WO2004005448A1 - Portioned liquid cleaning agent and detergent preparations - Google Patents

Abstract

The invention relates to portioned liquid cleaning agent and detergent preparations consisting of (a) a water-soluble casing, (b) a liquid phase that is surrounded by said casing and (c) encapsulated active ingredients that are dispersed in the liquid phase.

Description

 Portioned liquid detergent and cleaning agent preparations

Field of the Invention

The invention is in the field of detergents and relates to liquid preparations in water-soluble sachets which contain microencapsulated active ingredients.

State of the art

Detergents and cleaning agents have gone through a wide range of forms in recent years. While powdery detergents and liquid cleaners dominated the market 10 years ago, both liquid detergents and solid cleaners have now become established. In addition to the packaging, the optical distinguishing features are the specific design of the products. For example, in addition to fine powders with a high bulk density, rounded granules ("megapearls"), tablets with one, two or three components are available for the solid forms, whereas the spectrum for liquid preparations has so far been considerably smaller. In addition to classic liquid products that are metered directly via a measuring cap, there are sprayable formulations with low viscosity or, conversely, viscous gels, which have the advantage that they do not run off so quickly on vertical surfaces. Apart from such practical considerations, market activity is not infrequently controlled by simply having to offer the consumer a new product, whereby the superiority over the previous state of the art sometimes comes to the fore. The opposite is often the case, i.e. for the manufacture of such a product with an at least satisfactory, i.e. same quality, problems have to be overcome, the solution of which then represents the actual innovation.

Liquid preparations, especially liquid detergents, have been on the market for a short time and are available in the form of sachets. The actual liquid surfactant phase is enclosed in a polymer shell, which dissolves in the wash liquor and thereby releases the surface-active compounds. Most surfactants, however, are solids that are sold in the form of more or less dilute aqueous pastes. In order to a problem immediately becomes apparent in the production of such portioned liquid detergents: the incorporation, for example, of anionic or amphoteric surfactants into the formulation is unsuccessful, since this would require the presence of water. However, this is out of the question, since otherwise the portion bag would dissolve long before its actual predetermined end. For this reason, customary portioned liquid detergents contain all or practically exclusively nonionic surfactants, especially those of the fatty alcohol polyglycol ether type, since these are liquid even in the anhydrous state. Now it is a peculiarity of quasi conventional liquid detergents that they have a high content of non-ionic surfactants, since they are easy to assemble and in particular have the advantage of inverse solubility, ie they have better water solubility at lower temperatures than in Warmth. Liquid detergents are therefore preferred for washing at 30 to 60 ° C. Conversely, of course, this also reveals their weakness: they are of little use in the field of cooked laundry, and they are hardly effective when it comes to removing greasy dirt.

The problem for the manufacturer of new portioned liquid detergents and cleaning agents therefore arises that he can only use surfactant preparations which are liquid and water-free or practically water-free at the same time, since otherwise the water-soluble casing dissolves prematurely. For this purpose, almost exclusively non-ionic surfactants come into question, but they only cover part of the desired performance spectrum with regard to their application properties.

The object of the present invention was therefore to improve the known portioned preparations on the market to such an extent that the use, in particular, of anionic, amphoteric or zwitterionic or cationic surfactants and of active ingredients which are otherwise difficult or impossible dissolve or disperse in the usual nonionic surfactant phase. The new agents accessible in this way should not only distinguish themselves from other portioned preparations, but also from conventional liquid products on the market, by virtue of their advantageous technical properties, and if possible they should also have an interesting, appealing appearance. Description of the invention

The invention relates to portioned liquid detergent and cleaning agent preparations, such as, for example, liquid detergent, dishwashing detergent, universal detergent or softener, consisting of

(a) a water-soluble envelope,

(b) a liquid phase enclosed by the shell, and

(c) encapsulated active ingredients dispersed in the liquid phase.

The encapsulation of surfactants that are only liquid in aqueous solution or of active ingredients that cannot be dissolved or dispersed in the liquid phase, or only to a small extent, shows a way of changing the formulation of known portioned liquid detergents and cleaning agents to supplement the components that could not be incorporated so far due to the necessary entry of water. The active ingredients lead to a significant improvement in the application properties of the preparations - in some cases even compared to conventional liquid products - because the active ingredients are delayed but then released in a concentrated manner so that, for example, a locally very high concentration is generated in the wash liquor. Another advantage of the preparations is that sensitive active ingredients or ingredients that are incompatible with other components can be incorporated in a microencapsulated manner without decomposition or chemical reactions. The capsules can be dispersed homogeneously and stably in the liquid phase, for example with the use of polymeric thickeners. If they additionally (or also exclusively) contain dyes, preparations with a particularly appealing appearance are obtained, for example if yellow-colored microcapsules are present in a green-colored liquid matrix.

Water soluble shell

The preparations are portioned in such a way that the liquid phase is enclosed by a solid shell, which preferably consists of at least one water-soluble polymer. The term "water-soluble" is to be understood in such a way that the shell completely dissolves in an aqueous environment within a period of 1 to 20 minutes, depending on the water temperature. The shell preferably consists entirely or predominantly of polyvinyl alcohol. Liquid phase

An essential characteristic of the liquid phase enclosed by the casing is that it is anhydrous or has such a low water content that the casing does not prematurely dissolve or become permeable. As a rule, therefore, water contents can have a maximum of 5, preferably a maximum of 3 and in particular a maximum of 1% by weight. The liquid phase is usually a non-ionic surfactant phase.

Nonionic surfactants

Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, (hydroxy) mixed ethers or mixed formals, alk (en) yloligoglycosides, fatty acids, especially vegetable hydrolysates, especially fatty acid-N-alkyl glucose amines Wheat-based products), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution. Fatty alcohol polyglycol ethers, alkoxylated fatty acid lower alkyl esters, hydroxy mixed ethers or alkyl oligoglucosides are preferably used.

> Fatty alcohol polyglycol ether

The preferred fatty alcohol polyglycol ethers follow the formula (I)

R ¹ O (CH ₂ CHR ² O) "ιH (I)

in which R ^{1 is} a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms, R ^{2 is} hydrogen or methyl and nl is

Numbers from 1 to 20 stands. Typical examples are the addition products of an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide with capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostanol , Oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures. Especially Addition products of 3, 5 or 7 moles of ethylene oxide with technical coconut oil alcohols are preferred.

> Alkoxylated fatty acid lower alkyl esters

Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula (II)

R ³ CO (OCH ₂ CHR ⁴ ) _n2 OR ⁵ (II)

in which R ³ CO stands for a linear or branched, saturated and / or unsaturated acyl radical with 6 to 22 carbon atoms, R ⁴ for hydrogen or methyl, R ⁵ for linear or branched alkyl radicals with 1 to 4 carbon atoms and n2 for numbers of 1 to 20 stands. Typical examples are the formal insert products of an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide in the methyl, ethyl, propyl, isopropyl, butyl and tert-butyl esters of caproic acid, caprylic acid,

2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroseline acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, uric acid and mixtures thereof, and eronic acid and mixtures thereof. The products are usually prepared by inserting the alkylene oxides into the carbonyl ester bond in the presence of special catalysts, e.g. calcined hydrotalcite. Reaction products of an average of 5 to 10 moles of ethylene oxide into the ester linkage of technical coconut fatty acid methyl esters are particularly preferred.

> Hydroxy mixed ether

Hydroxy mixed ethers (HME) are known nonionic surfactants with an asymmetrical ether structure and polyalkylene glycol components, which can be obtained, for example, by subjecting olefin epoxides to a ring-opening reaction with fatty alcohol polyglycol ethers. Typically following hydroxy mixed ethers of the general formula

OH CH ₃

R ⁶ CH-CHR ⁷ O (CH ₂ CH2θ) _n3 (CH ₂ CHO) _m (CH ₂ CH ₂ O) _n4 R ⁸ (TO) in which R ^{6 represents} a linear or branched alkyl radical having 2 to 18, preferably 10 to 16 carbon atoms, R ^{7 represents} hydrogen or a linear or branched alkyl radical having 2 to 18 carbon atoms, R ^{8 represents} a linear or branched alkyl and / or alkenyl radical with 1 to 22, preferably 8 to 18 carbon atoms, n3 and n4 independently of one another for 0 or numbers from 1 to 60, preferably 2 to 25 and in particular 5 to 15 and m for 0 or numbers from 0.5 to 5, preferably 1 to 2, with the provisos that the sum of the carbon atoms in the radicals R and R is at least 6 and preferably 12 to 18 and the sum (n3 + m + n4) is different from 0. As can be seen from the formula, the HME ring opening products can be either from internal olefins (R ⁷ not hydrogen) or terminal olefins (R ⁷ is hydrogen), the latter being preferred in view of the easier preparation and the more advantageous application properties. Likewise, the polar part of the molecule can be a polyethylene or a polypropylene chain; Mixed chains of PE and PP units are also suitable, be it in statistical or block distribution. Typical examples are ring opening products of 1,2-hexenepoxide, 2,3-hexenepoxide, 1,2-octene epoxide, 2,3-octene epoxide, 3,4-octene epoxide, 1,2-decene epoxide, 2,3-decene epoxide, 3,4 -Decenepoxid, 4,5-Decenepoxid, 1,2-Dodecenepoxid, 2,3-Dodecenepoxid, 3,4-Dodecenepoxid, 4,5-Dodecenepoxid, 5,6-Dodecenepoxid, 1,2-Tetradecenepoxid, 2,3-Tetradecenepoxid , 3,4-Tetradecenepoxid, 4,5-Tetradecenepoxid, 5,6-Tetradecenepoxid, 6,7-Tetradecenepoxid, 1,2-Hexadecen epoxide, 2,3-Hexadecenepoxid, 3,4-Hexadecenepoxid, 4,5-Hexadecenepoxid , 5,6-hexadecene epoxide, 6,7-hexadecene epoxide, 7,8-hexadecene epoxide, 1,2-octadecene epoxide, 2,3-octadecene epoxide, 3,4-octadecenepoxide, 4,5-octadecene epoxide, 5,6-octadecene epoxide , 6,7-octadecene epoxide, 7,8-octadecene epoxide and 8,9-octadecene epoxide and their mixtures with addition products of on average 1 to 50, preferably 2 to 25 and in particular 5 to 15 moles of ethylene oxide and / or 1 to 10, preferably 2 to 8 and in particular 3 to 5 mol of propylene oxide to saturated and / o the unsaturated primary alcohols having 6 to 22, preferably 12 to 18 carbon atoms, such as, for example, capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, elesyl alcoholo, oleyl alcoholo, alolidyl alcohol, aloleyl alcohol, oleyl alcohol, allyol alcohol , Linolyl alcohol, Linolenyl alcohol, Elaeostearyl alcohol, Arachyl alcohol, Gadoleyl alcohol, Behenyl alcohol, Erucyl alcohol and Brassidyl alcohol and their technical mixtures. Hydroxy mixed ethers which have proven to be particularly suitable from an application point of view follow the formula (III) in the

> R ⁶ for a linear alkyl radical with 8 to 10 carbon atoms, R ⁷ for hydrogen, R ⁸ for a linear alkyl radical with 8 to 10 carbon atoms, n3 for 0, m stands for numbers from 0.5 to 2 and n4 for numbers from 20 to 40, such as the commercial products Dehypon® KE 3447 and Dehypon® KE 3557 (Cognis).

> R ^{6 is} a linear alkyl radical having 8 to 10 carbon atoms, R ^{7 is} hydrogen, R ^{8 is} a branched alkyl radical having 8 to 10 carbon atoms, n3 and m are 0 and n4 are numbers from 20 to 40;

> R ^{6 is} a linear alkyl radical with 8 to 10 carbon atoms, R ^{7 is} hydrogen, R ^{8 is} a linear alkyl radical with 8 to 10 carbon atoms, n3 and m are 0 and n4 are numbers from 40 to 60.

Alkyl and / or alkenyl oligo glycosides

Alkyl and alkenyl oligoglycosides, which are also preferred nonionic surfactants, usually follow the formula (IV),

R ⁹ O- [G] _p (IV)

in which R ^{9 represents} an alkyl and or alkenyl radical having 4 to 22 carbon atoms, G represents a sugar radical having 5 or 6 carbon atoms and p represents numbers from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry. The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (IV) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p in a given compound must always be an integer and here can assume the values p = 1 to 6, the value p for a certain alkyl oligoglycoside is an analytically determined arithmetic parameter, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and is in particular between 1.2 and 1.4. The alkyl or alkenyl radical R ⁹ can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capronic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol, as well as their technical mixtures, such as are obtained, for example, from hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl- ligoglucosides of chain length C ₈ -C ₁₀ (DP = 1 to 3), which are obtained as a preliminary step in the separation of technical C ₈ -C ₁₈ coconut fatty alcohol by distillation and contaminated with a proportion of less than 6% by weight of C ₁₂ alcohol can be as well as alkyl oligoglucosides based on technical C _{9 /} π-oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ⁹ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and the technical mixtures described above, which can be obtained as described above, and their technical mixtures. Alkyl oligoglucosides are preferred

Base of hardened C _12/14 coconut alcohol with a DP of 1 to 3.

thickener

In a preferred embodiment of the invention, it is desirable to give the preparations such a high viscosity that the microcapsules remain stable, ie do not sediment over time. The term increased viscosity is understood to mean a rheology which ensures the stabilization of the microcapsules in the liquid (non-surfactant) phase. Such viscosities (determined according to Brookfield, RVT viscometer, 20 ° C., spindle 1, 10 rpm) are above 100 and preferably above 500 mPas, preferably in the range from 200 to 2,000 and in particular 500 to 1,000 mPas. Suitable thickeners are all those substances which give the surfactant preparations a correspondingly high viscosity. However, they are preferably polymeric compounds since they are able to build up a three-dimensional network in the aqueous preparations in which the microcapsules are stabilized. Typical examples are Aerosil types (hydrophilic silicas), polysaccharides, especially xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl and hydroxypropyl cellulose, furthermore higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, ( eg Carbopole® and Pemulen types from Goodrich; Synthalene® from Sigma; Keltrol types from Kelco; Sepigel types from Seppic; Salcare types from Allied Colloids), polyacrylamides, polymers, polyvinyl alcohol and polyvinylpyrrolidone. Bentonites such as Bentone® Gel VS-5PC (Rheox), which is a mixture of cyclopentasiloxane, disteardimonium hectorite and propylene carbonate, have also proven to be particularly effective. The proportion of these thickeners in the liquid phase can be 0.1 to 5, preferably 0.5 to 3 and in particular 1 to 2% by weight. microcapsules

The term “microcapsule” is understood by the person skilled in the art to mean spherical aggregates with a diameter in the range from approximately 0.0001 to approximately 5 mm, which contain at least one solid or liquid core which is enclosed by at least one continuous shell. More precisely, they are finely dispersed liquid or solid phases coated with film-forming polymers, in the production of which the polymers are deposited on the material to be encased after emulsification and coacervation or interfacial polymerization. According to another method, melted waxes are taken up in a matrix (“microsponge”), which as microparticles can additionally be coated with film-forming polymers. The microscopic capsules, also called nanocapsules, can be dried like powders. In addition to mononuclear microcapsules, multinuclear aggregates are also , also known as microspheres, which contain two or more cores distributed in the continuous shell material, mono-core or multi-core microcapsules can also be enclosed by an additional second, third, etc. The shell can consist of natural, semisynthetic or synthetic materials Enveloping materials are, for example, gum arabic, agar agar, agarose, maltodextrins, alginic acid or its salts, for example sodium or calcium alginate, fats and fatty acids, cetyl alcohol, collagen, chitosan, lecithins, gelatin, albumin, shellac, polysaccharides, such as starch or dextran , Polypeptides, protein ydrolysate, sucrose and waxes. Semi-synthetic wrapping materials include chemically modified celluloses, especially cellulose esters and ethers, e.g. Cellulose acetate, ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose and carboxymethyl cellulose, as well as starch derivatives, especially starch ethers and esters. Synthetic covering materials are, for example, polymers such as polyacrylates, polyamides, polyvinyl alcohol or polyvinyl pyrrolidone.

Examples of microcapsules of the prior art are the following commercial products (the shell material is given in brackets): Hallcrest microcapsules (gelatin, gum arabic), Coletica Thalaspheres ^' (maritime "collagen), Lipotec millicapsules (alginic acid, agar agar), Induchem Unispheres (lactose, microcrystalline cellulose, hydroxypropylmethylcellulose); Unicerin C30 (lactose, microcrystalline cellulose, hydroxypropylmethylcellulose), Kobo Glycospheres (modified starch, fatty acid esters, phospholipids), Softspheres (modified agar-agar) and Kuhs Probipheres Nanospheres Primasponges (chitosan, alginates) and Primasys (phospholipids) Chitosan microcapsules and processes for their production are the subject of earlier patent applications by the applicant [WO 01/01926, WO 01/01927, WO 01/01928, WO 01/01929], their teaching hereby expressly included: microcapsules which are preferably used in the preparation according to the invention are included, have average diameters in the Range from 0.0001 to 5, preferably 0.001 to 0.5 and in particular 0.005 to 0.1 mm, consist of an envelope membrane and a matrix containing the active substances, and can be obtained, for example, by

(al) a matrix is prepared from gel formers, chitosans and active ingredients, (a2) if appropriate, the matrix is dispersed in an oil phase,

(a3) the dispersed matrix is treated with aqueous solutions of anionic polymers and, if appropriate, the oil phase is removed in the process.

or

(bl) a matrix is prepared from gel formers, anionic polymers and active ingredients,

(b2) optionally dispersing the matrix in an oil phase,

(b3) the dispersed matrix is treated with aqueous chitosan solutions and, if appropriate, the oil phase is removed in the process.

or

(cl) processed aqueous active substance preparations with oil bodies in the presence of emulsifiers to form O / W emulsions,

(c2) treating the emulsions thus obtained with aqueous solutions of anionic polymers,

(c3) the matrix thus obtained is brought into contact with aqueous solutions of chitosans or cation polymers and, if appropriate

(c4) the encapsulation products thus obtained are separated from the aqueous phase.

gelling agent

In the context of the invention ^"werdeιϊ as a gelling agent preferably those materials in consideration gen gezo-, the characteristic point to form gels in aqueous solution at temperatures above 40 ° C. Typical examples which are heteropolysaccharides and proteins. Preferred thermogelling heteropolysaccharides are agaroses The question of which agar agar to be obtained from red algae can also be present together with up to 30% by weight of non-gel-forming agaropectins The main constituent of the agaroses are linear polysaccharides from D-galactose and 3,6-anhydro-L galactose, which are alternately linked by β-1,3- and β-1,4-glycosidically The heteropolysaccharides preferably have a molecular weight in the range from 110,000 to 160,000 and are both colored and tasteless. Alternatives are pectins, xanthans (also xanthan gu) and their mixtures. Preference is furthermore given to those types which still form gels in 1% by weight aqueous solution, which do not melt below 80 ° C. and solidify again above 40 ° C. The various types of gelatin from the group of thermogelating proteins are examples.

chitosan

Chitosans are biopolymers and belong to the group of hydrocoids. From a chemical point of view, these are partially deacetylated chitins of different molecular weights that contain the following - idealized - monomer unit:

In contrast to most hydrocolloids, which are negatively charged in the range of biological pH values, chitosans are cationic biopolymers under these conditions. The positively charged chitosans can interact with oppositely charged surfaces and are therefore used in cosmetic hair and body care products as well as pharmaceuticals Preparations used. The production of chitosans is based on chitin, preferably the shell remnants of Krastentiere, which are available in large quantities as cheap raw materials. The chitin is used in a process that was first developed by Hackmann et al. has been described, - usually first deproteinized by adding bases, demineralized by adding mineral acids and finally deacetylated by adding strong bases, it being possible for the molecular weights to be distributed over a broad spectrum. Those types are preferably used which have an average molecular weight of 10,000 to 500,000 or 800,000 to 1,200,000 Daltons and / or a Brookfield viscosity (1% by weight in glycolic acid) below 5000 mPas, a degree of deacetylation in the range have from 80 to 88% and an ash content of less than 0.3% by weight. For reasons of better water solubility, the chitosans are generally used in the form of their salts, preferably as glycolates. cationic polymers

Instead of chitosan, cationic polymers can also be used to form the membrane. Suitable cationic polymers are, for example, cationic cellulose derivatives, such as, for example, a quaternized hydroxyethyl cellulose, which is available from Amerchol under the name Polymer JR 400®, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers, such as, for example, Lu - viquat® (BASF), genpolypeptide condensation products of polyglycols and amines, quaternized collagen, such as Lauryldimom ^'to hydroxypropyl Hydrolyzed collagen (Lamequat®L / Grunau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers, for example amodimethicones, copolymers of adipic acid and minohydroxypropyldiethylentriamin dimethylaniline (Cartaretine® / Sandoz), copolymers of acrylic acid with Dimethyldiallylammom ^'monium chloride (Merquat® 550 / Chemviron), polyaminopolyamides and crosslinked water-soluble polymers thereof, condensation products of dihaloalkyls, for example dibromobutane, with bis-dialkylamines, for example bis Dimethylamino-l, 3-propane, cationic guar gum, such as Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 from Celanese, quaternized ammonium salt polymers such as Mirapol® A-15, Mirapol® AD -1, Mirapol® AZ-1 from Miranol and amphoteric copolymers of (meth) acrylic acid, (meth) acrylic acid esters and unsaturated tetraalkylammonium compounds, such as Polyquartampho® 149 (Cognis).

drugs

The active substances which are suitable for microencapsulation can be divided into two groups, namely those

> which could not be dissolved or could not be sufficiently dissolved without the addition of water or would react with the constituents of the liquid phase and those which -> are soluble and chemically stable in the liquid phase, but should only be released in a targeted manner during use.

The first group includes ionic, i.e. anionic, cationic, amphoteric or zwitterionic surfactants, which are insoluble in the nonionic surfactant phase and could otherwise only be introduced as aqueous solutions. Typical examples of suitable anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, alkyl ether sulfates, glycerol ether sulfates, fatty acid ether sulfates, hydroxymether ether sulfates, (hydroxymether ether sulfates, hydroxyl ether sulfates, hydroxyl ether sulfates, hydroxyl ether sulfates, hydroxyl ether sulfates, hydroxyl ether sulfates, hydroxyl ether sulfates, hydroxyl ether sulfates, hydroxyl ether sulfates, hydroxyl ether sulfates, hydroxyl ether sulfates, hydroxyl ether sulfates, hydroxyl ether sulfates, hydroxyl ether sulfates, hydroxyl ether sulfates, hydroxyl ether sulfates, Fatty acid amide (ether) sulfates, mono- and dialkylsulfosuccinates, mono- and dialkylsulfosuccinates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethonates, fatty acid sarcosinates, fatty acid taurides, N-acyl amino acids, such as acyl lactarate, such as acyl lactarate, for example acyl lactarate, acyl acyl aspartates , Alkyl oligoglucoside sulfates, protein fatty acid condensates (especially vegetable products based on wheat) and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, these can have a conventional, but preferably a narrow, homolog distribution. Typical examples of cationic surfactants are quaternary ammonium compounds, such as, for example, dimethyldistearylammonium chloride, and esterquats, in particular quaternized fatty acid trialkanolamine ester salts. Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, niazolinium betaines and sulfobetaines. The surfactants mentioned are exclusively known compounds. For reasons of application technology, fatty alcohol (polyglycol ether) sulfates, monoglyceride sulfates, mono- and / or dialkyl sulfosuccinates, fatty acid glutamates, esterquats, alkylamidobetaines, amphoacetals and / or protein fatty acid condensates, the latter preferably based on wheat proteins, are particularly preferred. Of course, the microcapsules can also contain nonionic surfactants if they should not be a direct component of the liquid phase for other reasons.

The second group includes substances which are intended to protect and care for the skin when the preparations are used, for example during the manual rinsing process, or which are used, for example, to attach to the fibers during washing and to finish them. These include biogenic agents and antioxidants, such as vitamin E and its derivatives (e.g. tocopherol, tocopherol acetate, tocopherol palmitate), vitamin A and its derivatives (e.g. carotenes), caffeine, ascorbic acid, (deoxy) ribonucleic acid and their fragmentation products, ß -Glucans, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, chitosan, menthol, squalane, vegetable oils (e.g. jojoba oil), vegetable proteins and their hydrolysis products as well as plant extracts and vitamin complexes. The use of squalane, chitosan, menthol, retinol (vitamin A), caffeine, vegetable proteins and their hydrolysis products, carolina and jojoba oil is particularly preferred, since these do not contribute to the balance of the cutane hydrolipids, prevent water loss and, for example, the skin give a soft and elastic feel after rinsing. It is also preferred to use substances that protect the fibers, in particular color stabilizers, such as Polyvinyl pyrrolidone, poly (4-vinyl pyridinium betaine) or poly (4-vibyl pyridine oxide).

Finally, substances which do not make a direct contribution to the performance of the agents, but instead come from aesthetic reasons, can also be considered as active ingredients to be encapsulated. which are added, such as colorants, color pigments, perfume oils and flavors. Mixtures of natural and synthetic fragrances are mentioned as perfume oils. Natural fragrances are extracts of flowers (lily, lavender, rose, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, coriander, caraway, juniper), fruit peel (bergamot, lemon, Oranges), roots (mace, angelica, celery, cardamom, costus, iris, calmus), wood (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme), Needles and twigs (spruce, fir, pine, mountain pine), resins and balms (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials, such as civet and castoreum, are also suitable. Typical synthetic fragrance compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylethylphenylglycinate, allylcyclohexylproylateylateylateylateylateylateylateylateylateylatepylpropionate. The ethers include, for example, benzyl ethyl ether

Aldehydes e.g. the linear alkanals with 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the Jonone, α-isomethylionon and methylcedryl ketone, to the alcohols

Anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpinol, the hydrocarbons mainly include terpenes and balms. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Essential oils of lower volatility, which are mostly used as aroma components, are also suitable as perfume oils, e.g. Sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labolanum oil and lavandin oil. Bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol, benzylacetone, cyclamenaldehyde, linalool, boisambrene forte, ambroxan, tndol, hedione, sandelice, lemon oil, mandarin oil, cycloalene oil, allyl oil oil, orange oil oil, orange oil oil, orange oil oil, orange oil oil , Muscatel sage oil, ß-damascone, geranium oil bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilllate, irotyl and floramate alone or in mixtures, used. Suitable flavors are, for example, peppermint oil, spearmint oil, anise oil, star anise oil, caraway oil, eucalyptus oil, fennel oil, lemon oil, winter green oil, clove oil, menthol and the like.

The proportion of active substances in the microcapsules can be 1 to 30, preferably 5 to 25 and in particular 15 to 20% by weight. oil phase

The matrix can optionally be dispersed in an oil phase before the membrane is formed. Guerbet alcohols based on fatty alcohols with 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C ₆ -C ₂₂ fatty acids with linear C ₆ -C ₂₂ fatty alcohols, esters of branched C ₆ come as oils for this purpose, for example -C ₁₃ carboxylic acids with linear C ₆ -C fatty alcohols, such as, for example, myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palateate, cetyl styrate, cetyl styrate, cetyl styrate, cetyl styrene stearyl stearate, Stearyhsostearat, stearyl oleate, stearyl behenate, Stearylerucat, isostearyl, isostearyl palmitate, Isostearylstearat, isostearyl isostearate, Isostearyloleat, isostearyl behenate, Isostearyloleat, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, Oleylbehenat, oleyl erucate, Behenyhnyristat, behenyl palmitate, behenyl, Behenylisostearat, behenyl oleate, behenyl behenate, Behenyler ucat, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate and erucylerucate. In addition, esters of linear C ₆ -C fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of hydroxycarboxylic acids with linear or branched C ₆ -C ₂₂ fatty alcohols, in particular dioctyl malates, esters of linear and / or branched fatty acids with polyhydric acids are suitable Alcohols (such as propylene glycol, dimer diol or trimer triol) and / or Guerbet alcohols, triglycerides based on Ce-Cio fatty acids, liquid mono- / di- / triglyceride mixtures based on C ₆ -C ₁₈ fatty acids, esters of C6-C ₂₂ - Fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, especially benzoic acid, esters of C ₂ -C ₁₂ dicarboxylic acids with linear or branched alcohols with 1 to 22 carbon atoms or polyols with 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols , substituted cyclohexanes, linear and branched C ₆ -C ₂ fatty alcohol carbonates, Guerbet carbonates, esters of benzoic acid with linear and nd / or branched C ₆ -C ₂₂ alcohols (eg Finsolv® TN), linear or branched, symmetrical or unsymmetrical dialkyl ethers with 6 to 22 carbon atoms per alkyl group, ring opening products of epoxidized fatty acid esters with polyols, silicone oils and / or aliphatic or naphthenic hydrocarbons, such as squalane, squalene or dialkylcyclohexanes. anionic polymers

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

15

The average molecular weight of the alginic acids or alginates is in the range from 150,000 to 250,000. Salts of alginic acid are to be understood as meaning both their complete and their partial neutralization products, in particular the alkali metal salts and among them preferably the sodium alginate (“algin”) and the ammonium and alkaline earth metal salts, mixed alginates such as Na around magnesium or natri are particularly preferred In an alternative embodiment of the invention, however, anionic chitosan derivatives, such as carboxylation and especially succinylation products, are also suitable for this purpose, or alternatively poly (meth) acrylates with average molecular weights in the range from 5,000 to 50,000 Dalton as well as the various carboxymethyl celluloses in question.Instead of the anionic polymers, anionic surfactants or low molecular weight inorganic salts such as pyrophosphates can also be used for the formation of the envelope membrane.

emulsifiers

Suitable emulsifiers are, for example, nonionic surfactants from at least one of the following groups:

> Adducts of 2 to 30 mol ethylene oxide and / or 0 to 5 mol propylene oxide with linear fatty alcohols with 8 to 22 carbon atoms, with fatty acids with 12 to 22 carbon atoms, of alkylphenols with 8 to 15 carbon atoms in the alkyl group and alkylamines with 8 to 22 carbon atoms in the alkyl radical;

> Alkyl and / or alkenyl oligoglycosides with 8 to 22 carbon atoms in the alk (en) yl radical and their ethoxylated analogs; > Adducts of 1 to 15 moles of ethylene oxide with castor oil and / or hardened castor oil;

> Adducts of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil;

> Partial esters of glycerol and / or sorbitan with unsaturated, linear or saturated, branched fatty acids with 12 to 22 carbon atoms and / or hydroxycarboxylic acids with 3 to 18 carbon atoms and their adducts with 1 to 30 mol ethylene oxide;

> Partial esters of polyglycerol (average degree of self-condensation 2 to 8), polyethylene glycol (molecular weight 400 to 5000), trimethylolpropane, pentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides with (e.g. / or unsaturated, linear or branched fatty acids with 12 to 22 carbon atoms and / or hydroxycarboxylic acids with 3 to 18 carbon atoms and their adducts with 1 to 30 moles of ethylene oxide;

> Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol and / or mixed esters of fatty acids with 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol or polyglycerol.

> Mono-, di- and trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates and their salts;

> Wool wax alcohols; > Polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;

> Block copolymers e.g. Polyethylene glycol 30 dipolyhydroxystearate;

> Polymer emulsifiers, e.g. Pemulen types (TR-1, TR-2) from Goodrich;

> Polyalkylene glycols as well

> Glycerine carbonate. - -

> Ethylene oxide addition products

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

> Alkyl and / or alkenyl oligoglycosides

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

> Partial glycerides

Typical examples of suitable partial glycerides are rid Hydroxystearinsäuremonoglyce-, hydroxystearic acid diglyceride, isostearic acid, Isostearinsäuredigly- cerid, oleic acid monoglyceride, oleic acid diglyceride, Ricinolsäuremoglycerid, diglyceride Ricinolsäure-, Linolsäuremonoglycerid, Linolsäurediglycerid, Linolensäuremonoglycerid, Linolensäurediglycerid, Erucasäuremonoglycerid, Erucasäurediglycerid, Weinsäuremo- noglycerid, Weinsäurediglycerid, Citronensäuremonoglycerid, Citronendiglycerid, Malic acid monoglyceride, malic acid diglyceride and their technical mixtures, which may still contain minor amounts of triglyceride from the manufacturing process. Addition products of 1 to 30, preferably 5 to 10, mol of ethylene oxide onto the partial glycerides mentioned are also suitable.

sorbitan

Sorbitan monoisostearate, sorbitan sesquiisostearate, sorbitan diisostearate, sorbitan triisostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, sorbitan monoerucate, sorbitan sesquitane sucrose, sorbitan

Sorbitan trierucate, sorbitan monoricinoleate, sorbitan sesquiricinoleate, sorbitan diricinoleate, sorbitan triricinoleate, sorbitan monohydroxystearate, sorbitan sesquihydroxystearate, sorbitan dehydroxystearate, sorbitan trihyditan monostearate sorbitan sorbitan sorbitan qui-tartrate, sorbitan ditartrate, sorbitan tritartrate, sorbitan monocitrate, sorbitan sesquicitrate, sorbitan dicitrate, sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate, sorbitan dimaleate, sorbitan trimaleate and their technical mixtures. Addition products of 1 to 30, preferably 5 to 10, mol of ethylene oxide onto the sorbitan esters mentioned are also suitable.

polyglycerol

Typical examples of suitable polyglycerol esters are polyglyceryl-2 dipolyhydroxystearate (Dehymuls® PGPH), polyglycerol-3-diisostearate (Lameform® TGI), polyglyceryl-4 isostearate (Isolan® GI 34), polyglyceryl-3 oleate, diisostearoyl polygly- ceryl-3 diisostearate (Isolan® PDI), polyglyceryl-3 methylglucose distearate (Tego Care® 450), polyglyceryl-3 beeswax (Cera Bellina®), polyglyceryl-4 caprate (polyglycerol caprate T2010 / 90), polyglyceryl-3 cetyl Ether (Chimexane® NL), Polyglyceryl-3 Distearate (Cremophor® GS 32) and Polyglyceryl Polyricinoleate (Admul® WOL 1403) Polyglyceryl Dimerate Isostearate and their mixtures. Examples of other suitable polyol esters are the mono-, di- and triesters of trimethylolpropane or pentaerythritol with lauric acid, coconut fatty acid, tallow fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like which are optionally reacted with 1 to 30 mol of ethylene oxide.

Anionic emulsifiers

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

Amphoteric and cationic emulsifiers

Zwitterionic surfactants can also be used as emulsifiers. Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example coconut alkyl dimethylammomumglycinate, N-acylaminopropyl-N, N- dimethylammom ^' umglycinate, for example the cocoacylaminopropyldimethylamomumglycinate, and 2-alkyl-3-carboxylmethyl-3-hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. The fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine is particularly preferred. Suitable emulsifiers are ampholytic surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a C _8/18 alkyl or acyl group, contain at least one free amino group and at least one COOH or SO H group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid in each case about 8 to 18 carbon atoms in the alkyl group .. particularly preferred ampholytic surfactants are N-coconut alkylaminopropionate, cocoacylaminoethyl aminopropionate and C _1/18 -

Sarcosine. Finally, cationic surfactants are also suitable as emulsifiers, those of the esterquat type, preferably methylquaternized difatty acid triethanolamine ester salts, being particularly preferred.

Manufacturing process microcapsules

To produce the microcapsules, a 1 to 10, preferably 2 to 5% by weight aqueous solution of the gel former, preferably of the agar, is usually prepared and heated under reflux. At boiling point, preferably at 80 to 100 ° C., a second aqueous solution is added, which contains the chitosan in amounts of 0.1 to 2, preferably 0.25 to 0.5% by weight and the active ingredients in amounts of 0 , 1 to 25 and in particular 0.25 to 10 wt .-% contains; this mixture is called the matrix. The loading of the microcapsules with active ingredients can therefore also be 0.1 to 25% by weight, based on the capsule weight. If desired, water-insoluble constituents, for example inorganic pigments, can also be added at this point in time to adjust the viscosity, these being generally added in the form of aqueous or aqueous / alcoholic dispersions. To emulsify or disperse the active ingredients, it may also be useful to add emulsifiers and / or solubilizers to the matrix. After the matrix has been produced from gelling agent, chitosan and active ingredients, the matrix can optionally be very finely dispersed in an oil phase under high shear in order to produce the smallest possible particles in the subsequent encapsulation. It has proven to be particularly advantageous to heat the matrix to temperatures in the range from 40 to 60 ° C. during the oil phase is cooled to 10 to 20 ° C. In the last step, which is now mandatory again, the actual encapsulation then takes place, ie the formation of the envelope membrane by bringing the chitosan in the matrix into contact with the anionic polymers. For this purpose it is advisable to optionally disperse the matrix in the oil phase at a temperature in the range from 40 to 100, preferably 50 to 60 ° C. with an aqueous, about 1 to 50 and preferably 10 to 15% by weight aqueous solution of the anion polymer to treat and - if necessary - to remove the oil phase at the same time or subsequently. The resulting aqueous preparations generally have a microcapsule content in the range from 1 to 10% by weight. In some cases, it can be advantageous if the solution of the polymers contains further ingredients, for example emulsifiers or preservatives. After filtration, microcapsules are obtained which have an average diameter in the range of preferably about 1 mm. It is advisable to sieve the capsules to ensure that the size is distributed as evenly as possible. The microcapsules thus obtained can have any shape in the production-related framework, but they are preferably approximately spherical. Alternatively, the anionic polymers can also be used to produce the matrix and encapsulated with the chitosans.

In an alternative process for producing the microcapsules according to the invention, an O / W emulsion is first prepared which, in addition to the oil body, water and the active ingredients, contains an effective amount of emulsifier. To prepare the matrix, a corresponding amount of an aqueous anion polymer solution is added to this preparation with vigorous stirring. The membrane is formed by adding the chitosan solution. The entire process preferably takes place in the weakly acidic range at pH = 3 to 4. If necessary, the pH is adjusted by adding mineral acid. After membrane formation, the pH is raised to 5 to 6, for example by adding triethanolamine or another base. This leads to an increase in viscosity, which is caused by the addition of further thickeners, such as polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, higher molecular weight polyethylene glycone mono- and diesters of fat. acids, polyacrylates, polyacrylamides and the like can still be supported. Finally, the microcapsules are separated from the aqueous phase, for example by decanting, filtering or centrifuging. To prepare the portioned preparations, the liquid phase is first loaded with the microcapsules. The mixture is then enclosed in the polymer shell by means of machines specially designed for this purpose. The sachets usually have a weight of 1 to 10 and in particular 2 to 5 g. The dimensions can be between 1 x 1 to 5 x 5 cm, the portion bags can be square, round or oval in shape.

Industrial applicability

Another object of the present invention relates to the use of microencapsulated active ingredients for the production of portioned liquid detergents and cleaning agents, which can be, for example, liquid detergents, dishwashing detergents, Universaheimger or finishing agents. The microcapsules can be used in amounts of 0.1 to 10, preferably 1 to 8 and in particular 3 to 5% by weight, based on the portioned preparations.

Examples

A nonionic surfactant phase was loaded with various microcapsules and then enclosed in a polyvinyl alcohol shell. The sachets had dimensions of 4 x 4 cm, weighed about 5 g and were square in shape. Table 1 below contains a number of formulation examples. The recipes mean the following:

1) liquid detergent 2) manual dishwashing detergent

3) detergent

4) finishing agent

Table 1 Composition of portioned detergents and cleaning agents

1) reaction product of 1,2-dodecene epoxide and octanol + lPO + 40EO

Primaspheres® A: Chitosan microcapsules loaded with alkyl sulfate Primaspheres® B: CMtosan microcapsules loaded with alkyl ether sulfate Primaspheres® C: CMtosan microcapsules loaded with retinol Primaspheres® D: CWtosarimicro capsules loaded with esterquats

Claims

 claims 1. Portioned liquid detergent and cleaning agent preparations consisting of (a) a water-soluble envelope, (b) a liquid phase enclosed by the shell, and (c) encapsulated active ingredients dispersed in the liquid phase. 2. Preparations according to claim 1, characterized in that the shell consists of at least one water-soluble polymer. 3. Preparations according to claims 1 and / or 2, characterized in that the shell consists entirely or predominantly of polyvinyl alcohol. 4. Preparations according to at least one of claims 1 to 3, characterized in that the liquid phase is anhydrous. 5. Preparations according to at least one of claims 1 to 3, characterized in that the liquid phase has a water content of at most 5% by weight. 6. Preparations according to at least one of claims 1 to 5, characterized in that the liquid phase is a surfactant phase. 7. Preparations according to at least one of claims 1 to 6, characterized in that the liquid phase is a nonionic surfactant phase. 8. Preparations according to claim 7, characterized in that the liquid phase contains nonionic surfactants which are selected from the group formed by fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglyceride (hydroxy) Mixed ethers or mixed formals, alk (en) yl oligoglycosides, fatty acid N-alkyl glucamides, protein hydrolyzates, polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. , Preparations according to Claim 8, characterized in that they contain fatty alcohol polyglycol ethers of the formula (I) as nonionic surfactants, R ^ CHaCHR ² ©) ,, !!! (I) in which R ^{1 is} a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms, R ^{2 is} hydrogen or methyl and nl is a number from 1 to 20. 10. Preparations according to claims 8 and / or 9, characterized in that they contain alkoxylated fatty acid lower alkyl esters of the formula (II) as nonionic surfactants, R ³ CO (OCH ₂ CHR ⁴ ) _n2 OR ⁵ (II) in which R ³ CO stands for a linear or branched, saturated and / or unsaturated acyl radical with 6 to 22 carbon atoms, R ⁴ for hydrogen or methyl, R ⁵ for linear or branched alkyl radicals with 1 to 4 carbon atoms and n2 for numbers of 1 to 20 stands. 11. Preparations according to at least one of claims 8 to 10, characterized in that they contain hydroxy mixed ethers of the formula (III) as nonionic surfactants, OH CH ₃ R ⁶ CH-CHR ⁷ O (CH ₂ CH ₂ θ) „ ₃ (CH ₂ CHO) _m (CH ₂ CH ₂ O) _n4 R ⁸ (III) in which R ^{6 is} a linear or branched alkyl radical having 2 to 18 carbon atoms, R ^{7 is} hydrogen or a linear or branched alkyl radical having 2 to 18 carbon atoms, R. represents a linear or branched alkyl and / or alkenyl radical having 1 to 22 carbon atoms, n3 and n4 independently of one another represents 0 or numbers from 1 to 60 and m represents 0 or numbers from 0.5 to 5, with the provisos that the sum of the carbon atoms in the radicals R ⁶ and R ^{7 is} at least 6 and preferably 12 to 18 and the sum (n3 + m + n4) is different from 0. 12. Preparations according to at least one of claims 8 to 11, characterized in that they contain alkyl and / or alkenyl oligoglycosides of the formula (IV) as nonionic surfactants, R ⁹ O- [G] _p (IV) in which R ^{9 represents} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G represents a sugar radical having 5 or 6 carbon atoms and p represents numbers from 1 to 10. 13. Preparations according to at least one of claims 1 to 12, characterized in that the liquid phase further contains thickeners. 14. Preparations according to at least one of claims 1 to 13, characterized in that they contain thickeners which are selected from the group formed by hydrophilic silicas, polysaccharides, carboxymethyl celluloses, hydroxyethyl and hydroxypropyl celluloses, higher molecular weight polyethylene glycohno-no- and diesters of fatty acids, polyacrylates, polyacrylamides, polyvinyl alcohols, polyvinyl pyrrolidones and bentonites. 15. Preparations according to at least one of claims 1 to 14, characterized in that they contain the thickeners - based on the liquid phase - in amounts of 0.1 to 5 wt .-%. 16. Preparations according to at least one of claims 1 to 15, characterized in that they contain microcapsules with average diameters in the range from 0.0001 to 5 mm, consist of an envelope membrane and a matrix containing the active ingredients, which are obtainable as a result , that he (al) a matrix is prepared from gel formers, chitosans and active ingredients, (a2) if appropriate, the matrix is dispersed in an oil phase, (a3) the dispersed matrix is treated with aqueous solutions of anionic polymers and, if appropriate, the oil phase is removed in the process. or (b1) a matrix is prepared from gel formers, anionic polymers and active substances, (b2) if appropriate, the matrix is dispersed in an oil phase, (b3) the dispersed matrix is treated with aqueous chitosan solutions and, if appropriate, the oil phase is removed in the process. or (cl) processed aqueous active substance preparations with oil bodies in the presence of emulsifiers to form O / W emulsions, (c2) the emulsions thus obtained are treated with aqueous solutions of anionic polymers, (c3) the matrix thus obtained is brought into contact with aqueous solutions of chitosans or cationic polymers and, if appropriate (c4) the encapsulation products thus obtained are separated from the aqueous phase. 17. Preparations according to claim 16, characterized in that they contain microencapsulated active substances which are selected from the group formed by ionic or nonionic surfactants, biogenic active substances, dyes, fiber protection agents, color pigments, perfume oils, aromas and mixtures thereof. 18. Preparations according to claims 16 and / or 17, characterized in that they contain microencapsulated ionic surfactants which are selected from the group formed by soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates , Sulfo fatty acids, alkyl sulfates, alkyl ether sulfates, glycerol ether sulfates, fatty acid ether sulfates, hydroxymixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinates, amine carboxylic acid sulfates, sulfoniflyglycerides, sulfoniflyglycerides, sulfoniflysiflycerides, sulfoniflysiflycerides thereof, sulfonate sulfonates , Fatty acid ethionates, fatty acid sarcosinates, fatty acid taurides, N-acyl amino acids, alkyl oligoglucoside sulfates, protein fatty acid condensates, alkyl (ether) phosphates, quaternary ammonium compounds, ester quats, alkyl betaines, alkyl amido betaines, aminopropionates, aminoglyium betaines and imidazolinobetaine, imidazolinobetaine. 19. Preparations according to at least one of claims 16 to 18, characterized in that they contain microencapsulated biogenic active substances which are selected from the group formed by squalane, chitosan, menthol, retinol (vitamin A), caffeine, vegetable proteins and their hydrolysis products, carolines, antioxidants, plant extracts and vegetable oils and their mixtures. 20. Preparations according to at least one of claims 16 to 19, characterized in that the proportion of active ingredients in the capsules is 1 to 30 wt .-%. 21. Preparations according to at least one of claims 1 to 20, characterized in that they contain the microcapsules - based on the liquid phase - in amounts of 0.1 to 10 wt .-%. 22. Preparations according to at least one of claims 1 to 21, characterized in that the portion bags have a weight of 1 to 10 g. 23. Preparations according to at least one of claims 1 to 22, characterized in that the portion bags have dimensions of 1 x 1 to 5 x 5 cm. 24. Preparations according to at least one of claims 1 to 23, characterized in that the sachets are square, round or oval shaped. 25. Use of microencapsulated active ingredients for the production of portioned liquid washing and cleaning agents. 26. Use according to claim 25, characterized in that the preparations are liquid detergents. 27. Use according to claim 25, characterized in that the preparations represent dishwashing agents. 28. Use according to claim 25, characterized in that the preparations are universal cleaners. 29. Use according to claim 25, characterized in that the preparations are excipients. 30. Use according to at least one of claims 25 to 29, characterized in that the microcapsules - based on the portioned preparations - in amounts of 0.1 to 10 wt .-%.