EP1449912A1 - Aqueous compositions containing microencapsulated active substances - Google Patents

Abstract

Aqueous composition containing microencapsulated active compounds (I) that inhibit resoiling of textiles. An independent claim is also included for a method for reducing the resoiling of textiles by finishing the fibers, yarn or fabrics with microencapsulated soil-repellant polymers that contain ethylene terephthalate and/or poly(ethylene glycol) terephthalate groups.

Description

Field of the Invention

The invention is in the field of laundry treatment agents and relates to new preparations with microencapsulated active ingredients that make it difficult to re-soiling Process for treating textiles and the use of special microencapsulated Active ingredients for laundry equipment.

State of the art

Today's consumer demands on laundry treatment products are constantly increasing posed. The times when you were content with it, different spots to be completely removed from a wide variety of tissues - even if possible low temperatures - are over. Today's usual laundry treatment products have to be the most complex Simultaneously meet requirements that begin with the care of the laundry and with the Care of the wearer ends. The never ending number of patent publications on this Topic makes it clear that technology is still far from that of the consumer to set goals to their fullest satisfaction.

In this context, it is sort of a detail that the consumer not only is the spotless removal of dirt required, he also expects that his textiles are protected from being soiled again. Exist in the act "soil repellants" of this type and are offered by a wide variety of manufacturers on the market. What they have in common is that they are polymers that are essentially ethylene terephthalate and / or have polyethylene glycol terephthalate groups. The disadvantage is, however, that such substances cannot be formulated arbitrarily. Especially with longer storage and temperature influence, segregation occurs, which is still in the best case cause the preparations to become cloudy. Such products need to be used shaken intensely and mixed again, which the normal consumer seldom with special Interest in buying rewarded. In particular, transparent formulations that have this appearance can also be kept permanently, or not at all produce.

The object of the present invention was therefore to create new aqueous preparations to provide with which textiles can be equipped so that a Re-soiling is prevented or at least made more difficult ("soil repellant effect") without that this has the disadvantages of the prior art. In particular, the Active ingredients easily incorporated and the resulting aqueous preparations are stable on storage his. Another wish was still to use such active substances that over have additional positive effects in connection with the textile finish.

Description of the invention

The invention relates to aqueous preparations, for example fabric softener, Liquid detergent or laundry detergent, with microencapsulated active ingredients, which are characterized by the fact that the active substances are substances which Prevent or at least complicate the re-soiling of textiles.

The problem of poor formulation and poor shelf life could can be solved in that the preparations according to the invention contain the known active ingredients now contained in microencapsulated form. In this way, transparent and produce stable agents over a long period of time. Contain the microcapsules additionally Dyes, for example, transparent preparations that contain the active ingredients Form of clearly visible, for example blue or red colored spherical structures contain what may be desired for aesthetic reasons, because it is the consumer Presence of active excipients immediately in mind. The microencapsulated active ingredients pull on the fibers; the capsules are gradually broken open mechanically and then release the active ingredient in portions. In a preferred embodiment of the The present invention uses microencapsulated active ingredients in which the shell consists entirely or at least predominantly of chitosan. Chitosan also tends to to pull on fibers. Because it has nourishing and antibacterial properties with the use of chitosan microcapsules the desired additional benefit reached.

drugs

As soil-repellants such substances come into question that preferably contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, wherein the molar ratio of ethylene terephthalate to polyethylene glycol terephthalate is in the range of 50: 50 to 90: 10 can be. The molecular weight of the linking polyethylene glycol units is in particular in the range from 750 to 5000, i.e. the degree of ethoxylation of the Polymers containing polyethylene glycol groups can be approximately 15 to 100. The polymers are characterized by an average molecular weight of about 5000 to 200,000 and can have a block structure, but preferably a random structure. preferred Polymers are those with molar ratios of ethylene terephthalate / polyethylene glycol terephthalate from about 65:35 to about 90:10, preferably from about 70:30 to 80:20. Also preferred are those polymers that link molecular weight polyethylene glycol units from 750 to 5000, preferably from 1000 to about 3000 and a molecular weight of the polymer from about 10,000 to about 50,000. Examples of commercially available Polymers are the products Milease® T (ICI) or Repelotex® SRP 3 (Rhône-Poulenc).

microcapsules

The term "microcapsule" describes spherical aggregates with a Understand diameters in the range of about 0.0001 to about 5 mm, the at least one contain solid or liquid core, which is enclosed by at least one continuous shell is. More precisely, they are finely dispersed with film-forming polymers liquid or solid phases, in the production of which the polymers change after emulsification and coacervation or interfacial polymerization on the material to be encased knock down. Another method involves melting waxes in a matrix added ("microsponge"), which as microparticles additionally with film-forming polymers can be enveloped. Leave the microscopic capsules, also called nanocapsules drying like powder. In addition to mononuclear microcapsules, there are also multinuclear aggregates, also known as microspheres, known, the two or more cores in the continuous shell material distributed included. Single-core or multi-core microcapsules can also have an additional second, third, etc. envelope. The shell can be made from natural, semi-synthetic or synthetic materials. Wrapping materials are, of course, for example Gum arabic, agar-agar, agarose, maltodextrins, alginic acid or its salts, e.g. Sodium or calcium alginate, fats and fatty acids, cetyl alcohol, collagen, chitosan, Lecithins, gelatin, albumin, shellac, polysaccharides, such as starch or dextran, polypeptides, Protein hydrolysates, sucrose and waxes. Semi-synthetic wrapping materials are below other chemically modified celluloses, especially cellulose esters and ethers, e.g. cellulose acetate, Ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose and Carboxymethyl cellulose, and starch derivatives, especially starch ethers and esters. synthetic Envelope 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, hydroxypropylmethyl cellulose); Unicerin C30 (lactose, microcrystalline cellulose, hydroxypropylmethylcellulose), Kobo Glycospheres (modified starch, fatty acid esters, phospholipids), Softspheres (modified agar agar) and Kuhs Probiol Nanospheres (phospholipids) as well as Primaspheres and Primasponges (Chitosan, Alysol phosphates ) and Alginate ,

(a1) aus Gelbildnern, Chitosanen und Wirkstoffen eine Matrix zubereitet,

(a2) gegebenenfalls die Matrix in einer Ölphase dispergiert,

(a3) die dispergierte Matrix mit wässrigen Lösungen anionischer Polymere behandelt und gegebenenfalls dabei die Ölphase entfernt.

oder

(b1) aus Gelbildnern, anionischen Polymeren und Wirkstoffen eine Matrix zubereitet,

(b2) gegebenenfalls die Matrix in einer Ölphase dispergiert,

(b3) die dispergierte Matrix mit wässrigen Chitosanlösungen behandelt und gegebenenfalls dabei die Ölphase entfernt.

oder

(c1) wässrige Wirkstoffzubereitungen mit Ölkörpern in Gegenwart von Emulgatoren zu O/W-Emulsionen verarbeitet,

(c2) die so erhaltenen Emulsionen mit wässrigen Lösungen anionischer Polymere behandelt,

(c3) die so erhaltene Matrix mit wässrigen Chitosanlösungen in Kontakt bringt und

(c4) die so erhaltenen Verkapselungsprodukte von der wässrigen Phase abtrennt.

As already explained, there is a particular benefit in using microencapsulated active ingredients, the shell of which is at least partially formed by chitosan. Chitosan microcapsules and processes for their preparation are the subject of earlier patent applications by the applicant [WO 01/01926, WO 01/01927, WO 01/01928, WO 01/01929]. Microcapsules with 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, consisting of a shell membrane and a matrix containing the active substances, can be obtained, for example, by

(a1) a matrix is prepared from gel formers, chitosans and active ingredients,

(a2) optionally dispersing the matrix 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 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

(c1) 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) brings the matrix thus obtained into contact with aqueous chitosan solutions and

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

• gelling agent

For the purposes of the invention, such substances are preferably considered as gel formers drawn, which show the property in aqueous solution at temperatures above of 40 ° C to form gels. Typical examples are heteropolysaccharides and proteins. Agaroses are preferably used as thermogelating heteropolysaccharides in question, which together in the form of the agar agar to be obtained from red algae 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 linked alternately 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 colorless and tasteless. As alternatives Pectins, xanthans (also xanthan gum) and mixtures thereof can be used. Those types which are still in 1% by weight aqueous solution are also preferred Form gels that do not melt below 80 ° C and are already above of 40 ° C solidify again. From the group of thermogeling proteins the different types of gelatin are mentioned as examples.

• Chitosans

Im Gegensatz zu den meisten Hydrokolloiden, die im Bereich biologischer pH-Werte negativ geladen sind, stellen Chitosane unter diesen Bedingungen kationische Biopolymere dar. Die positiv geladenen Chitosane können mit entgegengesetzt geladenen Oberflächen in Wechselwirkung treten und werden daher in kosmetischen Haar- und Körperpflegemitteln sowie pharmazeutischen Zubereitungen eingesetzt. Zur Herstellung der Chitosane geht man von Chitin, vorzugsweise den Schalenresten von Krustentieren aus, die als billige Rohstoffe in großen Mengen zur Verfügung stehen. Das Chitin wird dabei in einem Verfahren, das erstmals von Hackmann et al. beschrieben worden ist, üblicherweise zunächst durch Zusatz von Basen deproteiniert, durch Zugabe von Mineralsäuren demineralisiert und schließlich durch Zugabe von starken Basen deacetyliert, wobei die Molekulargewichte über ein breites Spektrum verteilt sein können. Vorzugsweise werden solche Typen eingesetzt, wie die ein durchschnittliches Molekulargewicht von 10.000 bis 500.000 bzw. 800.000 bis 1.200.000 Dalton aufweisen und/oder eine Viskosität nach Brookfield (1 Gew.-%ig in Glycolsäure) unterhalb von 5000 mPas, einen Deacetylierungsgrad im Bereich von 80 bis 88 % und einem Aschegehalt von weniger als 0,3 Gew.-% besitzen. Aus Gründen der besseren Wasserlöslichkeit werden die Chitosane in der Regel in Form ihrer Salze, vorzugsweise als Glycolate eingesetzt.Chitosans are biopolymers and belong to the group of hydrocolloids. 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 remains of crustaceans, 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.

• oil phase

The matrix can optionally be dispersed in an oil phase before the membrane is formed. Suitable oils for this purpose are, for example, Guerbet alcohols based on fatty alcohols having 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 -C ₁₃ carboxylic acids with linear C ₆ -C ₂₂ -fatty alcohols, such as myristyl myristate, myristyl palmitate, myristyl stearate, Myristylisostearat, myristyl, Myristylbehenat, Myristylerucat, cetyl myristate, cetyl palmitate, cetyl stearate, Cetylisostearat, cetyl oleate, cetyl behenate, Cetylerucat, Stearylmyristat, stearyl palmitate, stearyl stearate, Stearylisostearat , 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, behenyl myristate, behenyl palmitate, behenyl, Behenylisostearat, behenyl oleate, behenyl behenate, Behenyleru cat, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate and erucylerucate. In addition, esters of linear C ₆ -C ₂₂ 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 are also suitable polyhydric alcohols (such as propylene glycol, dimer diol or trimer triol) and / or Guerbet alcohols, triglycerides based on C ₆ -C ₁₀ fatty acids, liquid mono- / di- / triglyceride mixtures based on C ₆ -C ₁₈ fatty acids, esters of C ₆ -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 ₂₂ fatty alcohol carbonates, Guerbet carbonates, esters of benzoic acid with lin earen and / or branched C ₆ -C ₂₂ alcohols (e.g. 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:

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 both theirs understand complete as well as their partial neutralization products, in particular the alkali salts and among them preferably the sodium alginate ("Algin") and the ammonium and alkaline earth salts. Mixed alginates, such as e.g.

Sodium / magnesium or sodium / calcium alginates. In an alternative embodiment However, the invention also includes anionic chitosan derivatives for this purpose, such as. Carboxylation and especially succinylation products in question. Alternatively, poly (meth) acrylates with average molecular weights also come in the range of 5,000 to 50,000 daltons as well as the various carboxymethyl celluloses in question. Instead of using anionic polymers for training the envelope membrane also anionic surfactants or low molecular weight inorganic Salts such as pyrophosphates can be used.

• emulsifiers

• Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/ oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C-Atomen, an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe sowie Alkylamine mit 8 bis 22 Kohlenstoffatomen im Alkylrest;
• Alkyl- und/oder Alkenyloligoglykoside mit 8 bis 22 Kohlenstoffatomen im Alk(en)ylrest und deren ethoxylierte Analoga;
• Anlagerungsprodukte von 1 bis 15 Mol Ethylenoxid an Ricinusöl und/oder gehärtetes Ricinusöl;
• Anlagerungsprodukte von 15 bis 60 Mol Ethylenoxid an Ricinusöl und/oder gehärtetes Ricinusöl;
• Partialester von Glycerin und/oder Sorbitan mit ungesättigten, linearen oder gesättigten, verzweigten Fettsäuren mit 12 bis 22 Kohlenstoffatomen und/oder Hydroxycarbonsäuren mit 3 bis 18 Kohlenstoffatomen sowie deren Addukte mit 1 bis 30 Mol Ethylenoxid;
• Partialester von Polyglycerin (durchschnittlicher Eigenkondensationsgrad 2 bis 8), Polyethylenglycol (Molekulargewicht 400 bis 5000), Trimethylolpropan, Pentaerythrit, Zuckeralkoholen (z.B. Sorbit), Alkylglucosiden (z.B. Methylglucosid, Butylglucosid, Laurylglucosid) sowie Polyglucosiden (z.B. Cellulose) mit gesättigten und/oder ungesättigten, linearen oder verzweigten Fettsäuren mit 12 bis 22 Kohlenstoffatomen und/oder Hydroxycarbonsäuren mit 3 bis 18 Kohlenstoffatomen sowie deren Addukte mit 1 bis 30 Mol Ethylenoxid;
• Mischester aus Pentaerythrit, Fettsäuren, Citronensäure und Fettalkohol und/oder Mischester von Fettsäuren mit 6 bis 22 Kohlenstoffatomen, Methylglucose und Polyolen, vorzugsweise Glycerin oder Polyglycerin.
• Mono-, Di- und Trialkylphosphate sowie Mono-, Di- und/oder Tri-PEGalkylphosphate und deren Salze;
• Wollwachsalkohole;
• Polysiloxan-Polyalkyl-Polyether-Copolymere bzw. entsprechende Derivate;
• Block-Copolymere z.B. Polyethylenglycol-30 Dipolyhydroxystearate;
• Polymeremulgatoren, z.B. Pemulen-Typen (TR-1,TR-2) von Goodrich;
• Polyalkylenglycole sowie
• Glycerincarbonat.

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

• Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear fatty alcohols with 8 to 22 carbon atoms, with fatty acids with 12 to 22 carbon atoms, with 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;
• Addition products of 1 to 15 moles of ethylene oxide with castor oil and / or hardened castor oil;
• Addition products 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 polyglucosaturated (e.g. cellulose) or unsaturated (e.g. cellulose) , 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 trialkylphosphates and mono-, di- and / or tri-PEGalkylphosphate and their salts;
• Lanolin alcohol;
• Polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;
• Block copolymers, for example polyethylene glycol 30 dipolyhydroxystearate;
• Polymer emulsifiers, for example Pemulen types (TR-1, TR-2) from Goodrich;
• Polyalkylene glycols as well
• Glycerol carbonate.

The microcapsules are usually prepared in a 1 to 10, preferably 2 to 5 % By weight aqueous solution of the gel former, preferably the agar, and heated this under reflux. At boiling point, preferably at 80 to 100 ° C, a second added aqueous solution containing the chitosan in amounts of 0.1 to 2, preferably 0.25 up to 0.5% by weight and the active compounds in amounts of 0.1 to 25 and in particular 0.25 to 10 % By weight; this mixture is called the matrix. The loading of the microcapsules with active ingredients can therefore also 0.1 to 25 wt .-% based on the capsule weight be. If desired, water-insoluble ones can also be used at this time to adjust the viscosity Components, for example inorganic pigments, are added, where they are usually added in the form of aqueous or aqueous / alcoholic dispersions. To emulsify or disperse the active ingredients, it may also be useful add emulsifiers and / or solubilizers to the matrix. After making the Matrix of gelling agent, chitosan and active ingredients, the matrix can optionally in an oil phase be dispersed very finely under strong shear in order to be encapsulated in the following to produce the smallest possible particles. It has proven to be particularly advantageous to heat the matrix to temperatures in the range of 40 to 60 ° C while the Cool the oil phase to 10 to 20 ° C. In the last step, which is now mandatory again, the actual encapsulation, i.e. the formation of the envelope membrane by bringing the Chitosans in the matrix with the anionic polymers. To do this, it is recommended that the matrix dispersed 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 To treat wt .-% aqueous solution of the anion polymer and - if necessary - simultaneously or to remove the oil phase afterwards. The resulting aqueous Preparations generally have a microcapsule content in the range from 1 to 10% by weight on. In some cases it can be advantageous if the solution of the polymers is further Contains ingredients, such as emulsifiers or preservatives. After filtration microcapsules are obtained which preferably have an average diameter in the range of have about 1 mm. It is advisable to sift the capsules to get one if possible ensure even size distribution. The microcapsules obtained in this way can manufacturing-related frames have any shape, but they are preferably approximate spherical. Alternatively, the anionic polymers can also be used to prepare the Insert the matrix and encapsulate it with the chitosans.

An alternative method is to produce the microcapsules according to the invention an O / W emulsion is first prepared, which in addition to the oil body, water and Active ingredients contain an effective amount of emulsifier. This is used to manufacture the matrix Preparation with vigorous stirring with an appropriate amount of an aqueous anion polymer solution added. The membrane is formed by adding the chitosan solution. The the entire process preferably takes place in the weakly acidic range at pH = 3 to 4. If 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 by adding further thickeners, e.g. Polysaccharides, in particular Xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and Hydroxyethylcellulose, higher molecular weight polyethylene glycol mono- and diesters of fatty acids, Polyacrylates, polyacrylamides and the like can still be supported. Finally the microcapsules are removed from the aqueous phase, for example by decanting, Filter or centrifuge separated.

Aqueous preparations

The preparations can usually contain microencapsulated active ingredients in amounts of 0.1 up to 10, preferably 1 to 8 and in particular 2 to 5% by weight, based on the composition. In the simplest case, the agents are aqueous solutions that are only which contain microcapsules and, if appropriate, suitable thickeners. This is for example in the case of laundry aftertreatment agents. In other cases, i.e. with or liquid detergents, the preparations can above all be anionic, nonionic, contain cationic and / or amphoteric or zwitterionic surfactants.

Anionic surfactants

Typical examples of anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, Olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, Alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates, Monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, Mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acylamino acids such as acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, Alkyl oligoglucoside sulfates, protein fatty acid condensates (especially vegetable products Wheat base) and alkyl (ether) phosphates. If the anionic surfactants polyglycol ether chains contain, these can be a conventional, but preferably a narrow homolog distribution exhibit. Alkylbenzenesulfonates, alkylsulfates, soaps, Alkane sulfonates, olefin sulfonates, methyl ester sulfonates and mixtures thereof are used.

• alkylbenzenesulfonates

Preferred alkylbenzenesulfonates follow the formula (I) R ¹ -Ph-SO ₃ X in which R ^{1 is} a branched but preferably linear alkyl radical having 10 to 18 carbon atoms, Ph is a phenyl radical and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Of these, dodecylbenzenesulfonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures in the form of the sodium salts are particularly suitable.

• Alkyl and / or alkenyl sulfates

Alkyl and / or alkenyl sulfates, which are also often referred to as fatty alcohol sulfates, are to be understood as meaning the sulfation products of primary and / or secondary alcohols, which preferably follow the formula (II) R ² O-SO ₃ X in which R ^{2 represents} a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X represents an alkali metal and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical examples of alkyl sulfates which can be used in the context of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, aryl selenyl alcohol, elaidyl alcohol, Behenyl alcohol and erucyl alcohol and their technical mixtures, which are obtained by high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis. The sulfation products can preferably be used in the form of their alkali metal salts and in particular their sodium salts. Alkyl sulfates based on C _16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium salts are particularly preferred. In the case of branched primary alcohols, these are oxo alcohols, as are obtainable, for example, by converting carbon monoxide and hydrogen to alpha-containing olefins using the shop process. Such alcohol mixtures are commercially available under the trade names Dobanol® or Neodol®. Suitable alcohol mixtures are Dobanol 91®, 23®, 25®, 45®. Another possibility are oxo alcohols, such as those obtained by the classic Enichema or Condea oxo process by adding carbon monoxide and hydrogen to olefins. These alcohol mixtures are a mixture of strongly branched alcohols. Such alcohol mixtures are commercially available under the trade name Lial®. Suitable alcohol mixtures are Lial 91®, 111®, 123®, 125®, 145®.

• soaps

Soaps are to be understood as meaning fatty acid salts of the formula (III) R ³ CO-OX in which R ³ CO represents a linear or branched, saturated or unsaturated acyl radical having 6 to 22 and preferably 12 to 18 carbon atoms and again X represents alkali and / or alkaline earth metal, ammonium, alkylammonium or alkanolammonium. Typical examples are the sodium, potassium, magnesium, ammonium and triethanolammonium salts 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, elaoleic acid, petoleic acid, linoleic acid, petoleic acid, linoleic acid, petoleic acid, linoleic acid, linoleic acid, Linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures. Coconut or palm kernel fatty acid is preferably used in the form of its sodium or potassium salts.

Nonionic surfactants

Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, Fatty acid polyglycol ester, fatty acid amide polyglycol ether, fatty amine polyglycol ether, alkoxylated triglycerides, mixed ethers or mixed formals, alk (en) yl oligoglycosides, Fatty acid-N-alkylglucamides, protein hydrolyzates (especially vegetable products based on wheat), Polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. Provided the nonionic surfactants contain polyglycol ether chains, these can be a conventional, but preferably have a narrow homolog distribution. Preferably become fatty alcohol polyglycol ethers, alkoxylated fatty acid lower alkyl esters or alkyl oligoglucosides used.

• Fatty alcohol polyglycol ether

The preferred fatty alcohol polyglycol ethers follow the formula (IV) R ⁴ O (CH ₂ CHR ⁵ O) _n1 H in which R ^{4 represents} a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms, R ^{5 represents} hydrogen or methyl and n1 represents numbers from 1 to 20. 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, oleyl alcohol, isostyl alcohol , Petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures. Addition products of 3, 5 or 7 moles of ethylene oxide onto technical coconut oil alcohols are particularly preferred.

• Alkoxylated fatty acid esters

Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula (V) R ⁶ CO- (OCH ₂ CHR ⁷ ) _n2 OR ⁸ in which R ⁶ CO is a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R ^{7 is} hydrogen or methyl, R ^{8 is a} linear or branched alkyl radical having 1 to 4 carbon atoms and n2 is a number from 1 to 20 stands. Typical examples are the formal insert products of on average 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, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and technical grade and erucas. The products are usually prepared by inserting the alkylene oxides into the carbonyl ester bond in the presence of special catalysts, such as, for example, 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.

• alkyl and / or alkenyl oligoglycosides

Alkyl and alkenyl oligoglycosides, which are also preferred nonionic surfactants, usually follow the formula (VI), R ⁹ O- [G] _p in which R ^{8 is} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number 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 (VI) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p must always be an integer in a given compound and especially here can assume the values p = 1 to 6, the value p for a specific 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 and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosides of chain length C ₈ -C ₁₀ (DP = 1 to 3) are preferred, which are obtained as a preliminary step in the separation of technical C ₈ -C ₁₈ coconut fatty alcohol by distillation and with a proportion of less than 6% by weight of C ₁₂ - Alcohol can be contaminated and alkyl oligoglucosides based on technical C _9/11 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 their technical mixtures, which can be obtained as described above. Alkyl oligoglucosides based on hardened C _12/14 coconut alcohol with a DP of 1 to 3 are preferred.

Cationic surfactants

in der R¹⁰CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹¹ und R¹² unabhängig voneinander für Wasserstoff oder R¹⁰CO, R¹¹ für einen Alkylrest mit 1 bis 4 Kohlenstoffatomen oder eine (CH₂CH₂O)_m4H-Gruppe, m1, m2 und m3 in Summe für 0 oder Zahlen von 1 bis 12, m4 für Zahlen von 1 bis 12 und Y für Halogenid, Alkylsulfat oder Alkylphosphat steht. Typische Beispiele für Esterquats, die im Sinne der Erfindung Verwendung finden können, sind Produkte auf Basis von Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Isostearinsäure, Stearinsäure, Ölsäure, Elaidinsäure, Arachinsäure, Behensäure und Erucasäure sowie deren technische Mischungen, wie sie beispielsweise bei der Druckspaltung natürlicher Fette und Öle anfallen. Vorzugsweise werden technische C_12/18-Kokosfettsäuren und insbesondere teilgehärtete C_16/18-Talg- bzw. Palmfettsäuren sowie elaidinsäurereiche C_16/18-Fettsäureschnitte eingesetzt. Zur Herstellung der quaternierten Ester können die Fettsäuren und das Triethanolamin im molaren Verhältnis von 1,1 : 1 bis 3 : 1 eingesetzt werden. Im Hinblick auf die anwendungstechnischen Eigenschaften der Esterquats hat sich ein Einsatzverhältnis von 1,2 : 1 bis 2,2 : 1, vorzugsweise 1,5 : 1 bis 1,9 : 1 als besonders vorteilhaft erwiesen. Die bevorzugten Esterquats stellen technische Mischungen von Mono-, Di- und Triestern mit einem durchschnittlichen Veresterungsgrad von 1,5 bis 1,9 dar und leiten sich von technischer C_16/18- Talg- bzw. Palmfettsäure (Iodzahl 0 bis 40) ab. Aus anwendungstechnischer Sicht haben sich quaternierte Fettsäuretriethanolaminestersalze der Formel (VII) als besonders vorteilhaft erwiesen, in der R¹⁰CO für einen Acylrest mit 16 bis 18 Kohlenstoffatomen, R¹¹ für R¹⁰CO, R¹² für Wasserstoff, R¹³ für eine Methylgruppe, m1, m2 und m3 für 0 und Y für Methylsulfat steht.Typical examples of cationic surfactants are, in particular, tetraalkylammonium compounds, such as, for example, dimethyldistearylammonium chloride or hydroxyethyl hydroxycetyldimmonium chloride (Dehyquart E), or else esterquats, which are typically a constituent of finishing agents. These are, for example, quaternized fatty acid triethanolamine ester salts of the formula (VII) ,

in which R ¹⁰ CO for an acyl radical with 6 to 22 carbon atoms, R ¹¹ and R ¹² independently of one another for hydrogen or R ¹⁰ CO, R ¹¹ for an alkyl radical with 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _m4 H- Group, m1, m2 and m3 in total for 0 or numbers from 1 to 12, m4 for numbers from 1 to 12 and Y for halide, alkyl sulfate or alkyl phosphate. Typical examples of ester quats that can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachic acid, behenic acid and erucic acid and their technical mixtures, such as they occur, for example, in the pressure splitting of natural fats and oils. Technical C _12/18 coconut _fatty acids and in particular partially hardened C _16/18 tallow or palm fatty acids as well as C _16/18 fatty acid _cuts rich in elaidic acid are preferably used. The fatty acids and the triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1 to produce the quaternized esters. With regard to the application properties of the ester quats, an application ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1, has proven to be particularly advantageous. The preferred esterquats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C _16/18 - tallow or palm fatty acid (iodine number 0 to 40). From an application point of view, quaternized fatty acid triethanolamine ester salts of the formula (VII) have proven to be particularly advantageous in which R ¹⁰ CO for an acyl radical having 16 to 18 carbon atoms, R ¹¹ for R ¹⁰ CO, R ¹² for hydrogen, R ¹³ for a methyl group, m1 , m2 and m3 stands for 0 and Y for methyl sulfate.

in der R¹⁴CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹⁵ für Wasserstoff oder R¹⁴CO, R¹⁶ und R¹⁷ unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m5 und m6 in Summe für 0 oder Zahlen von 1 bis 12 und Y wieder für Halogenid, Alkylsulfat oder Alkylphosphat steht. Als weitere Gruppe geeigneter Esterquats sind schließlich die quatemierten Estersalze von Fettsäuren mit 1,2-Dihydroxypropyldialkylaminen der Formel (IX) zu nennen,

in der R¹⁸CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹⁹ für Wasserstoff oder R¹⁸CO, R²⁰, R²¹ und R²² unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m7 und m8 in Summe für 0 oder Zahlen von 1 bis 12 und X wieder für Halogenid, Alkylsulfat oder Alkylphosphat steht. Schließlich kommen als Esterquats noch Stoffe in Frage, bei denen die Ester- durch eine Amidbindung ersetzt ist und die vorzugsweise basierend auf Diethylentriamin der Formel (X) folgen,

in der R²³CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R²⁴ für Wasserstoff oder R²³CO, R²⁵ und R²⁶ unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen und Y wieder für Halogenid, Alkylsulfat oder Alkylphosphat steht. Derartige Amidesterquats sind beispielsweise unter der Marke Incroquat® (Croda) im Markt erhältlich.In addition to the quaternized fatty acid triethanolamine ester salts, quaternized ester salts of fatty acids with diethanolalkylamines of the formula (VIII) are also suitable as esterquats.

in which R ¹⁴ CO for an acyl radical with 6 to 22 carbon atoms, R ¹⁵ for hydrogen or R ¹⁴ CO, R ¹⁶ and R ¹⁷ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m5 and m6 in total for 0 or numbers from 1 to 12 and Y again represents halide, alkyl sulfate or alkyl phosphate. Finally, the quaternized ester salts of fatty acids with 1,2-dihydroxypropyl dialkylamines of the formula (IX) should be mentioned as a further group of suitable ester quats,

in which R ¹⁸ CO for an acyl radical with 6 to 22 carbon atoms, R ¹⁹ for hydrogen or R ¹⁸ CO, R ²⁰ , R ²¹ and R ²² independently of one another for alkyl radicals with 1 to 4 carbon atoms, m7 and m8 in total for 0 or numbers from 1 to 12 and X again represents halide, alkyl sulfate or alkyl phosphate. Finally, suitable esterquats are substances in which the ester bond is replaced by an amide bond and which preferably follow the formula (X) based on diethylene triamine

in which R ²³ CO represents an acyl radical having 6 to 22 carbon atoms, R ^{24 represents} hydrogen or R ²³ CO, R ²⁵ and R ²⁶ independently of one another represent alkyl radicals having 1 to 4 carbon atoms and Y again represents halide, alkyl sulfate or alkyl phosphate. Such amide ester quats are available on the market, for example, under the Incroquat® (Croda) brand.

Amphoteric or zwitterionic surfactants

in der R²⁷ für Alkyl- und/oder Alkenylreste mit 6 bis 22 Kohlenstoffatomen, R²⁸ für Wasserstoff oder Alkylreste mit 1 bis 4 Kohlenstoffatomen, R²⁹ für Alkylreste mit 1 bis 4 Kohlenstoffatomen, q1 für Zahlen von 1 bis 6 und Z für ein Alkali- und/oder Erdalkalimetall oder Ammonium steht. Typische Beispiele sind die Carboxymethylierungsprodukte von Hexylmethylamin, Hexyldimethylamin, Octyldimethylamin, Decyldimethylamin, Dodecylmethylamin, Dodecyldimethylamin, Dodecylethylmethylamin, C_12/14-Kokosalkyldimethylamin, Myristyldimethylamin, Cetyldimethylamin, Stearyldimethylamin, Stearylethylmethylamin, Oleyldimethylamin, C_16/18-Talgalkyldimethylamin sowie deren technische Gemische. Weiterhin kommen auch Carboxyalkylierungsprodukte von Amidoaminen in Betracht, die der Formel (XII) folgen,

in der R³⁰CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen und 0 oder 1 bis 3 Doppelbindungen, R³¹ für Wasserstoff oder Alkylreste mit 1 bis 4 Kohlenstoffatomen, R³² für Alkylreste mit 1 bis 4 Kohlenstoffatomen, q2 für Zahlen von 1 bis 6, q3 für Zahlen von 1 bis 3 und Z wieder für ein Alkali- und/oder Erdalkalimetall oder Ammonium steht. Typische Beispiele sind Umsetzungsprodukte von Fettsäuren mit 6 bis 22 Kohlenstoffatomen, namentlich Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Gemische, mit N,N-Dimethylaminoethylamin, N,N-Dimethylaminopropylamin, N,N-Diethylaminoethylamin und N,N-Diethylaminopropylamin, die mit Natriumchloracetat kondensiert werden. Bevorzugt ist der Einsatz eines Kondensationsproduktes von C_8/18-Kokosfettsäure-N,N-dime-thylaminopropylamid mit Natriumchloracetat. Weiterhin kommen auch Imidazoliniumbetaine in Betracht. Auch bei diesen Substanzen handelt es sich um bekannte Stoffe, die beispielsweise durch cyclisierende Kondensation von 1 oder 2 Mol Fettsäure mit mehrwertigen Aminen wie beispielsweise Aminoethylethanolamin (AEEA) oder Diethylentriamin erhalten werden können. Die entsprechenden Carboxyalkylierungsprodukte stellen Gemische unterschiedlicher offenkettiger Betaine dar. Typische Beispiele sind Kondensationsprodukte der oben genannten Fettsäuren mit AEEA, vorzugsweise Imidazoline auf Basis von Laurinsäure oder wiederum C_12/14-Kokosfettsäure, die anschließend mit Natriumchloracetat betainisiert werden. Examples of suitable amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. Examples of suitable alkyl betaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (XI)

in which R ²⁷ for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms, R ²⁸ for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R ²⁹ for alkyl radicals with 1 to 4 carbon atoms, q1 for numbers from 1 to 6 and Z for a Alkali and / or alkaline earth metal or ammonium. Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, Dodecylethylmethylamin, C _12/14 -Kokosalkyldimethylamin, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, stearyl, oleyl, C _16/18 tallow alkyl dimethyl amine and technical mixtures thereof. Carboxyalkylation products of amidoamines which follow the formula (XII) are also suitable,

in which R ³⁰ CO for an aliphatic acyl radical with 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, R ³¹ for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R ³² for alkyl radicals with 1 to 4 carbon atoms, q2 for numbers from 1 to 6, q3 for numbers from 1 to 3 and Z again represents an alkali and / or alkaline earth metal or ammonium. Typical examples are reaction products of fatty acids with 6 to 22 carbon atoms, namely caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, gadoleic acid and arachic acid, arachic acid and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylaminopropylamine, which are condensed with sodium chloroacetate. It is preferred to use a condensation product of C _8/18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate. Imidazolinium betaines are also suitable. These substances are also known substances which can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines such as, for example, aminoethylethanolamine (AEEA) or diethylene triamine. The corresponding carboxyalkylation products are mixtures of different open-chain betaines. Typical examples are condensation products of the above-mentioned fatty acids with AEEA, preferably imidazolines based on lauric acid or again C _12/14 coconut fatty acid, which are subsequently betainized with sodium chloroacetate.

thickener

In a preferred embodiment of the invention, it is desired to use the preparations impart such a high viscosity that the microcapsules remain stably dispersed, i.e. do not sediment over time. The term increased viscosity is therefore a to understand such rheology which stabilizes the microcapsules in the aqueous (surfactant) phase ensures. Such viscosities are usually (determined according to Brookfield, RVT viscometer, 20 ° C, spindle 1, 10 rpm) 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 the substances that make up the formulations give correspondingly high viscosity. However, they are preferably polymeric Compounds, since these are able to form a three-dimensional in the aqueous preparations To build a network 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, also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, (e.g. Carbopole® and Pemulen types from Goodrich; Synthalene® from Sigma; Keltrol types from Kelco; Seppic Sepigel types; Salcare types by Allied Colloids), polyacrylamides, polymers, polyvinyl alcohol and polyvinyl pyrrolidone. As Bentonites, such as Bentone® Gel VS-5PC (Rheox) proven to be a mixture of cyclopentasiloxane, disteardimonium hectorite and propylene carbonate. The proportion of these thickeners in the aqueous preparations can be 0.1 to 5, preferably 0.5 to 3 and in particular 1 to 2% by weight.

Industrial applicability

Two other objects of the present invention relate to preventing re-soiling of textiles, in which the fibers, yarns or textile fabrics are used with microencapsulated active ingredients that are selected from the group that is formed is made of polymers ("soil repellants"), the ethylene terephthalate and / or polyethylene glycol terephthalate groups have, as well as the use of microencapsulated polymers ("soil repellants"), the ethylene terephthalate and / or polyethylene glycol terephthalate groups have, for the production of laundry treatment agents.

Examples example 1

In a 500 ml three-necked flask with stirrer and reflux condenser, 3 g of agar-agar dissolved in 200 ml of water. Then the mixture was within about 30 min with vigorous stirring, first with a solution of 10 g glycerol, 90 ml water and then with a preparation of 2.5 g of sodium alginate in the form of a 10 wt .-% aqueous Solution, 3 g Milease® T, 0.5 g Phenonip® and 0.5 g Polysorbate-20 (Tween® 20, ICI) in 64 g Water added. The matrix obtained was filtered, heated to 60 ° C and in a 1 wt .-% Solution of chitosan glycolate dropped in water. Same to obtain microcapsules The preparations were then sieved in diameter.

Example 2

In a 500 ml three-necked flask with stirrer and reflux condenser, 3 g of agar-agar dissolved in 200 ml of water. Then the mixture was within about 30 min with vigorous stirring, first with a solution of 10 g glycerol, 90 ml water and then with a preparation of 2.5 g of sodium alginate in the form of a 10 wt .-% aqueous Solution, 3 g Repelotex® SRP 3, 0.5 g Phenonip® and 0.5 g Polysorbate-20 (Tween® 20, ICI) added to 64 g of water. The matrix obtained was filtered, heated to 60 ° C. and placed in a 1st % By weight solution of chitosan glycolate in water. For the preservation of microcapsules The preparations of the same diameter were then sieved.

1,2) Flüssigwaschmittel

3) Avivagemittel

4) Wäschenachbehandlungsmittel

Zusammensetzung wässriger Zubereitungen Zusammensetzung 1 2 3 4 C_12/18-Kokosalkohol+5EO
Dehydol® LT5 25,0 25,0 - - C_12/18-Kokosalkohol+7EO
Dehydol® LT7 10,0 - - - Mischether )
Dehypon® KE 3447 - 10,0 - - Dipalmoylmethylethoxymonium Methosulfate
Dehyquart® AU 54 - 25,0 - Carbopol 0,49 0,49 0,49 Farbstoff 0,01 0,01 0,01 Mikrokapseln Bsp. 1 1,0 - 1,0 - Mikrokapseln Bsp. 2 - 1,0 - 1,0 Wasser          ad 100 Table 1 below contains a number of formulation examples. The recipes mean the following:

1,2) liquid detergent

3) finishing agent

4) Laundry after-treatment agent

Composition of aqueous preparations composition 1 2 3 4 C _12/18 coconut alcohol + 5EO
Dehydol® LT5 25.0 25.0 - - C _12/18 coconut alcohol + 7EO
Dehydol® LT7 10.0 - - - mixed ethers )
Dehypon® KE 3447 - 10.0 - - Dipalmoylmethylethoxymonium methosulfate
Dehyquart® AU 54 - 25.0 - Carbopol 0.49 0.49 0.49 dye 0.01 0.01 0.01 Microcapsules Ex. 1 1.0 - 1.0 - Microcapsules Ex. 2 - 1.0 - 1.0 water ad 100

Claims (12)

Aqueous preparations with microencapsulated active ingredients, characterized in that the active ingredients are substances which prevent textiles from being soiled again. Preparations according to claim 1, characterized in that it is fabric softener. Preparations according to claim 1, characterized in that it is liquid detergent. Preparations according to claim 1, characterized in that it is laundry aftertreatment. Preparations according to at least one of claims 1 to 4, characterized in that the active substances are polymers ("soil repellants") which contain ethylene terephthalate and / or polyethylene glycol terephthalate groups. Preparations according to claim 5, characterized in that the polymers contain ethylene terephthalate / polyethylene glycol terephthalate units in a molar ratio of 65:35 to 90:10. Preparations according to at least one of claims 1 to 6, characterized in that they contain microcapsules with average diameters in the range from 0.0001 to 5 mm, consisting of an envelope membrane and a matrix containing the active ingredients, which are obtainable by (a1) a matrix is prepared from gel formers, chitosans and active ingredients, (a2) optionally dispersing the matrix 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 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 (c1) 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) brings the matrix thus obtained into contact with aqueous chitosan solutions and (c4) the encapsulation products thus obtained are separated from the aqueous phase. Preparations according to at least one of Claims 1 to 7, characterized in that they contain the microencapsulated active ingredients in amounts of 0.1 to 10% by weight, based on the composition. Preparations according to at least one of claims 1 to 8, characterized in that they further contain anionic, nonionic, cationic and / or amphoteric or zwitterionic surfactants. Preparations according to at least one of claims 1 to 9, characterized in that they further contain thickeners. Process for preventing re-soiling of textiles, in which the Equips fibers, yarns or textile fabrics with microencapsulated active ingredients, which are selected from the group formed by polymers ("soil repellants"), which have ethylene terephthalate and / or polyethylene glycol terephthalate groups. Use of microencapsulated polymers ("soil repellants"), the ethylene terephthalate and / or have polyethylene glycol terephthalate groups for the preparation of laundry treatment agents.