DE102010028826A1 - Producing microcapsules, useful to incorporate active substance in cosmetics, comprises combining organic phase of epoxide and hydrophobic active substance, with water phase of water and compound reactive with the epoxide and polymerizing - Google Patents

Abstract

Producing an active substance-containing microcapsules comprises: (a) combining an organic phase comprising at least one di- or polyfunctional epoxide (monomer-I), and hydrophobic active substances, with a water phase comprising water, and compounds (monomer-II) reacting with at least one of the di- or polyfunctional epoxides (monomer-I), in the presence of at least a surfactant; (b) carrying out a polymerization reaction, preferably polyaddition reaction between the monomers-I and -II, and (c) optionally separating the obtained active material containing microcapsules. Producing an active substance-containing microcapsules having an average particle diameter of greater than 1 mu m to 500 mu m by interfacial polymerization, comprises: (a) combining an organic phase comprising at least one di- or polyfunctional epoxide (monomer-I having at least two epoxy groups (oxirane rings)), and hydrophobic active substances, with a water phase comprising water, and compounds (monomer-II having reactive functional groups in the polymerization, preferably polyaddition) reacting with at least one of the di- or polyfunctional epoxides (monomer I), under polymerization reaction, preferably polyaddition, by mixing of the two phases in the presence of at least a surfactant to form an oil-in-water emulsion; (b) carrying out a polymerization reaction, preferably polyaddition reaction between the monomers-I and -II in the presence of the hydrophobic active substances to be encapsulated and surfactant in the emulsion, where the encapsulation of the active substance in the obtained microcapsules is performed by the polymerization reaction, preferably polyaddition, and (c) optionally separating the obtained active material containing microcapsules. An independent claim is included for an active substance-containing microcapsule, obtained by the above method.

Description

The present invention is in the field of encapsulation of active ingredients. It relates to capsule systems in the form of encapsulated active substances and also relates to products such. As detergents or cleaners, cosmetics or adhesives containing such encapsulated active ingredients. The invention relates in particular to a process for the preparation of active ingredient-containing microcapsules based on epoxy resins by interfacial polymerization, furthermore it relates in particular to active ingredient-containing microcapsules based on epoxy resins, furthermore it relates in particular to products such. As detergents or cleaners, cosmetics or adhesives containing active ingredient-containing microcapsules based on epoxy resins.

Microcapsules have found their way into many technical products, e.g. As with carbonless paper or adhesive powders, which are tacky under pressure. Also in the detergent sector and in the field of cosmetics microcapsules can be used, for. B. to protect particularly sensitive substances, such as perfume oils, from the product matrix or to allow a controlled release of active ingredient.

Well-proven microcapsule systems have as capsule wall material melamine-formaldehyde resins, because they have some positive properties, such as. As a good resistance to chemicals, water, organic solvents and temperature. Process for the preparation of such capsules are for. In US 4,406,816 , in DE 19932144 A1 as in J. Microencapsulation, 2002, 19, 559 (authors: HY Lee, SJ Lee, IW Cheong and JH Kim) described. A fundamental disadvantage of this technology is the use of the toxicologically unacceptable formaldehyde. However, dispersions of microcapsules of melamine-formaldehyde resins contain free formaldehyde as a result of the preparation. To reduce the formaldehyde content, therefore, it is usual to add formaldehyde scavengers to microcapsule dispersions based on melamine-formaldehyde resins. However, a formaldehyde-free capsule technology is desirable.

From D. Crespy et. al. was in Macromolecules, 2007, 40, 3122 , The interfacial polymerization for encapsulation described namely the synthesis of polyurethane nanocapsules and the production of encapsulated silver particles.

The publications DE 100 37 656 A1 and DE 101 01 892 A1 describe processes for the preparation of active-substance-containing capsules by miniemulsion polymerization, resulting in capsules having a particle diameter of up to 500 nm. Miniemulsionspartikel are due to their small dimensions particularly suitable for the release of active ingredient via diffusion, describe it Theisinger et al. in Macromol. Chem. Phys. 2009, 210 in that the glass transition temperature of the shell polymer represents a significant contribution to the release kinetics at different temperatures.

In the published patent application DE 44 36 535 A1 discloses a process for the preparation of microcapsule dispersions by interfacial polyaddition in which an O / W emulsion is prepared from an oil phase containing the substance to be encapsulated, an oil-soluble emulsifier and a lipophilic substance capable of polyaddition, and from a water phase and after the preparation of this emulsion of the water phase added to the required for polyaddition reactants.

In US 4,626,471 describes a process for microencapsulation of colorless organic dye precursor molecules by in situ polymerization of polyfunctional amines with special multifunctional epoxy resins based on methylolated bisphenol-A or glycidyloxy-N, N-diglycidylaniline, in which first a solution of polyfunctional amine, epoxy resin and a solvent which can dissolve both substances. This solution is then dispersed in an aqueous phase.

Against this background, the object of the present invention was to provide further formaldehyde-free microcapsules which are suitable for incorporation into consumer products, in particular washing and cleaning agents and cosmetics, and which should be distinguished in particular by diffusion stability and anchability to substrates.

• (a) Vereinigen einer organischen Phase, welche mindestens ein di- oder polyfunktionelles Eiloxid (Monomer I, welches zumindest 2 Eiloxid-Gruppen (Oxiranringe) aufweist) sowie zu verkapselnde, hydrophobe Aktivstoffe umfasst, mit einer Wasserphase, welche neben Wasser noch zumindest eine mit dem di- oder polyfunktionellen Eiloxid (Monomer I) unter Polymerisationsreaktion, insbesondere Polyaddition, reagierende Verbindung (Monomer II, welches bei der Polymerisationsreaktion, insbesondere Polyaddition, reaktive funktionelle Gruppen aufweist) umfasst, unter Durchmischung der Phasen in Anwesenheit zumindest einer grenzflächenaktiven Substanz zur Bildung einer Öl-in-Wasser-Emulsion;
• (b) Durchführung einer Polymerisationsreaktion, insbesondere Polyadditionsreaktion, zwischen den Monomeren I und II in Gegenwart des zu verkapselnden hydrophoben Aktivstoffes und einer grenzflächenaktiven Substanz in der unter Schritt (a) bereitgestellten Emulsion, wobei hierdurch eine Verkapselung des Aktivstoffs in den durch Polymerisationsreaktion, insbesondere Polyaddition, erzeugten Mikrokapseln bewirkt wird; und
• (c) gegebenenfalls anschließend Abtrennung der auf diese Weise erhaltenen aktivstoffhaltigen Mikrokapseln,

This object is achieved by a process for preparing active ingredient-containing microcapsules having a mean particle diameter greater than 1 μm to 500 μm by interfacial polymerization, the process comprising the following process steps:

• (A) combining an organic phase comprising at least one di- or polyfunctional Eiloxid (monomer I, which has at least 2 Eiloxid groups (Oxiranringe)) and encapsulating, hydrophobic active substances, with a water phase, which in addition to water at least one with the di- or polyfunctional Eiloxid (monomer I) under polymerization reaction, in particular polyaddition, Reactive compound (monomer II, which in the polymerization reaction, in particular polyaddition, reactive functional groups comprises), with mixing of the phases in the presence of at least one surfactant to form an oil-in-water emulsion;
• (b) carrying out a polymerization reaction, in particular polyaddition reaction, between the monomers I and II in the presence of the hydrophobic active substance to be encapsulated and a surfactant in the emulsion provided under step (a), thereby encapsulating the active in the polymerization reaction, in particular polyaddition , produced microcapsules is effected; and
• (c) optionally subsequently separating the active substance-containing microcapsules obtained in this way,

For the purposes of the present invention, the term "average particle diameter" is to be understood as meaning the volume-average D ₅₀ particle diameter which can be determined by customary methods. The volume average D ₅₀ particle diameter is that point in the particle size distribution in which 50% by volume of the particles have a smaller diameter and 50% by volume of the particles have a larger diameter. The average particle diameters can be determined in particular by means of dynamic light scattering, which is usually carried out on dilute suspensions, z. B. 0.01 to 1 wt .-% capsules are carried out.

The method according to the invention makes it possible to provide diffusion-stable or diffusion-tight microcapsules based on epoxy resins. The microcapsules have good resistance to chemicals, water, organic solvents and temperature. They show a good anchoring on substrates. Microcapsules for the purposes of the invention are active-ingredient-containing polymer capsules which preferably have a core-shell structure, so that therefore a polymer shell encloses the active substance as the core. However, the term microcapsules encompasses not only capsules having a core-shell structure, but more generally polymer beads comprising an active substance. There are thus z. B. also includes such structures in which active is included in the capsule wall as such. It is only important that in the process according to the invention an inclusion of the active substance in a polymer matrix takes place, so that polymer beads result, which have a content of active ingredient. The release of the active substances from the capsule can preferably be effected selectively by mechanical action of force (such as friction or pressure), ie by destruction of the capsule structure, in particular of the capsule wall, whereas the diffusion of the active substances through the capsule walls is advantageously particularly low. This is an advantage over such capsules, which are produced via miniemulsion processes, since there capsules with diameters <1 micron result, which are translatorsich less inhibited because of their dimensioning than the microcapsules of the invention and therefore usually avoid a force from the outside rather and thus preferred to be moved as a whole instead of collapsing. The release of the active ingredients from the capsule by mechanical force (such as friction or pressure) but is particularly desired according to the invention, since it allows a simple release of active compound by a simple stimulus (eg.: Textilwäsche, in the course of the textiles are covered with the capsules, the active substance is released in a targeted manner when using the then dried textile, for example when rubbed with a suitable towel. The incorporation of the capsules prepared according to the invention into customary products, in particular from the field of detergents or cleaners, cosmetics and adhesives, is problem-free and results in storage-stable products. The microcapsules prepared according to the invention have a large loading potential. The amount of active substance can be varied over a wide range.

According to a highly preferred embodiment, the monomer I and the monomer II are used in a ratio such that the stoichiometric ratio of epoxy groups (oxirane rings) to the reactive functional groups of the monomer II which are reactive in the polymerization reaction, in particular polyaddition, is ≦ 1: 1, is preferably less than 1: 1.1, advantageously less than 1: 1.2, more preferably less than 1: 1.3, in particular less than 1: 1.4. A particularly advantageous stoichiometric ratio is z. B. at 1: 1.5, it can, for. B. even at 1: 2 or smaller ratios. A useful for an effective diffusion control lower limit for said stoichiometric ratio, which should preferably not be fallen below, is z. At 1: 5 or at 1: 4 or at 1: 3.

An excess of the in the polymerization reaction, especially polyaddition, reactive functional groups of the monomer II over that of the monomer I also allows a functionalization of the capsule wall material. For example, the corresponding use of amines, in particular polyamines, as monomer II leads to an amine functionalization of the capsule wall. As a result, in the application of such capsules particularly good interactions of the capsules with the target substrates, z. As textiles can be achieved. This favors z. As in textile washing an efficient use of the capsules because Increased affinity of the capsules for the textile results in improved deposition of the capsules on the textile. Another advantage of the functionalization of the capsule wall material is that the respective functions, such. As the amine function can be used as a reactant for a further chemical modification of the polymer shell.

Suitable monomers II are in particular di- and polyfunctional alkanols, di- and polyfunctional mercaptans and di- and polyfunctional amines. Accordingly, the reactive functional groups of the monomer II which are reactive in the polymerization reaction, in particular polyaddition, are in particular hydroxyl groups, thiol groups and amine groups.

The monomer I is in the water phase at 20 ° C, preferably less than 10 wt .-%, advantageously less than 5 wt .-%, in particular less than 1 wt .-%, soluble, for. B. to less than 0.5% by weight or less than 0.1 wt .-%, each based on the water phase. The active substance to be encapsulated by the method according to the invention is hydrophobic. Hydrophobic in the sense of the invention means that the active substance is substantially insoluble in water or at least sparingly soluble in water. This means that the active substance to be encapsulated in water at 20 ° C is preferably less than 10 wt .-%, advantageously less than 5 wt .-%, in particular less than 1 wt .-%, soluble, for. B. less than 0.5% by weight or less than 0.1 wt .-%. The lower the degree of water solubility of the active substance, the better the encapsulation of the active substance by the method according to the invention in general.

The active substance used according to the invention should preferably be soluble in organic media and solvents, in particular in the monomer I or at least dispersible. The active ingredient may be present under reaction conditions either as a liquid or as a solid, but preferably as a liquid.

According to a preferred embodiment of the invention, the average particle diameter of the resulting microcapsules is preferably 5-250 μm, advantageously 10-200 μm, in particular 15-100 μm. Preferred lower limits of the particle diameter may also be 30, 40 or 50 μm. The particle size and particle size distribution of the emulsified droplets in the oil-in-water emulsion determines the particle size and particle size distribution of the final polymerized products, i. H. the microcapsules. The size of the microcapsules can be adjusted in particular by the intensity of the mixing of the organic phase with the water phase. In general, as the number of revolutions increases, the size of the dispersed particles decreases. The desired conditions for the individual case, such. As temperature, pH or stirring speed can be easily determined by some experiments.

The emulsified is in principle subject to no particular restriction. However, it is necessary that a surfactant (surfactant and / or protective colloid) is used. Suitable protective colloids are preferably polymer systems which can prevent agglomeration, coagulation, flocculation of the emulsified or dispersed substances in dispersions. In addition to natural products such as gelatin, casein, starch and dextrin z. As well as cellulose derivatives, polyvinyl alcohols, polyacrylic acids, polyacrylamides, polyvinylpyrrolidones can be used as protective colloids. The size of the capsule can also be controlled by means of the concentration of the protective colloid, since this allows the viscosity of the aqueous, continuous phase to be varied within certain limits. With increasing viscosity of the aqueous phase or with decreasing viscosity of the material to be encapsulated, the droplet size and thus the size of the capsules generally decrease.

Particularly preferred protective colloids are polyvinyl alcohol (eg Mowiol 4-88 ex Kuraray), hydrophobically modified vinylpyrrolidone / vinyl acetate copolymers (eg Collacral VAL ex BASF) and polyethyleneimines (eg Lupasol P ex BASF).

The choice of the protective colloid also influences the interaction with the target surfaces during use (for example: textile surface during textile washing with a detergent containing microcapsules according to the invention).

The protective colloid is preferably added to the water phase before the emulsifying step. Based on the total resulting emulsion are preferably 0.01 to 15 wt .-%, in particular 0.1 to 5 wt .-% wt .-% protective colloid. The protective colloid, like the surfactants, also has a stabilizing function.

The dispersion or emulsification is carried out in a known manner, for example by homogenizing or dispersing.

In general, the reaction temperatures for the polymerization reaction, in particular polyaddition, in step (b) are advantageously about 20 to 100 ° C, preferably about 40 to 90 ° C, especially about 50 to 80 ° C. The reaction time is preferably from 0.01 to about 24 hours, advantageously from about 0.1 to 10 hours, especially from about 1 to about 5 hours. The polymerization reaction, in particular polyaddition, can be accelerated by thermal treatment, ie by increasing the reaction temperature.

The process steps (a) and (b) can be carried out either batchwise or continuously (for example as a batch process).

The process step (b) may optionally be followed by a process step (c) in which the active substance-containing microcapsules obtained in step (b) can be separated or isolated by known methods known to the person skilled in the art. In this case, no excessive shearing forces should be exerted on the microcapsules, so that they are not damaged. Separation methods which are suitable according to the invention are, for example, freeze-drying (lyophilization) or spray-drying under mild conditions.

According to a preferred embodiment, the monomer II is selected from the group of (i) di- and polyfunctional amines and mixtures thereof, (ii) di- and polyfunctional alkanols and mixtures thereof, (iii) di- and polyfunctional mercaptans and mixtures thereof, and (V) mixtures of the aforementioned compounds, wherein the use of di- and polyfunctional amines is particularly preferred. The monomers mentioned enable the effective construction of stable microcapsules.

In particular, it is also possible to use mixtures of difunctional and polyfunctional monomers II (in particular corresponding amines, alkanols, mercaptans). By the proportion of di- and polyfunctional compounds can be controlled specifically the properties of the resulting capsules, in particular degree of crosslinking, glass transition temperature, capsule stability and particle size.

According to a further preferred embodiment, the monomer II is a water-miscible, in particular a water-soluble di- or polyfunctional amine.

Preferred di- and polyfunctional amines are in particular selected from the group comprising diaminoethane, diethylenetriamine; 1,2-propylene diamine; isophoronediamine; 2,2-dimethylpropane-1,3-diamine; octamethylene; N- (2-aminoethyl) ethanolamine; Piperazine, O, O'-bis (2-aminopropyl) polypropylene glycol, (3- (2-aminoethylamino) propylamine), 1,3-diaminopropane, 3- (cyclohexylamino) propylamine; 3- (methylamino) propylamine; dipropylenetriamine; N, N-bis (3-aminopropyl) methylamine; N, N'-bis (3-aminopropyl) ethylenediamine.

A "water-miscible di- and polyfunctional amine" refers to those amines which can form homogeneous mixtures with water at 20 ° C in any ratio. If solutions are formed, one speaks of solubility instead of miscibility, ie of "water-soluble di- and polyfunctional amine".

Also usable are polyoxyalkylene, in particular polyoxyalkylenediamines with polyoxyethylene and / or polyoxypropylene units, where the amino groups are preferably terminal (eg., Jeffamine D 230 ^® by the company. Huntsman, a NH ₂ -terminated polypropylene oxide of the general formula NH ₂ -CH ( CH ₃ ) -CH ₂ - [O-CH ₂ -CH (CH ₃ )] n-NH ₂ with n = ca. 2.5). In particular those polyoxyalkylenediamines are preferred which are at least miscible with water, better still are water-soluble.

wobei y Werte von vorzugsweise 1–40 annehmen kann und die Summe aus x + z vorzugsweise von 1 bis 8 reichen kann und wobei y vorzugsweise größer ist als die Summe aus x + z. Diese Diamine sind kommerziell erhältlich von der Fa. Huntsman als Jeffamine^® des ED-Typs (z. B. Jeffamine ED-600 y = ca 9,0; x + z = ca. 3,6; Jeffamine ED-900 y = ca. 12,5; x + z = ca. 6,0; Jeffamine ED-2003 y = ca. 39; x + z = ca. 6,0). Solche Diamine sind sehr gut wasserlöslich und damit sehr gut geeignet.Particularly suitable are polyoxyalkylenediamines having the following general structure,

where y can take on values of preferably 1-40 and the sum of x + z can preferably range from 1 to 8 and where y is preferably greater than the sum of x + z. These diamines are commercially available from the Huntsman (as Jeffamine ^® ED-type, for example, Jeffamine ED-600 y = about 9.0;.. X + z = ca. 3.6; Jeffamine ED-900 y = about 12.5; x + z = about 6.0; Jeffamine ED-2003 y = about 39; x + z = approx. 6.0). Such diamines are very soluble in water and therefore very well suited.

Trifunctional amines (z. B. JEFFAMINE ^® T-403) are preferably used as long as they are at least miscible with water.

wobei n = 1 ist, (x + y + z) = 5–6 ist.JEFFAMINE ^® T-403 is a suitable triamine having the following formula,

where n = 1, (x + y + z) = 5-6.

Also tetrafunctional amines are preferably used, provided that they are at least miscible with water.

When the monomer II is a di- or polyfunctional alkanol, it may be, for example, 2,2-bis (4-hydroxyphenyl) propane (Eisphenol A) or its homologs or derivatives.

When the monomer II is a di- or polyfunctional mercaptan, it may in particular be selected from the group of optionally substituted alkyl dithiols (dithioalkanes), preferably those having terminal thiol groups (SH groups) such as 1,6-hexanedithiol.

The active ingredient content in the emulsion provided in step (a) is generally preferably from 0.01 to 50% by weight, in particular from 1 to 30% by weight, based on the emulsion.

The total monomer content in the emulsion provided in step (a) is generally preferably from 0.01% by weight to 30% by weight, in particular from 1 to 15% by weight, based on the emulsion.

Fragrance substances, essential oils, perfume oils, care oils and / or silicone oils are particularly suitable as the hydrophobic active substance contained in the microcapsule prepared according to the invention. Perfume-containing microcapsules are most preferred. In principle, however, it is also possible to incorporate other hydrophobic substances, in particular hydrophobic liquids, into the microcapsules. It is also possible that the microcapsule core in addition to the hydrophobic active substance, such as. B. a perfume oil, also comprises finely dispersed solids such. B. produced by flame hydrolysis silica nanoparticles (trade name Aerosil ^® ).

Possible usable active substances are also pharmaceutically active substances such as antibacterial, antiviral or fungicidal active substances; Antioxidants and biologically active substances; Vitamins and vitamin complexes; Enzymes and enzymatic systems; cosmetically active substances; washing and cleaning substances; biogenic agents and genes; polypeptides; Proteins and lipids; Waxes and fats; Foam inhibitors; Graying inhibitors and color proofing agents; Soilrepellent-agents; Bleach activators and optical brighteners; amines; and mixtures of the compounds listed above, in particular mixtures with dyes or coloring substances.

According to the invention, di- and / or polyfunctional epoxides are used as monomers I. It is also possible to use mixtures of such epoxides, in particular mixtures of di- and polyfunctional epoxides. Due to the content of polyfunctional epoxides in the starting mixture, the degree of crosslinking and thus the glass transition temperature of the resulting polymer can be controlled. Through the use of polyfunctional epoxides, such as tri- and / or tetrafunctional epoxies, a stronger cross-linking can be achieved with greater capsule stability of the end products.

mit N = 0–20. The usable epoxides (monomers I) may be, for example, difunctional epoxides, for example, derived from bisphenol A epoxides such as bisphenol A diglycidyl ether or epoxides of the epichlorohydrin-substituted bisphenols such as. B. the epoxide of the following formula

with N = 0-20.

This corresponds to a preferred embodiment of the invention. Such an epoxide is z. B. under the name Epikote E 828 ^® from the company. Shell commercially available.

(z. B. Denacol Ex-314^® von der Fa. Shell).The usable epoxides (monomers I) may also be polyfunctional epoxides, for example tri- and / or tetrafunctional epoxides. A suitable trifunctional epoxide according to the invention is, for example, the epoxide of the general formula

(z. B. Denacol Ex-314 ^® by the company. Shell).

(z. B. Denacol Ex-411^® von der Fa. Shell).An inventively suitable tetrafunctional epoxide is, for example, the epoxide of the general formula

(z. B. Denacol Ex-411 ^® by the company. Shell).

A particularly suitable epoxide in the context of the invention is the commercial product ^{DER® 331®} from DOW. This is a liquid epoxy resin. It is the reaction product of epichlorohydrin and bisphenol-A, hence a bisphenol A diglycidyl ether. The EEW value (EEW = epoxy equivalent weight in g / eq) of DER ^® 331 ^® is according to the manufacturer's instructions at 182-192 (determined in accordance with the manufacturer's instructions in accordance with ASTM D-1652 ).

A particularly suitable epoxy in accordance with the invention is also the commercial product THE ^® 431 Epoxy Novolac ^® by the company. DOW. This is a liquid epoxy resin. It is the reaction product of epichlorohydrin and phenol-formaldehyde novolac. The EEW value of DEN ^® 431 ^® is according to the manufacturer's instructions 172-179 (determined in accordance with the manufacturer's instructions in accordance with ASTM D-1652 ).

The surface-active substance (surfactant and / or protective colloid) used according to the invention is advantageously already present in the water phase before the water phase and the organic phase are combined. It is also possible that the organic phase contains surfactant (surfactant and / or protective colloid) before combining with the water phase, but this is less preferred. It is also possible to add the surfactant during the mixing of the phases.

The surface-active substance (surfactant and / or protective colloid) used according to the invention serves to stabilize the emulsion and is in particular selectable from the group of protective colloids of nonionic surfactants and ionic surfactants.

Suitable nonionic surfactants are in particular selected from the group of low molecular weight, nonpolymeric nonionic surfactants such as alkoxylated, preferably ethoxylated fatty alcohols, alkylphenols, fatty amines and fatty acid amides; alkoxylated triglycerides, mixed ethers and mixed formals; optionally partially oxidized alk (en) yloligoglycosides; Glucoronsäurederivaten; Fatty acid N-alkyl glucamides; Protein hydrolysates, in particular alkyl-modified protein hydrolysates; low molecular weight chitosan compounds; Zuckerestern; sorbitan; Amine oxides; and polymeric nonionic surfactants such as polyglycol ethers; alkylphenol polyglycol; fatty acid polyglycol esters; Fettsäureamidpolyglykolethern; fatty amine polyglycol ethers; polyol fatty acid esters; Polysorbates.

The ionic surfactants may be cationic or anionic surfactant. Examples of cationic surfactants suitable according to the invention are those compounds which are in particular selected from the group of quaternary ammonium compounds such as dimethyl distearyl ammonium chloride, Stepantex VL 90 (Stepan); Esterquats, especially quaternized fatty acid trialkanolamine ester salts; Salts of long-chain primary amines; quaternary ammonium compounds such as hexadecyltrimethylammonium chloride (CTMA-Cl); Dehyquart A (cetrimonium chloride, Cognis) or Dehyquart LDB 50 (lauryldimethylbenzylammonium chloride; Cognis).

Examples of anionic surfactants suitable according to the invention are those compounds which are in particular selected from the group of soaps; alkylbenzenesulfonates; alkane; olefin; alkyl ether; Glycerinethersulfonaten; -Methylestersulfonaten; sulfofatty; alkyl sulfates; fatty alcohol; glycerol ether; Fettsäureethersulfaten; hydroxy mixed; Monoglyceride (ether) sulfates; Fatty acid amide (ether) sulfates; Mono and dialkyl sulfosuccinates; Mono and dialkyl sulfosuccinamates; sulfotriglycerides; amide soaps; Ether carboxylic acids and their salts; Fettsäureisothionaten; Fettsäuresarcosinaten; fatty acid taurides; N-acyl amino acids such as acyl lactylates, acyl tartrates, acyl glutamates, acyl aspartates; oligoglucoside sulfates; Protein fatty acid condensates, in particular vegetable products based on wheat and alkyl (ether) phosphates.

The content of surfactant in the emulsion provided in step (a) is generally preferably 0.01 to 15 wt .-%, advantageously 0.1 to 10 wt .-%, in particular 0.2 to 5 wt .-%, based on the emulsion. Depending on the type and amount of the surfactant, the particle size of the emulsified particles and thus of the final product can be influenced.

Another object of the invention are active ingredient-containing microcapsules obtainable by a method as described above.

The active agent-containing microcapsules prepared by the processes according to the invention contain at least one active substance enclosed in a polymer matrix, in particular in a core-shell configuration. The microcapsules of the invention may also be referred to as polymer support systems or polymeric support systems.

The wall layers of the active-containing microcapsules prepared by the processes according to the invention comprise a polymer which is obtainable by polymerization reaction, in particular polyaddition, of epoxides and compounds which react under polymerization reaction, in particular polyaddition, (in particular amines, alcohols, mercaptans). The polymer is an epoxy resin. The capsules are suitable for release of the encapsulated active by mechanical stimulus, d. H. by rubbing or something similar.

The surface, in particular the surface condition, of the active substance-containing microcapsules can optionally be modified, the surface modification being carried out during the polymerization or being able to be carried out subsequently.

The modification of the surface properties of the capsules can be done chemically or physically. It may serve to substantiate the capsules, in particular for laundry, fibers and fabrics or for skin and hair. A physical modification takes place z. Example by the choice of a suitable surfactant, protective colloid and / or polymers, which is used directly in the emulsion production or is added later to the polymerized system. Also, a modification of the optionally later dried capsule material, for. As spray-dried material is possible. A functionalization in the polymerization reaction can be carried out by additions of functional monomers, which lead to a corresponding surface property. It can z. For example, monomers having cationic, anionic or nonionic hydrophilic substituents can be used. The delayed release effect of the systems according to the invention can, for. B. be further increased by the use of a coating of a polymer material or a salt.

According to the invention suitable substances for surface modification are organic or inorganic compounds of various kinds, such. Cationic polymers, polyquaternized polymers, cationic biopolymers, cationic silicone oils, alkylamidoamines, quaternary ester compounds ("esterquats"), also in each case in the form of their salts; anionic and nonionic polymers such as, for example, polymers having anionic groups and anionic polyelectrolytes, naturally occurring polymers, modified natural products, polysaccharides, biodegradable polymers, fully synthetic polymers, also in each case in the form of their salts; inorganic compounds such as zeolites, silicates, carbonates, bicarbonates, soda, alkali and Erdalkalisufalte and phosphates and all surfactants listed above, especially polymers nonionic surfactants with EO / PO blocks and polyethylene glycol and polyethylene glycol derivatives.

In particular, it is advantageous to introduce positive charges into the capsule wall. Since many surfaces have a slightly negatively charged surface potential, this simple modification can achieve a greatly improved attractive interaction. Permanent positive charges can be introduced by quaternary nitrogen atoms. Aminfunktionalisierung the introduction of pH-dependent positive charges is possible.

Likewise, the active substance-containing microcapsules prepared by the processes according to the invention can be stained. This can usually be done by also miteingelagert in addition to the active ingredients or dyes, which have been previously added to the emulsion.

By choosing the polymerization reaction parameters, it is possible to adjust the particle properties. By selecting suitable reactants, the particle properties can be optimized for the desired application. Thus, on the type of bi- or polyfunctional amines, mercaptans or alcohols and epoxides used, the properties of the resulting polymer such. As glass temperature, elasticity, stretch and extensibility and melting or decomposition temperature influence. Multifunctional monomers, in particular tri- and tetrafunctional epoxides and amines, lead to crosslinking of the polymer and thus to a strong increase in the molecular weight. This allows specific parameters of the polymer particles such as glass transition temperature and melting point to be influenced. The glass transition temperature of the polymer particles is interesting for later applications insofar as z. B. by the targeted softening of the polymer matrix, a diffusive release of the entrapped active can be activated. The particles are very dimensionally stable below the glass transition temperature and an active ingredient release by diffusion takes place, if at all, extremely slowly.

When the temperature rises above the glass transition temperature of the matrix, the particle softens and the release of the active substance by diffusion can possibly be accelerated. When setting the glass transition temperatures to the desired value, however, the following must be noted: Since the glass transition temperature of the polymers in bulk - here measurement - is always higher than in dispersion, because the surrounding water has an influence on the properties of the polymer chains, eg. As epoxy resin chains, this effect must be taken into account in the setting of the desired glass transition temperature. The lowering of the glass transition temperature by water is about 20 to 40 ° C. Furthermore, the reduction of the glass transition temperature must be taken into account by the addition of active; the lowering of the glass transition temperature by the addition of oils as active substances or active ingredients is for example about 20 to 60 ° C.

The microcapsules according to a preferred embodiment of the invention, an active ingredient content (in particular fragrances) of z. B. 0.01 to 95 wt .-%, preferably 0.1 to 90 wt .-%, in particular 1 to 80 wt .-%, based on the total weight of the capsules. Suitable lower limits may also be 5, 10, 15 or 25 wt .-%, suitable upper limits may also be at 70, 60 or 50 wt .-%.

The uses of the active substance-containing microcapsules prepared by the process according to the invention are very numerous. The capsules are very suitable for incorporation into various technical products. Thus, the active substance-containing microcapsules prepared by the process according to the invention can be used as polymer support systems or as delivery systems (encapsulation, transport or administration vehicles - often synonymously also referred to as "delivery systems" or "carrier systems"), in particular in US Pat Range of cosmetics and personal care (eg for deodorants, hair treatment agents, etc.), in the field of pharmacy, in adhesive processing and / or very particularly preferably in the field of detergents and cleaners (especially, for example, in dishwashing detergents, fabric softeners, Detergents, etc.), in particular for the controlled release of active substances.

Another object of the invention is therefore the use of the microcapsules according to the invention for the incorporation of active ingredients in products from the field of detergents and cleaners, cosmetics, pharmaceutics and adhesives.

This results in the sense of a preferred embodiment of the invention, the use of microcapsules for the controlled release of active ingredients or in the application of products from the field of detergents and cleaners, cosmetics, pharmaceutics and adhesives.

The present invention thus also cosmetics, personal care products, pharmaceuticals, adhesives and in particular washing or cleaning agents containing the capsule systems according to the invention, preferably microcapsules containing perfume oils, for. B. in amounts of 0.001 wt .-% to 25 wt .-%.

The use of the microcapsules according to the invention in detergents or cleaners is particularly preferred. The term detergents or cleaners includes, in particular, laundry detergents, textile treatment agents, fabric care agents, fabric softeners, dishwashing detergents (preferably those for automatic dishwashing) or hard surface cleaners. The incorporation of the microcapsules may, for. B. directly from the microcapsule dispersion, which can be in the target product, eg. As a fabric softener or a powder detergent, mixes. The incorporation of the microcapsules can also be done via dried microcapsules.

In addition to the microcapsules according to the invention, detergents or cleaners according to the invention preferably comprise at least one, preferably several, active components, in particular washing, care and / or cleaning active components, advantageously selected from the group comprising anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, acidifying agents , Alkalizing agents, anti-wrinkling compounds, antibacterial agents, antioxidants, anti-redeposition agents, antistatics, builders, bleaches, bleach activators, bleach stabilizers, bleach catalysts, ironing aids, cobuilders, fragrances, anti-shrinkage agents, electrolytes, enzymes, colorants, colorants, dyes, color transfer inhibitors, fluorescers, Fungicides, germicides, odor-complexing substances, adjuvants, hydrotropes, rinse aids, complexing agents, preservatives, corrosion inhibitors, optical brighteners, perfumes, perfume carriers, P gloss regulators, pH adjusters, repellents and impregnating agents, polymers, swelling and anti-slip agents, foam inhibitors, phyllosilicates, dirt repellents, silver protectants, silicone oils, UV protectants, viscosity regulators, thickeners, discoloration inhibitors, grayness inhibitors, vitamins and / or softeners.

The amounts of the individual ingredients in the detergents or cleaning agents according to the invention are in each case based on the intended use of the agent in question, and the person skilled in the art is familiar with the orders of magnitude of the quantities of ingredients to be used or can refer to the corresponding technical literature.

Depending on the intended use of the washing or cleaning agents according to the invention, for example, the surfactant content will be higher or lower. Usually z. For example, the surfactant content of, for example, detergents between LB. 10 and 50 wt .-%, preferably between 12.5 and 30 wt .-% and in particular between 15 and 25 wt .-%, while detergents for automatic dishwashing usually between z. B. 0.1 and 10 wt .-%, preferably between 0.5 and 7.5 wt .-% and in particular between 1 and 5 wt .-% surfactants.

The detergents or cleaners according to the invention may contain surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic surfactants. Suitable nonionic surfactants are in particular ethoxylation and / or propoxylation of alkyl glycosides and / or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups. Also suitable are ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides, which correspond to said long-chain alcohol derivatives with respect to the alkyl moiety, and of alkylphenols having from 5 to 12 carbon atoms in the alkyl radical.

Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations. Usable soaps are preferably the alkali salts of the saturated or unsaturated fatty acids having 12 to 18 carbon atoms. Such fatty acids can also be used in incompletely neutralized form. Useful surfactants of the sulfate type include the salts of the sulfuric acid half-esters of fatty alcohols containing 12 to 18 carbon atoms and the sudification products of said nonionic surfactants having a low degree of ethoxylation. Suitable surfactants of the sulfonate type include linear alkylbenzenesulfonates having 9 to 14 carbon atoms in the alkyl moiety, alkanesulfonates having 12 to 18 carbon atoms, and Olefinsulfonate with 12 to 18 carbon atoms, in the reaction of corresponding Monoolefins with sulfur trioxide are formed, as well as alpha-sulfofatty acid esters, which are formed in the sulfonation of fatty acid methyl or ethyl esters.

Cationic surfactants are preferably under the esterquats and / or the quaternary ammonium compounds (QUATS) according to the general formula (R ^I) (R ^II) (R ^III) (R ^IV) N ⁺ X ^- is selected, in which R ^I to R ^IV the same or different C _1-22 -alkyl, C _7-28 -Arylalkylreste or heterocyclic radicals, wherein two or in the case of an aromatic inclusion as in pyridine even three radicals together with the nitrogen atom, the heterocycle, z. A pyridinium or imidazolinium compound, and X ^{- represents} halide ions, sulfate ions, hydroxide ions or like anions. QACs are by reacting tertiary amines with alkylating agents, such as. As methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced. The alkylation of tertiary amines with a long alkyl radical and two methyl groups succeeds particularly easily, and the quaternization of tertiary amines with two long radicals and one methyl group can be carried out with the aid of methyl chloride under mild conditions. Amines which have three long alkyl radicals or hydroxy-substituted alkyl radicals are less reactive and are quaternized, for example, with dimethyl sulfate. Examples of suitable QACs are benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride), benzalkone B (m, p-dichlorobenzyl-dimethyl-C ₁₂ -alkylammonium chloride, benzoxonium chloride (benzyldodecyl-bis (2-hydroxyethyl) ammonium chloride) , Cetrimonium bromide (N-hexadecyl-N, N-trimethyl-ammonium bromide), Benzetonium chloride (N, N-dimethyl-N [2- [2- [p- (1,1,3,3-tetramethylbutyl) -phenoxy] -ethoxy] - ethyl] benzylammonium chloride), dialkyldimethylammonium chlorides, such as di-n-decyldimethylammonium chloride, didecyldimethylammonium bromide, dioctyldimethylammonium chloride, 1-cetylpyridinium chloride and thiazoline iodide, and mixtures thereof Preferred QACs are the benzalkonium chlorides having C ₈ -C ₂₂ -alkyl radicals, in particular C C ₁₂ -C ₁₄ alkylbenzyldimethylammonium chloride.

verstanden werden, in der R⁵ für einen Alkyl- oder Alkenylrest mit 12 bis 22 Kohlenstoffatomen und 0, 1, 2 oder 3 Doppelbindungen, R⁶ und R⁷ unabhängig voneinander für H, OH oder O(CO)R⁵, s, t und u jeweils unabhängig voneinander für den Wert 1, 2 oder 3 und X^– für ein Anion, insbesondere Halogenid, Methosulfat, Methophosphat oder Phosphat sowie Mischungen aus diesen, steht. Bevorzugt sind Verbindungen, die für R⁶ die Gruppe O(CO)R⁵ und für R⁵ einen Alkylrest mit 16 bis 18 Kohlenstoffatomen enthalten. Besonders bevorzugt sind Verbindungen, bei denen R⁷ zudem für OH steht. Beispiele für Verbindungen der Formel (IV) sind Methyl-N-(2-hydroxyethyl)-N,N-di(talgacyl-oxyethyl)ammonium-methosulfat, Bis-(palmitoyl)-ethyl-hydroxyethyl-methyl-ammoniummethosulfat oder Methyl-N,N-bis(acyloxyethyl)-N-(2-hydroxyethyl)ammonium-methosulfat. Werden quartemierte Verbindungen der Formel (IV) eingesetzt, die ungesättigte Gruppen aufweisen, sind die Acylgruppen bevorzugt, deren korrespondierende Fettsäuren eine Jodzahl zwischen 5 und 80, vorzugsweise zwischen 10 und 60 und insbesondere zwischen 15 und 45 aufweisen und/oder die ein cis/trans-Isomerenverhältnis (in Mol-%) von größer als 30:70, vorzugsweise größer als 50:50 und insbesondere größer als 70:30 haben. Handelsübliche Beispiele sind die von der Firma Stepan unter dem Warenzeichen Stepantex^® vertriebenen Methylhydroxyalkyldialkoyloxyalkylammoniummethosulfate oder die unter dem Handelsnamen Dehyquart^® bekannten Produkte der Firma Cognis Deutschland GmbH beziehungsweise die unter der Bezeichnung Rewoquat^® bekannten Produkte des Herstellers Goldschmidt-Witco.Esterquats are here preferably compounds of the general formula IV,

in which R ^{5 is} an alkyl or alkenyl radical having 12 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, R ⁶ and R ^{7 are} independently H, OH or O (CO) R ⁵ , s, t and u are each independently of the other the value 1, 2 or 3 and X ^{- is} an anion, in particular halide, methosulfate, methophosphate or phosphate and mixtures of these. Compounds containing an alkyl group having 16 to 18 carbon atoms for R ^{6 is} the group O (CO) R ⁵ and R ⁵ are preferred. Particularly preferred are compounds in which R ^{7 is} also OH. Examples of compounds of the formula (IV) are methyl N- (2-hydroxyethyl) -N, N-di (tallowacyl-oxyethyl) ammonium methosulfate, bis (palmitoyl) -ethyl-hydroxyethyl-methyl-ammonium methosulfate or methyl-N , N-bis (acyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulfate. If quaternized compounds of the formula (IV) which have unsaturated groups are used, preference is given to the acyl groups whose corresponding fatty acids have an iodine number between 5 and 80, preferably between 10 and 60 and in particular between 15 and 45 and / or which have a cis / trans Isomer ratio (in mol%) of greater than 30:70, preferably greater than 50:50 and in particular greater than 70:30 have. Commercial examples are sold by Stepan under the trade name Stepantex® ^® methylhydroxyalkyldialkoyloxyalkylammonium or those known under the trade name Dehyquart® ^® products from Cognis Germany GmbH or the known under the name Rewoquat ^® products by manufacturer Goldschmidt-Witco.

Surfactants are present in detergents or cleaners according to the invention in proportions of preferably from 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight. Particularly in laundering agents, preferably up to 30% by weight, in particular from 5% by weight to 15% by weight, of surfactants, among these preferably at least partially cationic surfactants, are used.

A washing or cleaning agent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder. The water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin as well as polymeric (poly-) carboxylic acids, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which may also contain polymerized small amounts of polymerizable substances without carboxylic acid functionality. Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight.

If desired, organic builder substances may be present in the detergents or cleaners according to the invention in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Quantities close to the stated upper limit are preferably used in paste-form or liquid, in particular water-containing, detergents or cleaners according to the invention. Detergents or cleaning agents according to the invention, such as laundry aftertreatment agents, such as. As fabric softener, may optionally also be free of organic builder.

Suitable water-soluble inorganic builder materials are, in particular, alkali metal silicates and polyphosphates, preferably sodium triphosphate. As water-insoluble, water-dispersible inorganic builder materials in particular crystalline or amorphous Alkalialumosilikate, in amounts of z. B. up to 50 wt .-%, preferably not more than 40 wt .-% and in liquid agents, in particular from 1 wt .-% to 5 wt .-%, used in the washing or cleaning agents according to the invention. Among these, preferred are the detergent grade crystalline sodium aluminosilicates, especially zeolite A, P and optionally X. Amounts near the above upper limit are preferably used in solid, particulate agents. In particular, suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m. Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates. The alkali metal silicates useful as builders in the detergents or cleaners according to the invention preferably have a molar ratio of alkali metal oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12, and may be present in amorphous or crystalline form.

Builder substances are preferably present in the detergents or cleaners according to the invention in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight. Inventive laundry after-treatment, such as. As fabric softener, are preferably free of inorganic builder.

Suitable peroxygen compounds are, in particular, organic peracids or peracid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which release hydrogen peroxide under the conditions of use, such as perborate, percarbonate and / or persilicate. If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped in a manner known in principle. Particular preference is given to using alkali percarbonate, alkali perborate monohydrate or, in particular, in liquid media, hydrogen peroxide in the form of aqueous solutions which contain from 3% by weight to 10% by weight of hydrogen peroxide. If a washing or cleaning agent according to the invention contains bleaches, such as preferably peroxygen compounds, these are present in amounts of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight. The addition of small amounts of known bleach stabilizers such as phosphonates, bristles or metaborates and metasilicates and magnesium acids such as magnesium sulfate may be useful.

As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran and enol esters, and also acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfruktose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated Lactams, for example N-benzoyl-caprolactam. Hydrophilic substituted acyl acetals and acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used. Such bleach activators can be used in the conventional amount range, preferably in amounts of from 1 wt .-% to 10 wt .-%, in particular 2 wt .-% to 8 wt .-%, based on the total agent, be contained.

Suitable enzymes which can be used in the detergents or cleaners are those from the class of the proteases, cutinases, amylases, pullulanases, hemicellulases, cellulases, lipases, oxidases and peroxidases and mixtures thereof. Particularly suitable are from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia derived enzymatic agents. The optionally used enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation. They are present in the washing or cleaning agents according to the invention, preferably not more than 5% by weight, in particular from 0.2% by weight to 2% by weight.

The detergents or cleaners may contain, for example, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Suitable salts are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which, instead of the morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the substituted diphenylstyrene type may be present, for example the alkali metal salts of 4,4'-bis (2-sulfostryry) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned brightener can be used.

Suitable foam inhibitors include, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffin waxes and mixtures thereof with silanated silicic acid or fatty acid alkylene diamides. It is also advantageous to use mixtures of various foam inhibitors, for example those of silicones, paraffins or waxes. The foam inhibitors, in particular silicone- and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffin waxes and bistearylethylenediamides are preferred.

In addition, the washing or cleaning agents may also contain components that positively influence the oil and Fettauswaschbarkeit from textiles, so-called soil release agents. This effect is particularly evident when a textile is soiled, which has been previously washed several times with a detergent containing this oil and fat dissolving component was washed. The preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic Cellulose ethers, and the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof with monomeric and / or polymeric diols, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof.

The washing or cleaning agents may also color transfer inhibitors, preferably in amounts of 0.1 wt .-% to 2 wt .-%, in particular 0.1 wt .-% to 1 wt .-%, containing, in a preferred embodiment of Invention Polymers of vinylpyrrolidone, vinylimidazole, vinylpyridine-N-oxide or copolymers thereof. Polyvinylpyrrolidones having molecular weights of from 15,000 to 50,000 as well as polyvinylpyrrolidones having molecular weights of more than 1,000,000, in particular from 1,500,000 to 4,000,000, N-vinylimidazole / N-vinylpyrrolidone copolymers, polyvinyl oxazolidones, copolymers based on vinyl monomers, and polyvinylpyrrolidones, are useful Carboxylic acid amides, pyrrolidone group-containing polyesters and polyamides, grafted polyamidoamines and polyethyleneimines, polymers containing amide groups from secondary amines, polyamine-N-oxide polymers, polyvinyl alcohols and copolymers based on acrylamidoalkenylsulfonic acids.

Graying inhibitors have the task of keeping suspended from the textile fiber dirt suspended in the fleet. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, other than the above-mentioned starch derivatives can be used, for example aldehyde starches. Preference is given to cellulose ethers, such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the washing or cleaning agent, used.

The organic solvents which can be used in the detergents or cleaners according to the invention, especially if they are in liquid or pasty form, include alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C-atoms, in particular ethylene glycol and propylene glycol, and mixtures thereof and the derivable from said classes of compounds ethers. Such water-miscible solvents are preferably present in the detergents or cleaners according to the invention in amounts of not more than 30% by weight, in particular from 6% by weight to 20% by weight.

For setting a desired, by the mixture of the other components not automatically resulting pH value, detergents or cleaning agents of the invention can system- and environmentally friendly acids, especially citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight, in the detergents or cleaners according to the invention.

The preparation of solid detergents or cleaning agents according to the invention presents no difficulties and can in principle be carried out in known manner, for example by spray-drying or granulation, wherein e.g. For example, peroxygen compound and bleach catalyst may be added later. The microcapsules according to the invention and optionally further fragrances are preferably introduced into the washing or cleaning agent at the end of the preparation. For the production of inventive detergents or cleaners having an increased bulk density, in particular in the range from 650 g / l to 950 g / l, a process comprising an extrusion step is preferred. The preparation of liquid detergents or cleaners according to the invention likewise presents no difficulties and can likewise be carried out in a known manner, the microcapsules according to the invention and optionally further fragrances preferably being introduced into the washing or cleaning agent at the end of the preparation.

According to a preferred embodiment, the teaching of the invention can be used to reduce the perfume fraction in consumer products such as detergents, cleansers and personal care products, because the incorporation of the perfumes in the microcapsules a particularly efficient perfuming can be ensured.

• (a) Aniontenside, wie vorzugsweise Alkylbenzolsulfonat, Alkylsulfat, z. B. in Mengen von vorzugsweise 5–30 Gew.-%
• (b) Nichtionische Tenside, wie vorzugsweise Fettalkoholpolyglycolether, Alkylpolyglucosid, Fettsäureglucamid z. B. in Mengen von vorzugsweise 0,5–15 Gew.-%
• (c) Gerüststoffe, wie z. B. Zeolith, Polycarboxylat, Natriumcitrat, in Mengen von z. B. 0–70 Gew.-%, vorteilhafterweise 5–60 Gew.-%, vorzugsweise 10–55 Gew.-%, insbesondere 15–40 Gew.-%,
• (d) Alkalien, wie z. B. Natriumcarbonat, in Mengen von z. B. 0–35 Gew.-% vorteilhafterweise 1–30 Gew.-%, vorzugsweise 2–25 Gew.-%, insbesondere 5–20 Gew.-%,
• (e) Bleichmittel, wie z. B. Natriumperborat, Natriumpercarbonat, in Mengen von z. B. 0–30 Gew.-% vorteilhafterweise 5–25 Gew.-%, vorzugsweise 10–20 Gew.-%,
• (f) Korrosionsinhibitoren, z. B. Natriumsilicat, in Mengen von z. B. 0–10 Gew.-%, vorteilhafterweise 1–6 Gew.-%, vorzugsweise 2–5 Gew.-%, insbesondere 3–4 Gew.-%,
• (g) Stabilisatoren, z. B. Phosphonate, vorteilhafterweise 0–1 Gew.-%, (h) Schauminhibitor, z. B. Seife, Siliconöle, Paraffine vorteilhafterweise 0–4 Gew.-%, vorzugsweise 0,1–3 Gew.-%, insbesondere 0,2–1 Gew.-%,
• (i) Enzyme, z. B. Proteasen, Amylasen, Cellulasen, Lipasen, vorteilhafterweise 0–2 Gew.-%, vorzugsweise 0,2–1 Gew.-%, insbesondere 0,3–0,8 Gew.-%,
• (j) Vergrauungsinhibitor, z. B. Carboxymethylcellulose, vorteilhafterweise 0–1 Gew.-%,
• (k) Verfärbungsinhibitor, z. B. Polyvinylpyrrolidon-Derivate, z. B. 0–2 Gew.-%,
• (l) Stellmittel, z. B. Natriumsulfat, vorteilhafterweise 0–20 Gew.-%,
• (m) Optische Aufheller, z. B. Stilben-Derivat, Biphenyl-Derivat, vorteilhafterweise 0–0,4 Gew.-%, insbesondere 0,1–0,3 Gew.-%,
• (n) ggf. weitere Riechstoffe
• (o) ggf. Wasser
• (p) ggf. Seife
• (q) ggf. Bleichaktivatoren
• (r) ggf. Cellulosderivate
• (s) ggf. Schmutzabweiser,

A preferred washing or cleaning agent according to the invention is a solid, in particular powdered, detergent which, in addition to the microcapsules according to the invention, may preferably contain components which, for. B. are selected from the following:

• (a) anionic surfactants, such as preferably alkylbenzenesulfonate, alkylsulfate, e.g. B. in amounts of preferably 5-30 wt .-%
• (b) Nonionic surfactants, such as, preferably, fatty alcohol polyglycol ethers, alkylpolyglucoside, fatty acid glucamide, e.g. B. in amounts of preferably 0.5-15 wt .-%
• (c) builders, such as. As zeolite, polycarboxylate, sodium citrate, in amounts of z. B. 0-70 wt .-%, advantageously 5-60 wt .-%, preferably 10-55 wt .-%, in particular 15-40 wt .-%,
• (d) alkalis, such as. For example, sodium carbonate, in amounts of z. B. 0-35 wt .-% advantageously 1-30 wt .-%, preferably 2-25 wt .-%, in particular 5-20 wt .-%,
• (e) bleaching agents, such as. For example, sodium perborate, sodium percarbonate, in amounts of z. B. 0-30 wt .-% advantageously 5-25 wt .-%, preferably 10-20 wt .-%,
• (f) corrosion inhibitors, e.g. For example, sodium silicate, in amounts of z. B. 0-10 wt .-%, advantageously 1-6 wt .-%, preferably 2-5 wt .-%, in particular 3-4 wt .-%,
• (g) stabilizers, e.g. As phosphonates, advantageously 0-1 wt .-%, (h) foam inhibitor, for. As soap, silicone oils, paraffins advantageously 0-4 wt .-%, preferably 0.1-3 wt .-%, in particular 0.2-1 wt .-%,
• (i) enzymes, e.g. B. proteases, amylases, cellulases, lipases, advantageously 0-2 wt .-%, preferably 0.2-1 wt .-%, in particular 0.3-0.8 wt .-%,
• (j) grayness inhibitor, e.g. B. carboxymethylcellulose, advantageously 0-1 wt .-%,
• (k) discoloration inhibitor, e.g. As polyvinylpyrrolidone derivatives, z. 0-2% by weight,
• (l) adjusting means, e.g. For example, sodium sulfate, advantageously 0-20 wt .-%,
• (m) optical brighteners, e.g. B. stilbene derivative, biphenyl derivative, advantageously 0-0.4 wt .-%, in particular 0.1-0.3 wt .-%,
• (n) optionally other fragrances
• (o) if necessary water
• (p) if necessary, soap
• (q) optionally bleach activators
• (r) optionally cellulosic derivatives
• (s) if necessary dirt deflector,

% By weight, based in each case on the total agent.

In another preferred embodiment of the invention, the washing or cleaning agent is in liquid form, preferably in gel form. Preferred liquid detergents or cleaners have water contents of z. B. 10-95 wt .-%, preferably 20-80 wt .-% and in particular 30-70 wt .-%, based on the total agent. In the case of liquid concentrates, the water content may also be particularly low, for. B. ≤ 30 wt .-%, preferably 20 wt .-%, in particular ≤ 15 wt .-%, wt .-% in each case based on the total agent. The liquid consumer products may also contain non-aqueous solvents.

• – Aniontenside, wie vorzugsweise Alkylbenzolsulfonat, Alkylsulfat, z. B. in Mengen von vorzugsweise 5–40 Gew.-%
• – Nichtionische Tenside, wie vorzugsweise Fettalkoholpolyglycolether, Alkylpolyglucosid, Fettsäureglucamid z. B. in Mengen von vorzugsweise 0,5–25 Gew.-%
• – Gerüststoffe, wie z. B. Zeolith, Polycarboxylat, Natriumcitrat, vorteilhafterweise 0–15 Gew.-%, vorzugsweise 0,01–10 Gew.-%, insbesondere 0,1–5 Gew.-%,
• – Schauminhibitor, z. B. Seife, Siliconöle, Paraffine, in Mengen von z. B. 0–10 Gew.-%, vorteilhafterweise 0,1–4 Gew.-%, vorzugsweise 0,2–2 Gew.-%, insbesondere 1–3 Gew.-%,
• – Enzyme, z. B. Proteasen, Amylasen, Cellulasen, Lipasen, in Mengen von z. B. 0–3 Gew.-%, vorteilhafterweise 0,1–2 Gew.-%, vorzugsweise 0,2–1 Gew.-%, insbesondere 0,3–0,8 Gew.-%,
• – Optische Aufheller, z. B. Stilben-Derivat, Biphenyl-Derivat, in Mengen von z. B. 0–1 Gew.-%, vorteilhafterweise 0,1–0,3 Gew.-%, insbesondere 0,1–0,4 Gew.-%,
• – ggf. weitere Riechstoffe
• – ggf. Stabilisatoren,
• – Wasser
• – ggf. Seife, in Mengen von z. B. 0–25 Gew.-%, vorteilhafterweise 1–20 Gew.-%, vorzugsweise 2–15 Gew.-%, insbesondere 5–10 Gew.-%,
• – ggf. Lösungsmittel (vorzugsweise Alkohole), vorteilhafterweise 0–25 Gew.-%, vorzugsweise 1–20 Gew.-%, insbesondere 2–15 Gew.-%, Gew.-% jeweils bezogen auf das gesamte Mittel.

A preferred washing or cleaning agent according to the invention is a liquid, in particular gel detergent which, in addition to the microcapsules according to the invention, may preferably contain components which, for. B. are selected from the following:

• - Aniontenside, such as preferably alkylbenzenesulfonate, alkyl sulfate, z. B. in amounts of preferably 5-40 wt .-%
• Nonionic surfactants, such as preferably fatty alcohol polyglycol ethers, alkylpolyglucoside, fatty acid glucamide z. B. in amounts of preferably 0.5-25 wt .-%
• - builders, such. B. zeolite, polycarboxylate, sodium citrate, advantageously 0-15 wt .-%, preferably 0.01-10 wt .-%, in particular 0.1-5 wt .-%,
• Foam inhibitor, e.g. As soap, silicone oils, paraffins, in amounts of z. B. 0-10 wt .-%, advantageously 0.1-4 wt .-%, preferably 0.2-2 wt .-%, in particular 1-3 wt .-%,
• - enzymes, eg. As proteases, amylases, cellulases, lipases, in amounts of z. B. 0-3 wt .-%, advantageously 0.1-2 wt .-%, preferably 0.2-1 wt .-%, in particular 0.3-0.8 wt .-%,
• - Optical brightener, z. B. stilbene derivative, biphenyl derivative, in amounts of z. B. 0-1 wt .-%, advantageously 0.1-0.3 wt .-%, in particular 0.1-0.4 wt .-%,
• - If necessary, further fragrances
• - stabilizers if necessary,
• - Water
• - If necessary, soap, in quantities of z. B. 0-25 wt .-%, advantageously 1-20 wt .-%, preferably 2-15 wt .-%, in particular 5-10 wt .-%,
• - If necessary, solvents (preferably alcohols), advantageously 0-25 wt .-%, preferably 1-20 wt .-%, in particular 2-15 wt .-%, wt .-% in each case based on the total agent.

• – Kationische Tenside, wie insbesondere Esterquats, z. B. in Mengen von 5–30 Gew.-%,
• – Cotenside, wie z. B. Glycerolmonostearat, Stearinsäure, Fettalkohole, Fettalkoholethoxylate, z. B. in Mengen von 0–5 Gew.-%, vorzugsweise 0,1–4 Gew.-%,
• – Emulgatoren, wie z. B. Fettaminethoxylate, z. B. in Mengen von 0–4 Gew.-%, vorzugsweise 0,1–3 Gew.-%,
• – ggf. weitere Riechstoffe
• – ggf. Farbstoffe, vorzugsweise im ppm-Bereich
• – ggf. Stabilisatoren, vorzugsweise im ppm-Bereich
• – Lösemittel, wie insbesondere Wasser, z. B. in Mengen von 60–90 Gew.-%,

A preferred washing or cleaning agent according to the invention is a liquid softener which, in addition to the microcapsules according to the invention, may preferably contain components which are selected from the following:

• - Cationic surfactants, such as in particular esterquats, z. In amounts of 5-30% by weight,
• - cosurfactants, such as. As glycerol monostearate, stearic acid, fatty alcohols, fatty alcohol ethoxylates, eg. In amounts of 0-5% by weight, preferably 0.1-4% by weight,
• - emulsifiers, such as. B. fatty amine ethoxylates, e.g. In amounts of 0-4 wt.%, Preferably 0.1-3 wt.%,
• - If necessary, further fragrances
• - If necessary, dyes, preferably in the ppm range
• - Stabilizers if necessary, preferably in the ppm range
• - Solvents, such as in particular water, for. In amounts of 60-90% by weight,

% By weight, based in each case on the total agent.

Examples:

In encapsulation experiments, in addition to toluene (Ex. No. 1), fragrances, namely α-damascone (Ex. No. 2-6) and phenylethyl alcohol (Ex. No. 7) were successfully encapsulated. Information on the microcapsules obtained can be found in Table 1. Table 1 Example no. Epoxide / amine shell Stoich. Cont. Epoxide / amine protective colloid surfactant active substance 1 DER 331 / DET 1: 1.5 2% Mow. 0.5% SDS toluene 2 DER 331 / DET 1: 1.5 2% Mow. 0.5% SDS α-Damascone 3 DER 331 / DET 1: 1.5 2.5% Mow. 0.5% SDS α-Damascone 4 DER 331 / DET 1: 1.5 3.0% Mow. 0.23% SDS α-Damascone 5 DER 331 / DET 1: 1.5 3.0% Coll. 0.3% SDS α-Damascone 6 DER 331 / DET 1: 1.5 3.0% Lup. 0.3% SDS α-Damascone 7 DER 331 / DET 1: 1.5 2.5% Mow. 0.5% SDS phenylethyl DET = diethylenetriamine
DER 331 = ^{DER® 331®} from DOW. This is a liquid epoxy resin. It is the reaction product of epichlorohydrin and bisphenol-A, hence a bisphenol A diglycidyl ether. The EEW value (EEW = epoxy equivalent weight in g / eq) of DER ^® 331 ^® is according to the manufacturer's instructions at 182-192 (determined in accordance with the manufacturer's instructions in accordance with ASTM D-1652 ).
SDS = Disponil SDS = sodium lauryl sulfate
Mow. = Mowiol 4-88 (which is a partially hydrolyzed polyvinyl alcohol, degree of hydrolysis 87.2-88.8% from KSE Kuraray Specialties Europe))
Coll. = Collacral VAL (which is a vinylpyrrolidone copolymer from BASF)
Lup. = Lupasol P (which is a polyethylenimine from BASF)

The% value in Table 1 with respect to protective colloid and surfactant refers in each case to the concentration in water. Description of individual experiments from Table 1: Example No. 2 G water phase water 96.5 Disponil SDS 0.5 diethylenetriamine 1.0 Mowiol4-88 2.0 Organic phase THE 331st 3.8 a-Damascone 6.0 total 109.8 Amine / epoxy ratio 1.5: 1

The homogeneous water phase was placed in the flask, with stirring (360 rpm) then the organic phase was added. It was heated to 70 ° C, after 30 minutes, the temperature was raised to 75 ° C, held there for 1 h, then the temperature was maintained at 80 ° C for 3 h. It was then cooled. The microcapsules were filtered off, washed with 30% ethanol and water and dried in a convection oven at room temperature. Example No. 3 G water phase water 96.0 Disponil SDS 0.5 diethylenetriamine 1.0 Mowiol 4-88 2.5 Organic phase THE 331st 3.8 a-Damascone 4.0 total 107.8 Amine / epoxy ratio 1.5: 1

The homogeneous water phase was introduced into the flask while stirring (360 rpm) the organic phase was added. The mixture was heated to 70 ° C, after 30 minutes, the temperature was then raised to 75 ° C, held there for 1 h, then the temperature was maintained at 80 ° C for 2 h, then cooled. The microcapsules were filtered off, washed with 30% ethanol and water and dried in a convection oven at room temperature. Example No. 4 G water phase water 95.77 Disponil SDS 0.23 diethylenetriamine 1.0 Mowiol 4-88 3.0 Organic phase THE 331st 3.8 a-Damascone 6.0 total 109.8 Amine / epoxy ratio 1.5: 1

The homogeneous water phase was introduced into the flask while stirring (360 rpm) the organic phase was added. The mixture was heated to 70 ° C, after 30 minutes, the temperature was raised to 75 ° C and held there for 1 h and then the temperature was maintained at 80 ° C for 2 h, then cooled. The microcapsules were filtered off, washed with 30% ethanol and water and dried in a convection oven at room temperature. Example No. 5 G water phase water 88.7 Disponil SDS 0.3 diethylenetriamine 1.0 Collacral VAL 30% 10.0 Organic phase THE 331st 3.8 a-Damascone 6.0 total 109.8 Amine / epoxy ratio 1.5: 1

The homogeneous water phase was placed in the flask, with stirring (360 rpm), the organic phase was added, it was heated to 70 ° C, after 30 minutes, the temperature was raised to 75 ° C and held for 1 h and then the temperature was still Held at 80 ° C for 2 h.

Then it was cooled. Microcapsules were filtered off, washed with 30% ethanol and water and dried in a convection oven at room temperature. Example No. 6 G water phase water 92.7 Disponil SDS 0.3 diethylenetriamine 1.0 Lupasol P (50%) 6.0 Organic phase THE 331st 3.8 a-Damascone 6.0 total 109.8 Amine / epoxy ratio 1.5: 1

The homogeneous water phase was introduced into the flask while stirring (360 rpm) the organic phase was added. The mixture was heated to 70 ° C., after 30 minutes the temperature was kept at 75 ° C. and held there for 1 h and then the temperature was kept at 80 ° C. for a further 2 h. Then it was cooled. Microcapsules were filtered off, washed with 30% ethanol and water and dried in a convection oven at room temperature.

The microcapsules obtained in each case showed a very good diffusion resistance, confirmed by washing tests with 30% ethanol and water. It was possible to realize proportions of encapsulated active substance (toluene, damascone, phenylethyl alcohol) of> 50% by weight, based on the total weight of the microcapsule.

QUOTES INCLUDE IN THE DESCRIPTION

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

Cited patent literature

• US 4406816 [0003]
• DE 19932144 A1 [0003]
• DE 10037656 A1 [0005]
• DE 10101892 A1 [0005]
• DE 4436535 A1 [0006]
• US 4626471 [0007]

Cited non-patent literature

• J. Microencapsulation, 2002, 19, 559 (authors: HY Lee, SJ Lee, IW Cheong and JH Kim) [0003]
• D. Crespy et. al. was reported in Macromolecules, 2007, 40, 3122 [0004]
• Theisinger et al. in Macromol. Chem. Phys. 2009, 210 [0005]
• ASTM D-1652 [0047]
• ASTM D-1652 [0048]
• ASTM D-1652 [0101]

Claims (14)

Process for the preparation of active-substance-containing microcapsules having an average particle diameter greater than 1 μm to 500 μm by interfacial polymerization, the process comprising the following process steps: (A) combining an organic phase which comprises at least one di- or polyfunctional epoxide (monomer I which has at least 2 epoxide groups (oxirane rings)) and hydrophobic active substances, with a water phase which, in addition to water, at least one with the di- or polyfunctional epoxide (monomer I), under polymerization reaction, in particular polyaddition, reacting compound (monomer II, which in the polymerization reaction, in particular polyaddition, reactive functional groups comprises), with mixing of the phases in the presence of at least one surfactant to form an oil-in -water emulsion (b) carrying out a polymerization reaction, in particular polyaddition reaction, between the monomers I and II in the presence of the hydrophobic active substance to be encapsulated and a surfactant in the emulsion provided under step (a), thereby encapsulating the active in the polymerization reaction, in particular polyaddition , produced microcapsules is effected; and (c) optionally subsequently separating the active substance-containing microcapsules obtained in this way. Process according to Claim 1, characterized in that the monomer I and the monomer II are used in a ratio such that the stoichiometric ratio of epoxide groups (oxirane rings) to the reactive functional groups of the monomer II which are ≤ 1 in the polymerization reaction, in particular polyaddition Is 1, preferably less than 1: 1.1, advantageously less than 1: 1.2, more preferably less than 1: 1.3, in particular less than 1: 1.4. A method according to claim 1 or 2, characterized in that the resulting active substance-containing microcapsules have average particle diameters of 5-250 microns, preferably 10-200 microns in particular 15-100 microns. Method according to one of claims 1 to 3, characterized in that the monomer II is selected from the group of (i) di- and polyfunctional amines and mixtures thereof, (ii) di- and polyfunctional alkanols and mixtures thereof, (iii) di - and polyfunctional mercaptans and mixtures thereof, and (iv) mixtures of the aforementioned compounds. A method according to any one of claims 1 to 4, characterized in that the monomer II is selected from di- or polyfunctional amines, in particular selected from the group comprising diaminoethane, diethylenetriamine; dimethylpropanediamine; 1,2-propylene diamine; isophoronediamine; 2,2-dimethylpropane-1,3-diamine; octamethylene; N- (2-aminoethyl) ethanolamine; Piperazine, O, O'-bis (2-aminopropyl) polypropylene glycol, (3- (2-aminoethylamino) propylamine), 1,3-diaminopropane, 3- (cyclohexylamino) propylamine; 3- (methylamino) propylamine; dipropylenetriamine; N, N-bis (3-aminopropyl) methylamine; N, N'-bis (3-aminopropyl) ethylenediamine, as well as mixtures of the aforementioned compounds. A method according to any one of claims 1 to 5, characterized in that the hydrophobic active substance comprises fragrances, essential oils, perfume oils, care oils and / or silicone oils. A process according to any one of claims 1 to 6, wherein the monomer I is a difunctional epoxide and is in particular derived from bisphenol A such as bisphenol A diglycidyl ether or an epichlorohydrin substituted bisphenol type epoxide is like the epoxide of the formula

with N = 0-20. Method according to one of claims 1 to 6, wherein the monomer I is a trifunctional epoxide, in particular an epoxide of the formula

Method according to one of claims 1 to 6, wherein the monomer I is a tetrafunctional epoxide, in particular an epoxide of the formula

Active substance-containing microcapsules obtainable by a process according to one of claims 1 to 9. Microcapsules according to claim 10, characterized in that the active substance content of the microcapsules 0.01 to 90 wt .-%, preferably 0.1 to 80 wt .-%, in particular 1 to 70 wt .-%, based on the total weight of the capsules , Use of the microcapsules according to claims 10 or 11 for the incorporation of active substances into products from the field of detergents or cleaners, cosmetics, pharmacy and adhesives. Use of the microcapsules according to claims 10 or 11 for the controlled release of active substances in the use of products from the field of detergents, cosmetics, pharmaceuticals and adhesives. Detergents or cleaning compositions comprising microcapsules according to claims 10 or 11.