thereof.

Other suitable fragrances include, but are not limited to, ambrettolide, ambroxan, anethole, anisalcohol, anisole, methyl anthranilate, ethyl benzoate, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerate, borneol, bornyl acetate, Boisambrene forte, α-bromostyrene, eugenol, eugenol methyl ether , Eucalyptol, farnesol, fenchyl acetate, geranyl acetate, geranyl formate, heptincarboxylic acid methyl ester, hydroquinone dimethyl ether, hydroxycinnamyl alcohol, indole, iron, isoeugenol, isoeugenol methyl ether, isosafrole, camphor, Karvakrol, Karvon, p-cresol methyl ether, coumarin, methyl anthranilate, methylchavikol, p-methylquinoline, Muskon , β-naphtholethyl ether, β-naphthol methyl ether, nerol, n-nonyl alcohol, pentadecanolide, β-phenylethyl alcohol, phenylacetaldehyde dimethyacetal, phenylacetic acid, pulegone, safrole, salicylic acid isoamyl ester, methyl salicylate, hexyl salicylate, cyclohexyl salicylate, santalol, sandelice, skatole , Terpineol, Thymen, thymol, troenan, γ-undelactone, cimat alcohol, cinnamic acid, cinnamic acid ethyl ester, cinnamic acid benzyl ester.

Further examples of more readily volatile fragrances are diphenyloxide, limonene, linalool, linalyl acetate and propionate, melusate, menthol, menthone, methyl-n-heptenone, pinene, terpinyl acetate, citral, citronellal.

Preferred according to the invention are alpha-pinene, lilial, citronellal, citronellol, ionone, alpha-damascone, beta-damascone, jasmon and mixtures thereof.

For controlled release, the nanocapsules are designed so that the polymer shell is pH-sensitive due to the incorporation of acidic monomers. After polymerization, the solutions have a pH in the range of 2 to 4, especially about 3. In protonated form and optionally by the use of a crosslinker, the polymer shell is a relatively impermeable diffusion barrier for the encapsulated substance. Deprotonate at increasing pH the acidic monomers in the polymer shell and thereby increase the hydrophilicity of the polymer shell. This swells in response to the attachment of water molecules and thus becomes more permeable to the encapsulated fragrances. In addition, the nanocapsules are temperature sensitive, depending on the T _{g of} the copolymer. Increasing the temperature leads to a higher mobility of the polymer chains in the shell and thereby to a widening of the polymer shell.

The term "pH sensitive" as used herein refers to the property of polymers to respond to changes in the pH of the surrounding medium with protonation or deprotonation of ionic groups, especially carboxyl groups in the polymer chain. This protonation or deprotonation is reversible and influences the encapsulation properties of the polymer by virtue of the changes in the hydrophilicity and the swellability with water molecules. Such materials swell in response to the increase in pH and thereby become more permeable.

In the following, the invention will be described by reference to certain specific embodiments. However, it is not intended that the invention be limited to these embodiments, but that it be readily adapted to use other monomers, stabilizers, surfactants, and initiators. Incidentally, this also applies to the explicitly mentioned and exemplary tested fragrances. Such embodiments are also within the scope of the invention.

In a first step (i) of the process according to the invention, a surfactant-stabilized preemulsion is prepared. The preemulsion contains the monomer mixture described above and at least one stabilizer, in particular a surfactant, and optionally one or more hydrophobic compounds in the form of an emulsion in an aqueous solvent. The aqueous solvent contains as main component (more than 50, in particular more than 80 vol .-%) of water or may consist of water. In various embodiments, the aqueous solvent may include one or more nonaqueous solvents, for example, selected from monohydric or polyhydric alcohols, alkanolamines, or glycol ethers, provided that they are miscible with water in the given concentration ranges.

These additional solvents are preferably selected from ethanol, n- or isoPropanol, butanols, glycol, propanediol or butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl , ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, diisopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures thereof. In the aqueous solvent, such solvents can be used in amounts of between 0.5 and 35 wt .-%, but preferably less than 30 wt .-% and in particular less than 25 wt .-%.

The monomers used in the processes described are in particular ethylenically unsaturated carboxylic acids and their alkyl esters.

In various embodiments, the at least one monoethylenically unsaturated C ₃ -C ₅ carboxylic acid monomer is selected from methacrylic acid (MAA), acrylic acid (AA), fumaric acid, methylmaleic acid, maleic acid, itaconic acid or mixtures of two or more thereof. Particularly preferred are methacrylic acid (MAA), acrylic acid (AA) or mixtures thereof. Most preferred is methacrylic acid.

In various embodiments, the at least one monoethylenically unsaturated C _3-5 carboxylic acid-C _1-10 alkyl ester monomer is an alkyl acrylate or methacrylate or a mixture thereof. Preference is given to methacrylic acid-C ₁ -C ₅ -alkyl ester monomers, in particular methyl methacrylate (MMA), methacrylic acid-n-butyl ester (BMA) or a mixture thereof. Very particular preference is given to a mixture of methyl methacrylate and n-butyl methacrylate, in particular in a weight ratio of from 3.5: 1 to 16: 1, preferably from 6: 1 to 16: 1. The alkyl radicals can generally be straight-chain or branched, unless stated specifically. The monomer bearing at least two ethylenically unsaturated groups may generally be any compound bearing two ethylenically unsaturated groups, for example two vinyl groups. Examples of suitable compounds include, but are not limited to, divinyl aromatics such as, in particular, divinylbenzenes or multiple esters of a polyol with ethylenically unsaturated carboxylic acids such as, in particular, di- or triesters of a C ₂ -C ₁₀ polyol having ethylenically unsaturated C ₃ -C ₅ - carboxylic acids. The latter are, in various embodiments, diesters of methacrylic acid or acrylic acid with 1,3-propanediol, 1,4-butanediol or 1,5-pentanediol, in particular a methacrylic acid ester of 1,4-butanediol. Preference is given to di- and triacrylates or di- and trimethacrylates of polyhydric alcohols.

The compounds mentioned serve as crosslinkers in the monomer mixtures. Such a three-dimensional crosslinking of the resulting polymer is important in order to ensure the structural integrity of the nanocapsule even when the polymer swells as the pH increases.

In various embodiments of the invention, with the monomer mixture in step (i), an ultrahydrophobic compound, in particular a C _12-28 hydrocarbon, more preferably a C _14-26 alkane, may also be emulsified in the continuous phase. C _14-26 monoalcohols or monocarboxylic acids may also be suitable. The ultrahydrophobic compound may also be a polymerizable C _12-28 hydrocarbon; possible compounds include, but are not limited to, lauryl (meth) acrylate (LA or LMA), tetradecyl (meth) acrylate (TDA or TDMA), hexadecyl ( meth) acrylate (HDA or HDMA), octadecyl (meth) acrylate (ODA or ODMA), eicosanyl (meth) acrylate, behenyl (meth) acrylate and mixtures thereof. If such ultrahydrophobic polymerizable compounds are used, they are not included in the calculation of the glass transition temperature analogous to the Fox equation (see above).

In various further embodiments of the invention, it is also possible with the monomer mixture in step (i) to emulsify further polymerizable compounds, for example vinylically unsaturated monomers, in particular styrene, into the continuous phase. When such additional polymerizable compounds are used, the amount is not more than 50% by weight based on the monomer mixture as defined above. Furthermore, such additional polymerizable compounds are included in the calculation of the glass transition temperature analogous to the Fox equation (see above).

1. (a) 2,5 bis 15,0 Gew.-%, insbesondere 5,0 bis 10,0 Gew.-% Methacrylsäure (MAA);
2. (b) 67,5 bis 80,0 Gew.-%, insbesondere 72,5 bis 80,0 Gew.-%, Methylmethacrylat (MMA);
3. (c) 5,0 bis 17,5 Gew.-%, insbesondere 5,0 bis 12,5 Gew.-%, n-Butylmethacrylat (BMA); und
4. (d) 0,0 bis 10,0 Gew.-%, insbesondere 0,5 bis 7 Gew.-%, 1,4-Butandiol-Dimethacrylat (BDDMA) verwendet.

In certain preferred embodiments, the monomer mixture used is a mixture of:

1. (a) 2.5 to 15.0% by weight, especially 5.0 to 10.0% by weight of methacrylic acid (MAA);
2. (b) 67.5 to 80.0 weight percent, especially 72.5 to 80.0 weight percent, methyl methacrylate (MMA);
3. (c) 5.0 to 17.5 wt%, especially 5.0 to 12.5 wt%, n-butyl methacrylate (BMA); and
4. (D) 0.0 to 10.0 wt .-%, in particular 0.5 to 7 wt .-%, 1,4-butanediol dimethacrylate (BDDMA) used.

Such mixtures give a polymer having the desired glass transition temperature (calculated as described above analogous to the Fox equation) of> 95 ° C., in particular> 100 ° C. At the same time, these monomer mixtures are hydrophobic enough to give stable miniemulsion droplets.

In step (i) of the process, at least one stabilizer is further used. The term "stabilizer" as used herein refers to a class of molecules that can stabilize the droplets in an emulsion, i. Can prevent coagulation and coalescence. The stabilizer molecules can be attached to the surface of the droplets or interact with this. In addition, (polymerizable) stabilizers can be used which can react covalently with the monomers used. If polymerizable stabilizers are used, they are not included in the calculation of the glass transition temperature analogous to the Fox equation (see above). Stabilizers generally contain a hydrophilic and a hydrophobic portion, wherein the hydrophobic part interacts with the droplet and the hydrophilic part is oriented towards the solvent. The stabilizers may be, for example, surfactants and may carry an electrical charge. In particular, they may be anionic surfactants, for example hydrophobically modified polyvinyl alcohol (PVA), or sodium dodecyl sulfate (SDS).

Alternative stabilizers that can be used in the methods described herein are known to those skilled in the art and include, for example, other known surfactants or hydrophobically modified polar polymers.

Accordingly, in some embodiments, the blends described herein may also contain other protective colloids, such as polyvinyl alcohols, especially hydrophobically modified polyvinyl alcohols, cellulose derivatives or vinylpyrrolidones. A detailed description of such compounds can be found, for. In Houben-Weyl, Methods of Organic Chemistry, Vol. 14/1, Macromolecular Materials, Georg-Thieme-Verlag, Stuttgart, 1961, pages 411-420 ,

The total amount of stabilizer / surfactant is typically up to 30% by weight, preferably 0.1 to 10% by weight, more preferably 0.2 to 6% by weight, based on the total amount of the monomers.

The stabilizer can be used in the form of an aqueous solution. This solution may correspond to the composition of the composition of the continuous phase as defined above.

The pre-emulsion is prepared by mixing the various constituents, for example with an Ultra-Turrax, and then homogenized in the second production step (ii). The homogenization and thus the preparation of the miniemulsion is preferably carried out by a high shear process, for example by means of a high-pressure homogenizer, for example with an energy input in the range of 10 ³ to 10 ⁵ J per second per liter of emulsion and / or shear rates of at least 1000000 / s. Shear rates can be readily determined by one skilled in the art by known methods.

The high shear process, as used herein, may be by any known method of dispersing or emulsifying in a high shear field. Examples of suitable processes can be found, for example, in DE 196 28 142 A1 , Page 5, lines 1-30, DE 196 28 143 A1 , Page 7, lines 30-58, and EP 0 401 565 A1 ,

Preferably, the homogenization is carried out by means of ultrasound or using a homogenizer.

In step (iii), the polymerization of the monomer mixture is carried out using appropriate polymerization processes, in particular by free-radical polymerization. For this purpose, polymerization initiators can be used. Useful initiators include, for example, thermally activatable, radiation-activatable, such as UV initiators, or redox-activatable, and are preferably selected from radical initiators. Suitable free radical initiators are known and available and include organic azo or peroxo compounds. The initiators are preferably water-soluble. When polymerization is initiated by a water-soluble initiator, free radicals are generated in the aqueous phase and diffuse to the water / monomer interface to initiate polymerization in the droplets. Examples of suitable initiators include, but are not limited to, peroxodisulfates such as potassium peroxodisulfate (KPS).

The polymerization may be carried out at elevated temperature, for example at a temperature in the range of 10-90 ° C, preferably 20-80 ° C, more preferably 40-75 ° C and most preferably 60-75 ° C. The polymerization can take place over a period of 0.1 to 24 hours, preferably 0.5 to 12 hours, more preferably 2 to 6 hours.

The term "about" as used herein in connection with a numerical value refers to a variance of ± 20%, preferably ± 10% of the corresponding value.

The amount of residual monomers may also be chemically generated by post-polymerization, preferably by the use of redox initiators such as those described in U.S. Pat DE-A 44 35 423 . DE-A 44 19 518 and DE-A 44 35 422 be described done. Suitable post-polymerization oxidizing agents include, without limitation: hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide or alkali peroxosulfates. Suitable reducing agents include, without limitation: sodium disulfite, sodium bisulfite, sodium dithionite, sodium hydroxymethanesulfite, formamidine sulfinic acid, acetone bisulfate, ascorbic acid and reducing saccharides, and water-soluble mercaptans such as mercaptoethanol. The post-polymerization with a redox initiator can be carried out in a temperature range of 10 to 100 ° C, in particular 20 to 90 ° C. The redox agents may be added independently or continuously over a period of 10 minutes to 4 hours. In order to increase the effectiveness of the redox agents, soluble salts of metals having different valences, such as iron, copper or vanadium salts, may be added to the reaction mixture. Usually, complexing agents which keep the metal salts in solution under the reaction conditions are also added.

In order to control the molecular weight of the polymers, a chain length regulator can be used. Suitable compounds are known in the art and include, for example, various thiols, e.g. 1-Dodecanethiol. Such chain length regulators can be used in the quantities necessary to control the chain length to the desired extent. Typical amounts are in the range of 0.1 to 5 wt .-%, preferably about 0.3 to 2.0 wt .-%, more preferably about 0.5 to 1.0 wt .-% based on the total monomer mass.

In another aspect, the invention relates to nanocapsules obtainable by the method described herein. These may, in various embodiments, contain one or more hydrophobic compounds. In particularly preferred embodiments, at least one hydrophobic fragrance is encapsulated in the nanocapsule. The fragrance can be selected from those described above.

From the nanocapsules, the perfume or any other compound enclosed therein by a change in pH, for example, an increase above a pH of 3, preferably above 6, more preferably above 7, above 8, above 9 or above 10, be released. The release can take place over a short period of time or continuously over a longer period of time. Also possible is a release by increasing the Temperature, in particular over the T _{g of} the polymer. At these temperatures, the polymer becomes permeable to the trapped molecules.

The nanocapsules described herein are useful for encapsulating a suitable compound or mixture of compounds, particularly one or more fragrances.

Such nanocapsules may then be used as components of numerous compositions containing such sustained or controlled release agents. This may, for example, be a washing or cleaning agent, an air-care agent, a cosmetic agent or an adhesive. Also possible is the use in pharmaceutical preparations. In the case of the latter, the encapsulated substance is a pharmaceutically active preparation or a pharmaceutically active compound. Such pharmaceutically active compounds are particularly suitable for the encapsulation, if they meet the criteria set out above for compounds to be encapsulated. Finally, the nanocapsules are also suitable for the encapsulation of a number of other substances, such as catalysts, initiators, inhibitors, dyes, expansion agents and the like. The prerequisite for the suitability as an ingredient is, on the one hand, sufficient hydrophobicity, for example as defined above, via the Hansen parameters δ _t and / or δ _h (preferably δ _t less than 20, in particular less than 19, and / or δ _h less than 10, in particular less than 6), and that the compound does not unduly disturb the polymerization reaction or is not modified in an undesired manner in this way. A compound to be encapsulated can be considered to be excessively disturbing in the polymerization if a total monomer conversion of 80%, preferably 90% and particularly preferably 95% is not exceeded even if post-polymerization or post-polymerization has taken place (see description above). Ideally, (headspace) gas chromatography, which can be used to determine the encapsulation efficiency as described in the examples, can serve as the determination method. In addition, this method not only allows the quantitative determination of the release kinetics, but also the determination of the conversion of most monomers. If in certain cases not all the comonomers used can be measured by chromatographic methods (difficult determination of the total monomer conversion), then the quantitative determination of individual comonomers is sufficient, which cumulatively make up at least 50% of the total monomer composition. In this case, a compound to be encapsulated is considered to be excessively disturbing if the cumulative conversion of at least 50% of the monomers used is <80%, preferably <90% and particularly preferably <95%.

Since the nanocapsules release the ingredient in a pH-dependent manner, the compositions containing the nanocapsules preferably have a pH or a form in which the nanocapsules closed, ie intact. Only when the pH of the composition or the environment in which the composition is released (such as wash liquor or as a drug into an organism) above a threshold value does the particles break up and the encapsulated ingredient is released.

In addition to the described nanocapsules, the detergents and cleaners may of course contain conventional ingredients of such agents. Here are primarily surfactants, builders and bleach, enzymes and other active substances to name. In particular, surfactants belong to the essential ingredients of detergents and cleaners.

Depending on the intended use of the agents according to the invention, the surfactant content will be higher or lower. Usually, the surfactant content of detergents is between 10 and 40 wt .-%, preferably between 12.5 and 30 wt .-% and in particular between 15 and 25 wt .-%, while detergents for automatic dishwashing between 0.1 and 10 wt .-%, preferably between 0.5 and 7.5 wt .-% and in particular between 1 and 5 wt .-% surfactants.

These surfactants come from the group of anionic, nonionic, zwitterionic or cationic surfactants, anionic and nonionic surfactants are clearly preferred for economic reasons and because of their power spectrum during washing and cleaning.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C _12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration. Also suitable are alkanesulfonates which are obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated Fatty acid glycerol esters are the sulfonation products of saturated fatty acids containing 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C ₁₀ -C ₂₀ - Oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred.

The sulfuric acid monoesters of straight-chain or branched C _7-21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11- alcohols having on average 3.5 mol of ethylene oxide (EO) or C _12-18 . Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below). Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

As further anionic surfactants are particularly soaps into consideration. Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants including the soaps may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases such as mono-, di- or triethanolamine, available. The anionic surfactants are preferably in the form of their sodium, potassium or magnesium salts, in particular in the form of the sodium salts.

In the selection of anionic surfactants are the freedom from formulation no conditions to be observed in the way. However, preferred agents have a content of soap which exceeds 0.2% by weight, based on the total weight of the detergent and cleaner produced in step d). Preferably used anionic surfactants are the alkylbenzenesulfonates and fatty alcohol sulfates, preferred detergent tablets 2 to 20 wt .-%, preferably 2.5 to 15 wt .-% and in particular 5 to 10 wt .-% fatty alcohol sulfate (s), each based on the Weight of the funds included

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position , or linear and methyl-branched radicals in the mixture may contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters as they are for example, in Japanese Patent Application JP 58/217598, or which are preferably prepared according to the method described in International Patent Application WO-A-90/13533.

Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG). Applicable alkyl polyglycosides satisfy the general formula RO (G) _z , in which R is a linear or branched, in particular 2-methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit with 5 or 6 C Atoms, preferably glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4. Preference is given to using linear alkyl polyglycosides, ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Further suitable surfactants are polyhydroxy fatty acid amides of the formula (III)

wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R ^{1 is} hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes. [Z] wird vorzugsweise durch reduktive Aminierung eines reduzierten Zuckers erhalten, beispielsweise Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können dann beispielsweise nach der Lehre der internationalen Anmeldung WO-A-95/07331 durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden.The group of polyhydroxy fatty acid amides also includes compounds of the formula (IV)

in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C _1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue. [Z] is preferably prepared by reductive amination of a reduced sugar, for example, glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be used, for example, according to the teaching of the international application WO-A-95/07331 be converted by conversion with fatty acid methyl esters in the presence of an alkoxide as catalyst into the desired Polyhydroxyfettsäureamide.

Another important group of detergent ingredients are the builders. This class of substances means both organic and inorganic builders. These are compounds which can both perform a carrier function in the compositions according to the invention and also act as a water-softening substance when used.

Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof. The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus, for example in the granules according to the invention, also serve to establish a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

Further suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol. This class of substances has already been described in detail above. The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content of (co) polymeric polycarboxylates in the compositions is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

To improve the water solubility, the polymers may also allylsulfonic acids, such as in the EP-B-0 727 448 Allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer. Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those according to DE-A-43 00 772 as monomers, salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to the DE-C-42 21 381 as monomers, salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives. Further preferred copolymers are those described in the German patent applications DE-A-43 03 320 and DE-A-44 17 734 be described and as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate. Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particularly preferred are polyaspartic acids or their salts and derivatives, of which in the German patent application DE-A-195 40 086 is disclosed that they also have a bleach-stabilizing effect in addition to Cobuilder properties.

Further suitable builder substances are polyacetals which are prepared by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups, for example as in the European patent application EP-A-0 280 223 described, can be obtained. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Both maltodextrins with a DE of between 3 and 20 and dry glucose syrups with a DE of between 20 and 37 and also so-called yellow dextrins and white dextrins with relatively high molecular weights in the range from 2000 to 30 000 g / mol are useful. A preferred dextrin is in the British patent application 94 19 091 described. The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and methods of their preparation are, for example, from the European patent applications EP-A-0 232 202 . EP-A-0 427 349 . EP-A-0 472 042 and EP-A-0 542 496 as well as the international patent applications WO 92/18542 . WO-A-93/08251 . WO-A-93/16110 . WO 94/28030 . WO-A-95/07303 . WO 95/12619 and WO 95/20608 known. Also suitable is an oxidized oligosaccharide according to the German patent application DE-A-196 00 018 , A product oxidized to C _{6 of} the saccharide ring may be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable co-builders. In this case, ethylenediamine-N, N'-disuccinate (EDDS), the synthesis of which, for example, in US 3,158,615 is described, preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates, as described, for example, in US Pat US 4,524,009 . US 4,639,325 in the European patent application EP-A-0 150 930 and Japanese Patent Application JP 93/339896 to be discribed. Suitable amounts are in zeolithhaltigen and / or silicate-containing formulations at 3 to 15 wt .-%.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Such co-builders are described, for example, in the international patent application WO 95/20029 described.

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral reacting sodium salts, e.g. as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP. The builder used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

In addition, all compounds capable of forming complexes with alkaline earth ions can be used as co-builders.

A preferred inorganic builder is fine crystalline, synthetic and bound water-containing zeolite. The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. However, zeolite X and mixtures of A, X and / or P, for example a cocrystal of zeolites A and X, are also suitable. The zeolite can be used as spray-dried powder or as undried, from their preparation still moist, stabilized suspension are used. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols having 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water. In preferred embodiments, zeolites are contained in the premix in amounts of from 10 to 94.5% by weight, with it being particularly preferred for zeolites to be present in amounts of from 20 to 70, in particular from 30 to 60% by weight.

Suitable partial substitutes for zeolites are phyllosilicates of natural and synthetic origin. Such layered silicates are, for example, from the patent applications DE-A-23 34 899 . EP-A-0 026 529 and DE-A-35 26 405 known. Its usability is not limited to any particular composition or structural formula. However, smectites, in particular bentonites, are preferred here. Crystalline, layered sodium silicates of the general formula NaMSi _x O _{2x + 1} · yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4, are suitable for the substitution of zeolites or phosphates. Such crystalline layered silicates are described, for example, in the European patent application EP-A-0 164 514 described. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

The preferred builder substances also include amorphous sodium silicates having a modulus of Na ₂ O: SiO _{2 of} from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2,6, which are delay-delayed and have secondary washing properties. The dissolution delay compared to conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous". This means that in X-ray diffraction experiments the silicates do not give sharp X-ray reflections typical of crystalline substances, but at most one or more maxima of the scattered X-rays which are several angstroms in width of the diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a Löseverzögerung compared to the conventional water glasses have, for example, in the German patent application DE-A-44 00 024 described. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates, wherein in particular the overdried silicates preferably also occur as a carrier in the granules according to the invention, or be used as a carrier in the process according to the invention.

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates. Their content is generally not more than 25 wt .-%, preferably not more than 20 wt .-%, each based on the finished agent. In some cases it has been shown that in particular tripolyphosphates even in small amounts up to a maximum of 10% by weight, based on the finished composition, in combination with other builder substances lead to a synergistic improvement in the secondary washing power.

In addition to the constituents mentioned, the detergents and cleaners according to the invention may additionally contain one or more substances from the groups of bleaches, bleach activators, enzymes, pH regulators, fluorescers, dyes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, dye transfer inhibitors, corrosion inhibitors and silver protectants contain. Suitable agents are known in the art.

This list of detergent ingredients is by no means exhaustive, but merely reflects the most essential ingredients of such agents. In particular, as far as liquid or gelatinous preparations are concerned, the agents may also contain organic solvents. Preferably, it is monohydric or polyhydric alcohols having 1 to 4 carbon atoms. Preferred alcohols in such agents are ethanol, 1,2-propanediol, glycerol and mixtures of these alcohols. In preferred embodiments, such agents contain from 2 to 12% by weight of such alcohols.

In principle, the agents can have different states of aggregation. In a preferred embodiment, the washing or cleaning agents are liquid or gel-like agents, in particular liquid detergents or liquid dishwashing detergents or cleaning gels, which may in particular also be gel-type cleaners for flushing toilets. Such gel-type cleaners for flushing toilets are described, for example, in the German patent application DE-A-197 158 72 described.

Other typical detergents that may contain the nanocapsules of the present invention are liquid or gel hard surface cleaners, especially so-called all-purpose cleaners, glass cleaners, floor or bathroom cleaners, and specific embodiments of such cleaners, including acidic or alkaline forms of all-purpose cleaners as well as glass cleaners with so-called Include anti-rain effect. These liquid cleaning agents can be present both in one and in several phases. In a particularly preferred embodiment, the cleaners 2 have different phases.

Cleaner is in the broadest sense a name for - mostly surfactant-containing - formulations with a very wide range of applications and dependent on very different composition. The main market segments are household cleaners, industrial (technical) and institutional cleaners. According to the pH value, a distinction is made between alkaline, neutral and acid cleaners, according to the offer form liquid and solid cleaners (also in tablet form). In contrast to dishwashing detergents, for example, which are also classified in the product group of cleaners, the so-called cleaners for hard surfaces, both in the concentrated state and in dilute aqueous solution in conjunction with mechanical energy, have an optimum application profile. Cold cleaners develop their performance without increased temperature. Decisive for the cleaning action are especially surfactants and / or alkali carriers, alternatively acids, possibly also solvents such as glycol ethers and lower alcohols. In general, the formulations also contain builders, bleaches, enzymes, germ-reducing or disinfecting additives, as well as perfume oils and dyes, depending on the type of cleaner. Cleaners may also be formulated as microemulsions. The cleaning success depends to a great extent on the - also geographically very different - type of dirt and the properties of the surfaces to be cleaned.

The cleaners may contain as surfactant anionic, nonionic, amphoteric or cationic surfactants or surfactant mixtures of one, more or all of these classes of surfactants. The cleaners contain surfactants in amounts, based on the composition, of 0.01 to 30 wt .-%, preferably 0.1 to 20 wt .-%, in particular 1 to 14 wt .-%, most preferably 3 to 10 wt. -%.

Suitable nonionic surfactants in such general-purpose cleaners are, for example, C ₈ -C ₁₈ -alkyl alcohol polyglycol ethers, alkylpolyglycosides and nitrogen-containing surfactants or mixtures thereof, in particular the first two. The compositions contain nonionic surfactants in amounts, based on the composition, of 0 to 30 wt .-%, preferably 0.1 to 20 wt .-%, in particular 0.5 to 14 wt .-%, most preferably 1 to 10 wt .-%. C _8-18 alkyl alcohol polypropyleneglycol / polyethyleneglycol ethers are known nonionic surfactants. They can be described by the formula RO- (CH ₂ CH (CH ₃ ) O) _p (CH ₂ CH ₂ O) _e -H in which R ⁱ is a linear or branched aliphatic alkyl and / or alkenyl radical having 8 to 18 carbon atoms, p is 0 or numbers from 1 to 3 and e is numbers from 1 to 20. The C _8-18 alkyl alcohol polyglycol ethers can be obtained by addition of propylene oxide and / or ethylene oxide to alkyl alcohols, preferably to fatty alcohols. Typical examples are polyglycol ethers in which R ^{i is} an alkyl radical having 8 to 18 carbon atoms, p is 0 to 2 and e is a number from 2 to 7. Preferred representatives are, for example, C ₁₀ -C ₁₄ fatty alcohol + 1PO + 6EO ether (p = 1, e = 6) and C ₁₂ -C ₁₈ fatty alcohol + 7EO ether (p = 0, e = 7) and mixtures thereof ,

It is also possible to use end-capped C ₈ -C ₁₈ -alkyl alcohol polyglycol ethers, ie compounds in which the free OH group has been etherified. The end-capped C _8-18 alkyl alcohol polyglycol ethers can be obtained by relevant methods of preparative organic chemistry. Preferably, C _8-18 -alkyl alcohol polyglycol ethers are reacted in the presence of bases with alkyl halides, in particular butyl or benzyl chloride. Typical examples are mixed ethers in which R is a technical fatty alcohol radical, preferably C _12/14 cocoalkyl radical, p is 0 and e is 5 to 10, which are closed with a butyl group.

Preferred nonionic surfactants are furthermore the alkylpolyglycosides already described above.

As other nonionic surfactants, nitrogen-containing surfactants may be contained, e.g. Fatty acid polyhydroxyamides, for example glucamides, and ethoxylates of alkylamines, vicinal diols and / or carboxylic acid amides having alkyl groups having 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms. The degree of ethoxylation of these compounds is generally between 1 and 20, preferably between 3 and 10. Preferred are ethanolamide derivatives of alkanoic acids having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms. Particularly useful compounds include the lauric, myristic and palmitic monoethanolamides.

Suitable anionic surfactants for general-purpose cleaners are C _8-18 -alkyl sulfates, C _8-18 -alkyl ether sulfates, ie the sulfation products of alcohol ethers and / or C _8-18 -alkylbenzenesulfonates, but also C _8-18 -alkanesulfonates, C _8-18 -α- Olefinsulfonates, sulfonated C _8-18 fatty acids, especially dodecylbenzenesulfonate, C _8-22 carboxylic _acid amide _ether sulfates, sulfonosuccinic mono- and di-C _1-12 alkyl esters, C _8-18 alkyl polyglycol ether carboxylates, C _8-18 N-acyl taurides, C _8-18 -N-sarcosinates and C _8-18 alkyl isethionates and mixtures thereof. They are in the form of their alkali metal and alkaline earth metal salts, in particular sodium, potassium and magnesium salts, as well as ammonium and mono-, di-, tri- or tetraalkylammonium salts and in the case of sulfonates also in the form of their corresponding acid, for example dodecylbenzenesulfonic acid, used. The funds included anionic surfactants in amounts, based on the composition, of 0 to 30 wt .-%, preferably 0.1 to 20 wt .-%, in particular 1 to 14 wt .-%, most preferably 2 to 10 wt .-%.

Because of their foam-damping properties, the all-purpose cleaners may also contain soaps, ie alkali or ammonium salts of saturated or unsaturated C _6-22 fatty acids. The soaps may be used in an amount of up to 5% by weight, preferably from 0.1 to 2% by weight.

Suitable amphoteric surfactants are, for example, betaines of the formula (R ⁱⁱ ) (R ⁱⁱⁱ ) (R ^iv ) N ⁺ CH ₂ COO ^- , in which R "is an alkyl radical optionally interrupted by hetero atoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms and R ⁱⁱⁱ and R ^{iv are} identical or different alkyl radicals having from 1 to 3 carbon atoms, in particular C _10-18 -alkyl-dimethylcarboxymethylbetaine and C _11-17 -alkylamidopropyl-dimethylcarboxymethylbetaine The agents contain amphoteric surfactants in amounts, based on the composition, of from 0 to 15 wt .-%, preferably 0.01 to 10 wt .-%, in particular 0.1 to 5 wt .-%.

Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R ^v ) (R ^vi ) (R ^vii ) (R ^viii ) N ⁺ X ^- , in which R ^v to R ^viii for four identical or different, in particular two long and two short-chain, alkyl radicals and X ^{- are} an anion, in particular a halide ion, for example, didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof. The compositions contain cationic surfactants in amounts, based on the composition, of 0 to 10 wt .-%, preferably 0.01 to 5 wt .-%, in particular 0.1 to 3 wt .-%.

In a preferred embodiment, the cleaners contain anionic and nonionic surfactants side by side, preferably C _8-18 -alkylbenzenesulfonates, C _8-18 -alkyl sulfates and / or C _8-18 -alkyl ether sulfates in addition to C _8-18 -alkyl alcohol polyglycol ethers and / or alkylpolyglycosides, in particular C. _8-18 alkyl benzene sulphonates in addition to C _8-18 alkyl alcohol polyglycol ethers.

Furthermore, cleaners according to the invention may contain builders. Examples of suitable builders are alkali metal gluconates, citrates, nitrilotriacetates, carbonates and bicarbonates, in particular sodium gluconate, citrate and nitrilotriacetate, and sodium and potassium carbonate and bicarbonate, and also alkali metal and alkaline earth metal hydroxides, in particular sodium and potassium hydroxide, ammonia and amines , in particular mono- and triethanolamine, or mixtures thereof. These include the salts of glutaric acid, succinic acid, adipic acid, tartaric acid and benzene hexacarboxylic acid and phosphonates and phosphates. The compositions contain builders in amounts, based on the composition, of from 0 to 20% by weight, preferably from 0.01 to 12% by weight, in particular from 0.1 to 8% by weight, very preferably from 0.3 to 5 Wt .-%, but where the amount of sodium hexametaphosphate is limited to 0 to 5% by weight, except for the agents used. As electrolytes, the builder salts are at the same time phase separation aids.

In addition to the components mentioned, cleaners according to the invention may contain other auxiliaries and additives, as are customary in such compositions. These include in particular polymers, soil release agents, solvents (eg, ethanol, isopropanol, glycol ethers), solubilizers, hydrotropes (eg, cumene sulfonate, octyl sulfate, butyl glucoside, butyl glycol), cleaning enhancers, viscosity regulators (eg, synthetic polymers such as polysaccharides, polyacrylates, in nature occurring polymers and their derivatives such as xanthan gum, other polysaccharides and / or gelatin), pH regulators (eg citric acid, alkanolamines or NaOH), disinfectants, antistatic agents, preservatives, bleach systems, enzymes, dyes and opacifiers or skin protection agents, such as EP-A-0 522 506 are described. The amount of such additives is usually not more than 12 wt .-% in the detergent. The lower limit of the use depends on the nature of the additive and can be up to 0.001 wt .-% and below, for example, in the case of dyes. The amount of auxiliaries is preferably between 0.01 and 7% by weight, in particular 0.1 and 4% by weight.

The pH of the all-purpose cleaners can be varied over a wide range, but preferred is a range of 2.5 to 12, especially 5 to 10.5. Under the pH value of the present invention, the pH of the agent in the form of the temporary emulsion to understand.

Such general purpose cleaner formulations can be modified for any purpose. A special embodiment are the glass cleaner. Essential in such cleaners is that no stains or edges remain. In particular, here is a problem that condenses after cleaning water on these surfaces and leads to the so-called fog effect. Likewise, it is undesirable if so-called rain stains remain on glass panes that are exposed to the rain. This effect is known as rain effect or anti-rain effect. These effects can be prevented by using suitable additives in glass cleaners.

In another preferred embodiment, the agents are powdery or granular agents. The compositions according to the invention can have any bulk densities. The range of possible bulk densities ranges from low bulk densities below 600 g / l, for example 300 g / l, over the range of average apparent weights of 600 to 750 g / l up to the range of high bulk densities of at least 750 g / l ..

Any of the methods known in the art may be used to prepare such agents.

Another object of the present invention are hair or skin treatment cosmetic compositions which preferably contain the nanocapsules described herein in the amounts already described above in connection with the other agents. In a preferred embodiment, the cosmetic agents are aqueous preparations which contain surface-active agents and which are suitable in particular for the treatment of keratin fibers, in particular human hair, or for the treatment of skin.

The mentioned hair treatment compositions are in particular means for the treatment of human hair. The most common agents of this category can be classified into shampoos, hair care products, hair hardening and hair styling agents as well as hair dyes and depilatories. Hair-washing and care products include, in particular, hair-care compositions which are preferred according to the invention and contain surfactants. These aqueous preparations are usually present in liquid to pasty form.

For the most important ingredient group, the surface-active agents or washing active ingredients, predominantly fatty alcohol polyglycol ether sulfates (ether sulfates, alkyl ether sulfates) are used, in part in combination with other, usually anionic surfactants. Shampoo surfactants should have except good cleansing power and resistance to water hardness skin and mucous membrane compatibility. According to the legal regulations, good biodegradability has to be given. In addition to the alkyl ether sulfates, preferred agents may additionally comprise further surfactants, such as alkyl sulfates, alkyl ether carboxylates, preferably having degrees of ethoxylation of from 4 to 10, and surface-active protein-fatty acid condensates.

To create a pleasant fragrance, the hair shampoos contain perfume oils. The shampoos may contain only the nanocapsules of the invention, but it is also preferred if the hair shampoos contain not only these, but also other fragrances. All the usual fragrances approved in hair shampoos can be used.

The aim of hair care products is to preserve the natural state of the newly regrown hair for as long as possible and to restore it when damaged. Characteristics that characterize this natural state are silky shine, low porosity, elastic yet soft body and a pleasantly smooth feeling. An important prerequisite for this is a clean, dandruff-free and not over-greasy scalp. One of the hair care products counts today a variety of different products whose main representatives are referred to as pretreatment, hair lotions, hairdressing aids, hair conditioners and spa packs.

The aqueous preparations for the treatment of skin are, in particular, preparations for the care of human skin. This care begins with the cleansing for which soaps are primarily used. Here one distinguishes solid, mostly lumpy and liquid soap. Accordingly, in a preferred embodiment, the cosmetic agents are in the form of shaped bodies containing surface-active ingredients. The most important ingredients of such shaped bodies are in a preferred embodiment, the alkali metal salts of the fatty acids of natural oils and fats, preferably with chains of 12-18 carbon atoms. Since lauric acid soaps foam particularly well, the lauric acid-rich coconut and palm kernel oils are preferred raw materials for the fine soap production. The Na salts of the fatty acid mixtures are solid, the K salts are soft paste. For saponification, the dilute soda or potash liquor is added to the fatty raw materials in stoichiometric ratio so that in the finished soap a caustic excess of max. 0.05% is present. In many cases, the soaps are no longer produced directly from the fats, but from the fatty acids obtained by lipolysis. Common soap additives are fatty acids, fatty alcohols, lanolin, lecithin, vegetable oils, partial glycerides and the like. fat-like substances for refatting the cleansed skin, antioxidants such as ascorbyl palmitate or tocopherol to prevent auto-oxidation of the soap (rancidity), complexing agents such as nitrilotriacetate for binding heavy metal traces that could catalyze auto-oxidative spoilage, perfume oils to obtain the desired fragrance notes , Dyes for coloring the soap bars and possibly special additives.

Liquid soaps are based on both K-salts of natural fatty acids and on synthetic anionic surfactants. They contain less aqueous active substances than solid soaps in aqueous solution, have the customary additives, if necessary with viscosity-regulating components as well as pearlescent additives. Because of their convenient and hygienic application from dispensers, they are preferably used in public washrooms and the like. Detergent lotions for particularly sensitive skin are based on mild-acting synthetic surfactants with additives of skin-care substances, pH-neutral or slightly acidic (pH 5.5).

To cleanse especially the facial skin, there are a number of other preparations, such as face lotions, cleansing lotions, milk, creams, pastes; Face packs serve partly for cleaning, but mainly for refreshment and care of the facial skin. Facial waters are mostly aqueous-alcoholic solutions with low surfactant levels and other skin-care substances. Cleansing lotions, milks, creams and pastes are usually based on O / W emulsions with relatively low levels of fat components with cleansing and nourishing additives. So-called Scruffing and exfoliating preparations contain mild keratolytic active substances for the removal of the upper dead skin-horn layers, partly with additions of abrasive powders. Almond bran, which has long been used as a mild skin cleanser, is still a component of such preparations today. Anti-bacterial and anti-inflammatory agents are also included in cleansing skin cleansing products as the sebum collections in comedones are a breeding ground for bacterial infections and prone to inflammation. The wide range of skin cleansing products on offer varies in composition and content of various active ingredients, adapted to the different skin types and to specific treatment goals.

Further inventively preferred cosmetic agents are agents for influencing the body odor. In particular, deodorants are meant here. Such deodorants can cover, remove or destroy odors. Unpleasant body odors are caused by bacterial decomposition of sweat, especially in the moist, warm armpits, where microorganisms find good living conditions. Accordingly, the most important ingredients of deodorants are germ-inhibiting substances. In particular, those germ-inhibiting substances are preferred which have a substantial selective activity against the bacteria responsible for the body odor. However, preferred active ingredients have only a bacteriostatic effect and kill the bacterial flora under any circumstances. In general, any suitable preservative with specific activity against gram-positive bacteria may be directed to the antimicrobial agents. These are, for example, Irgasan DP 300 (trichlorane, 2,4,4'-trichloro-2'-hydroxydiphenyl ether), chlorhexidine (1,1'-hexamethylenebis (5- (4'-chlorophenyl) -biguanide) and 3,4 Quaternary ammonium compounds are also suitable in principle Because of their high antimicrobial effectiveness, all of these substances are preferably used only in low concentrations of about 0.1 to 0.3 wt .-% and also have numerous fragrances Accordingly, fragrances having antimicrobial properties are preferably used in deodorants, in particular farnesol and phenoxyethanol, and it is therefore particularly preferred for the deodorants according to the invention to contain such self-bacteriostatic fragrances, whereby the fragrances can again be in the form of nanocapsules However, it is also possible that it is precisely these antibacterial fragrances not in the form of vo n nanocapsules are used and then in mixtures with other fragrances, which are present in nanocapsules used. Another group of key ingredients of deodorants are enzyme inhibitors that inhibit the degradation of sweat by enzymes, such as triethyl citrate or zinc glycinate. Essential ingredients of deodorants are also antioxidants that are designed to prevent oxidation of the sweat components.

In a further likewise preferred embodiment of the invention, the cosmetic agent is a hair setting agent which contains polymers for strengthening. It is particularly preferred if among the polymers at least one polyurethane is included.

In principle, all embodiments disclosed in connection with the nanocapsules as well as the agents of the invention are also applicable to the described methods and uses, and vice versa. For example, it is understood that all of the specific nanocapsules described herein are applicable to the means and methods mentioned and can be used as described herein.

The following examples are given to illustrate the invention, but the invention is not limited thereto.

Examples

Materials: All monomers, methyl methacrylate (MMA, Merck, ≥ 99% stab.), Butyl methacrylate (BMA, Merck, ≥ 99% stab.), Methacrylic acid (MAA, Acros, 99.5% stab) and 1,4-butanediol dimethacrylate (BDDMA, Aldrich, 95%) were used as received without further purification. Sodium dodecyl sulfate (SDS, Lancaster, 99%), hexadecane (HD, Merck ≥ 99%) and the initiator potassium peroxodisulfate (KPS, Merck, for analysis) were used as received. The fragrance α-pinene was obtained from the Henkel fragrance center and used without further purification. Deionized water was used for all experiments.

Example 1: Perfume Encapsulation

A mixture of the monomers MMA, BMA, MAA and BDDMA (total amount of monomers: 4 g) and 0.25 g of hexadecane were dissolved in 2 g of the fragrance α-pinene. A solution of 24 g of water with 0.023 g of SDS as a stabilizer was then added to the clear hydrophobic perfume / monomer / hexadecane mixture. To prepare the pre-emulsion, the mixture was homogenized three times with an Ultra-Turrax (grade 3). The mini-emulsion was prepared by sonicating the pre-emulsion for 120 s (pulsed: 10 s, 5 s rest) at 90% amplitude (Branson sonifier W450 Digital, 1/2 "tip) under ice-cooling The miniemulsion was filled into a round-bottomed flask and 0, The grafting was carried out at 72 ° C. for 5 h with stirring The monomer compositions are listed in% by weight (wt%), based on the total amount of monomers, in Table 1. The glass transition temperature T _g was as above calculated using the Fox equation. Table 1: Monomer composition (in wt%), calculated <i> T </ i><sub> g </ sub> polymer shell, capsule sizes (z-average), encapsulation efficiencies, and perfume release of S0-S11 samples , S0 S1 S2 S3 S4 S5 S6 S7 S8 S9 S10 S11 monomer % % % % % % % % % % % % MMA 82.5 80 75 72.5 67.5 60 50 35 87.5 85 82.5 81 BMA 7.5 5 10 12.5 17.5 25 35 50 5 5 5 5 MAA 10 10 10 10 10 10 10 10 2.5 5 7.5 9 BDDMA 0 5 5 5 5 5 5 5 5 5 5 5 T _g ¹ [° C] 106 109 103 100 95 87 77 63 102 104 107 108 Capsule diameter ² [nm] 166 186 168 176 192 182 154 178 170 164 172 175 EE _SC ³ [%] 88 91 90 73 73 30 30 8th 77 83 88 89 EE _HS-GC ⁴ [%] 88 90 78 70 28 18 8th 6 70 80 85 86 Release ⁵ [%] 88 90 72 67 28 18 3 0 2 12 41 65 Relative release ⁶ [%] 100 100 92 96 100 100 38 0 3 15 48 76 ¹ calculated by means of Fox equation;
² z-average (diameter) calculated by Dynamic Light Scattering (DLS);
³ Encapsulation efficiency determined by solids content of freeze-dried samples;
⁴ Encapsulation efficiency determined by headspace GC (closed capsules, pH3, 60 ° C, 30 min);
⁵ Released proportion of α-pinene after pH increase to pH 9 determined by means of headspace GC (60 ° C, 30 min) based on the amount of perfume used;
⁶ Released percentage of α-pinene after pH increase to pH 9 determined by headspace GC (60 ° C, 30 min) based on EE _GC results.

The solids content (SC) was determined gravimetrically by freeze-drying the samples. Previously, two different theoretical solids contents were calculated. SC1 without the mass of the fragrance and SC2 including the mass of the fragrance. Due to the determination of the solids content by freeze-drying, the nanocapsules remain intact and the encapsulated fragrance is co-determined in the measurement of the solids content SC2. Assuming a complete conversion in polymerization, the amount of encapsulated fragrance can be calculated by comparing the practically measured solid content SC with the above-mentioned theoretical values. The proportion of encapsulated fragrance compared to the amount used in the synthesis is given in Table 1 as Encapsulation Efficiency (EEsc) in percent.

The particle size was measured by Dynamic Light Scattering (DLS) using a Malvern Instrument Zetasizer Nano at an angle of 173 ° (backscatter) and 25 ° C. For the measurement, the emulsion was diluted with deionized water until a slightly turbid solution was obtained. The particle size is given as Z-mean [nm].

The theoretically calculated solids content SC1 was 14.3%. The indication of the encapsulation efficiency EEsc in Table 1 shows that the fragrance was entrapped and did not evaporate during lyophilization. The results show that the compositions used were able to encapsulate the fragrance with varying efficiency.

Example 2: Determination of liberated α-pinene

Sample preparation for headspace measurements: For the headspace measurements, 10% solutions of each sample were prepared by dilution with deionized water. For manual preparation, 10 μL of each diluted solution was added to a 20 mL headspace tube and capped quickly to prevent evaporation of the analyte. The sealed nanocapsules with an intrinsic pH of about 3 were measured in water. For the measurement of the opened nanocapsules, the diluted solutions were placed in tubes with a pH 9 buffer solution. Measurements at 60 ° C and an equilibration time of 30 minutes determined the maximum area for each measurement.

The efficiency of the encapsulation was quantitatively determined by headspace gas chromatography. This allows volatile substances to be analyzed over a solid or liquid sample. A quantitative analysis of the free fragrances over the sample can be done by means of an external standard. The GC measurements were performed on an Agilent 7890 gas chromatograph and an Agilent G1888 headspace sampler with a FID detector. An Agilent 19091 J-413 column was used with H ₂ as carrier gas. The oven temperature of the GC program was as follows: 40 ° C hold isothermal for 2 min, ramp 1: 10 ° C / min to 150 ° C, hold isothermal for 4 min, ramp 2: 20C ° / min to 250 ° C. The temperature in the headspace oven was 60 ° C and the equilibration time was 30 minutes (unless stated otherwise) with vigorous shaking.

The results of the measurements are in the FIGS. 1 (free and encapsulated fragrance at pH = 3) and 2 (free fragrance at pH = 3 and pH = 9 and released fragrance when raising the pH from 3 to 9) and 3 (free fragrance at pH = 3 and pH = 9 and released Fragrance when raising the pH from 3 to 9) as a graphical plot of the specific fragrance (α-pinene) amounts versus the T _{g of} the polymer or the amount of MAA in% by weight (wt%). The results show that the higher T _g polymers can more efficiently encapsulate the fragrance. The results show Furthermore, polymers with larger amounts of pH-sensitive groups with an increase in pH, the fragrance can release more efficiently.

Example 3: Determination of the encapsulation efficiency for further fragrances

The monomer mixture S1 used in Examples 1 and 2 was used for the encapsulation of other fragrances and the encapsulation efficiency was determined gravimetrically as described above. The results are shown in Table 2. Table 2: Encapsulation efficiency for other fragrances perfume Encapsulation efficiency EEsc α-pinene 91% lilial 77% citronellal 72% β-Damascone 72% α-Damascone 52% Ionon 46% Citronellol 25% dihydromyrcenol 4% geraniol 0% hexenol 0% α-pinene + β-damascone 80% α-pinene + ionone 69% α-pinene + dihydromyrcenol 29%

Table 3 gives the Hansen parameters for the fragrances tested. Table 3: Hansen parameters perfume .DELTA.D .DELTA.p .delta.h .delta.t citronellal 16.2 5.9 5.2 18.01 Citronellol 16.1 4.8 10.8 19.97 α-Damascone 17.1 5.7 5.8 18.94 β-Damascone 17.4 4.9 5.3 18.84 dihydromyrcenol 16 4.3 10.7 19.72 geraniol 16.3 4.1 11.3 20.25 hexenol 16 6.7 13.4 21.92 ionones 17.1 5.7 5.8 18.94 Jasmone 17 5.2 5.1 18,49 lilial 17.3 2.3 4.8 18,10 phenylethyl 18.8 7.6 13 24,09 α-pinene 15.6 4.3 0 16.18

The results show that the encapsulation efficiency correlates with the Hansen parameters.

Example 4: Encapsulation Efficiency with Butanediol Dimethacrylate (BDDMA) as Crosslinker

The following monomer composition (Table 4) was used to prepare nanocapsules analogously to Examples 1 and 2 Table 4: Monomer composition (in% by weight) S0 S12 S13 S14 S1 MMA 82.5 82 81.5 81 80 BMA 7.5 7 6.5 6 5 MAA 10 10 10 10 10 BDDMA 0 1 2 3 5 Tg (estimated) [° C] 106 107 107 108 109

The encapsulation efficiency of α-pinene was determined analogously to Example 2 (headspace: 30 minutes GG time, 60 ° C.). The results are shown in Tables 5 and 6. Table 5: Encapsulation efficiency as a function of the amount of crosslinker % By weight of crosslinker BDDMA Encapsulation efficiency EEsc 0 88 1 89 2 90 3 90 5 91 sample Z-Average [nm] (Zetasizer) SC2 [%] S0 166 20.1 S12 162 20.3 S13 169 20.3 S14 170 20.3 S1 186 20.3

Claims (17)

Process for the preparation of pH-sensitive nanocapsules, characterized in that the process comprises: (i) emulsifying a monomer mixture into a continuous aqueous phase, in particular water, which comprises at least one stabilizer, in particular at least one surfactant, to form a preemulsion, the monomer mixture comprising, based on the total weight of the monomer mixture: (a) 2.5 to 19.0% by weight, especially 5.0 to 10.0% by weight, of at least one monoethylenically unsaturated C _3-5 carboxylic acid monomer; (b) 71.0 to 97.5% by weight, especially 80.0 to 90.0% by weight, of at least one monoethylenically unsaturated C "_3-5" carboxylic acid C "_1-10" alkyl ester monomer; (c) 0.0 to 10.0 wt .-%, particularly 0.5 to 7 wt .-% of at least one monomer carrying at least two ethylenically unsaturated groups, preferably a divinyl benzene or di- or triester of a C ₂ -C ₁₀ polyol with ethylenically unsaturated C ₃ -C ₅ -carboxylic acids, in particular a di- or triester of a C ₂ -C ₁₀ -alkanediol or -triol with ethylenically unsaturated C ₃ -C ₅ -carboxylic acids,
wherein the monomers are selected such that the copolymer obtainable from the monomer mixture has a theoretical glass transition temperature T _g of 95 ° C or more, in particular 100 ° C or more, more preferably 105 ° C or more, calculated analogously to the Fox equation; (ii) homogenizing the preemulsion to form stabilized miniemulsion droplets containing the monomer mixture; (iii) polymerizing the monomers in the miniemulsion droplets to obtain pH-sensitive nanocapsules. A method for encapsulating at least one hydrophobic compound in pH-sensitive nanocapsules, characterized in that the method comprises: (i) emulsifying the at least one hydrophobic compound and a monomer mixture into a continuous aqueous phase, in particular water comprising at least one stabilizer, in particular at least one surfactant, to form a preemulsion, the monomer mixture comprising, based on the total weight of the monomer mixture: (a) 2.5 to 19.0% by weight, especially 5.0 to 10.0% by weight, of at least one monoethylenically unsaturated C _3-5 carboxylic acid monomer; (b) 71.0 to 97.5% by weight, especially 80.0 to 90.0% by weight, of at least one monoethylenically unsaturated C "_3-5" carboxylic acid C "_1-10" alkyl ester monomer; (c) 0.0 to 10.0 wt .-%, particularly 0.5 to 7 wt .-% of at least one monomer carrying at least two ethylenically unsaturated groups, preferably a divinyl benzene or di- or triester of a C ₂ -C ₁₀ polyol with ethylenically unsaturated C ₃ -C ₅ -carboxylic acids, in particular a di- or triester of a C ₂ -C ₁₀ -alkanediol or triol with ethylenically unsaturated C ₃ -C ₅ -carboxylic acids,
wherein the monomers are selected such that the copolymer obtainable from the monomer mixture has a theoretical glass transition temperature T _g of 95 ° C or more, in particular 100 ° C or more, more preferably 105 ° C or more, calculated analogously to the Fox equation; (ii) homogenizing the preemulsion to form stabilized miniemulsion droplets containing the monomer mixture; (iii) polymerizing the monomers in the miniemulsion droplets to obtain pH-sensitive nanocapsules including the at least one hydrophobic compound. A method according to claim 1 or 2, characterized in that the average size of the nanocapsules in the size range of 30 to 5000 nm, preferably 30 to 1000 nm, in particular 50 to 500 nm, particularly preferably 100 to 300 nm. A method according to claim 2 or 3, characterized in that the at least one hydrophobic compound (a) has a Hansen parameter δ _t of less than 20, in particular less than 19; (b) has a Hansen parameter δ _h of less than 10, in particular less than 6; and or (c) is a hydrophobic perfume or a hydrophobic perfume mixture selected from synthetic, semisynthetic or natural perfumes or perfume mixtures, in particular alpha-pinene, lilial, citronellal, citronellol, ionone, alpha-damascone, beta-damascone, jasmone and Mixtures thereof. Process according to at least one of claims 1 to 4, characterized in that the at least one monoethylenically unsaturated C ₃ -C ₅ -carboxylic acid monomer is selected from methacrylic acid (MAA), acrylic acid (AA), fumaric acid, methylmaleic acid, maleic acid, itaconic acid or Mixtures of two or more thereof, in particular methacrylic acid (MAA), acrylic acid (AA) or mixtures thereof. Process according to at least one of Claims 1 to 5, characterized in that the at least one monoethylenically unsaturated C _3-5 -carboxylic acid C _1-10 -alkyl ester monomer is an acrylic acid or methacrylic acid alkyl ester or a mixture thereof. A method according to any one of claims 1 to 6, characterized in that the at least one ethylenically unsaturated C _3-5 carboxylic acid C _1-10 alkyl ester monomer is a methacrylic acid C ₁ -C ₅ alkyl ester monomer, in particular a methyl methacrylate Monomer, a n-butyl methacrylate monomer or a mixture thereof, more preferably a mixture of methyl methacrylate and n-butyl methacrylate in a weight ratio of 3.5: 1 to 16: 1, preferably 6: 1 to 16: 1 , Process according to at least one of claims 1 to 7, characterized in that the at least one diester or triester of a C ₂ -C ₁₀ polyol with ethylenically unsaturated C ₃ -C ₅ -carboxylic acids, a diester of methacrylic acid or acrylic acid with 1,3- Propanediol, 1,4-butanediol or 1,5-pentanediol, in particular a methacrylic acid ester of 1,4-butanediol. Method according to at least one of claims 1 to 8, characterized in that in step (i) further an ultrahydrophobic compound, in particular a C _12-28 hydrocarbon, more preferably a C _14-26 alkane is emulsified in the continuous phase. Process according to at least one of Claims 1 to 9, characterized in that the monomer mixture used is a monomer mixture which comprises: (a) 2.5 to 15.0% by weight, especially 5.0 to 10.0% by weight of methacrylic acid (MAA); (b) 67.5 to 80.0 weight percent, especially 72.5 to 80.0 weight percent, methyl methacrylate (MMA); (c) 5.0 to 17.5 wt%, especially 5.0 to 12.5 wt%, n-butyl methacrylate (BMA); and (D) 0.0 to 10.0 wt .-%, in particular 0.5 to 7 wt .-%, 1,4-butanediol dimethacrylate (BDDMA). A method according to any one of claims 1 to 10, characterized in that the monomer mixture is used as a solution of the monomers in an organic solvent, preferably a water-immiscible solvent. Method according to at least one of claims 1 to 11, characterized in that the at least one stabilizer is a surfactant, preferably an anionic surfactant, more preferably sodium dodecyl sulfate (SDS). Method according to at least one of claims 1 to 12, characterized in that for the polymerization, a polymerization initiator is added to the miniemulsion, in particular a water-soluble radical generator, more preferably potassium peroxodisulfate (KPS). Nanocapsule obtainable according to one of claims 1 to 13. Nanocapsule according to claim 14, characterized in that at least one hydrophobic fragrance is encapsulated in the nanocapsule. Composition, in particular washing or cleaning agent, air care agent, cosmetic or adhesive, containing the nanocapsule according to claim 14 or 15. Use of the nanocapsule according to claim 14 or 15 for the encapsulation of a fragrance.

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