EP3085763A1 - Method for the production of capsules with a polymer matrix - Google Patents

Abstract

The present invention relates to a process for the preparation of capsules from a polymeric matrix, the capsules thus obtained and their use, and liquid detergents or cleaners comprising corresponding capsules.

Description

The present invention relates to a process for the preparation of capsules from a polymeric matrix, the capsules thus obtained and their use, and liquid detergents or cleaners comprising corresponding capsules.

Polymers or particulate agents of various chemical nature play an increasingly important role in modern detergents. These are often polymers that increase the cleaning performance of a detergent or unfold a care effect. Examples of such active ingredients are, for example, soil-repellent polymers, grayness inhibitors, primary detergency boosters, Softener or Antiknitter active substances. Particulate active ingredients which are described in the prior art as a constituent of detergents are, for example, microcapsules or microparticles (for example bentonites for softening).

In the formulation of liquid washing or cleaning agents, the problem often arises that the corresponding polymeric or particulate active ingredients are not soluble in the liquid matrix, or else should not be soluble. The formulation of clear and aesthetically pleasing opaque products is therefore not possible in many cases. In addition, intolerances between the individual active substance components may occur during incorporation of certain active ingredients into liquid detergents and cleaners. This can lead to undesirable discoloration, agglomeration, odor problems or even destruction of the active washing substances.

Although it would be possible to disperse the polymeric or particulate active substances as a solid in liquid detergents or cleaners, in many cases it leads to a less aesthetic product since the active ingredient is often dispersed in the form of irregularly shaped particles, as flakes or precipitate. In addition, it may happen that the active ingredient partially dissolves and in this way leads to a phase separation of the liquid product. The consumer, however, requires liquid washing or cleaning agents that look visually appealing even after storage and transport at the time of use and also have an optimal effect. This implies that the ingredients of the liquid detergent and cleaning agent have previously neither sedimented, decomposed or volatilized.

The production of active ingredient loaded capsules is for example in WO 2006/034758 A1 described. Here, a solution of the polymeric matrix material is produced. In particular, an enzyme is introduced as an active ingredient into this solution. Subsequently, the crosslinking of the polymer takes place in a curing bath, which leads to the formation of the drug-loaded polymeric matrix.

Matrix capsules with active ingredients are also available in WO 2007/017070 A1 described. The matrix contains aluminum silicate and a silica, so that it dissolves without residue in the washing program.

Such, known from the prior art method is applicable, as long as the active ingredient does not overly the viscosity of the polymer-drug mixture, so that the resulting polymer-drug mixture remains processable. Among other things, this limits the drug concentration to be achieved in the capsules.

The object of the present invention is therefore to provide a process for the preparation of capsules of a polymeric matrix and an active ingredient, which contain larger amounts of an active ingredient than is possible with the methods described in the prior art. These capsules can then be introduced into a liquid detergent which has the capsules and thus the active substance in an aesthetically pleasing and recognizable form for the consumer.

1. a) Bereitstellen einer fließfähigen Lösung wenigstens eines Polymers,
2. b) Bereitstellen einer Lösung oder Suspension des wenigstens einen Wirkstoffs,
3. c) In-Kontakt bringen der Lösung aus Schritt a) mit der Suspension aus Schritt b) und
4. d) Vernetzen des Polymers.

Surprisingly, it has been found that the object is achieved by bringing a solution of a polymer into contact with a solution or suspension comprising the active ingredient. In a first embodiment, the present invention therefore relates to a process for the preparation of capsules comprising a polymeric matrix and an active ingredient, which comprises the following steps:

1. a) providing a flowable solution of at least one polymer,
2. b) providing a solution or suspension of the at least one active substance,
3. c) bringing the solution from step a) into contact with the suspension from step b) and
4. d) crosslinking of the polymer.

In this case, a suspension is a heterogeneous mixture of a liquid and finely divided solids (in the present case the at least one active substance), which are slurried in the liquid (suspending agent) and held in suspension. Suspensions in water are often referred to as slurry or (from English) slurry

Surprisingly, it has been found that capsules of a polymeric matrix and an active substance can be produced with the method according to the invention, which have a high active ingredient content.

A high active ingredient content is reflected in the mass ratio of matrix to active ingredient. The mass ratio of matrix to drug, which with the inventive method can be made is 1: 1 to 1:60, in particular 1: 3 to 1:50, more preferably 1: 5 to 1:40. With the method according to the invention it is thus possible to produce capsules which have a higher proportion of active ingredient in relation to the matrix, or at least comprise matrix and active ingredient in the same proportion. The mass ratio according to the invention relates to the dry matter of the matrix and the active ingredient. The proportion by weight of any solvents contained is not considered.

The capsules according to the invention comprise a polymeric matrix. If matrix is mentioned in the present application, this is to be understood as meaning the crosslinked polymeric material of which the matrix is composed. The term polymer describes the material of the matrix, but in the uncrosslinked state.

According to the invention, in a first step, first a flowable solution of a polymer is provided. At least one polymer is dissolved in a suitable solvent for this purpose. It is preferably a 0.5 to 10% polymer solution, preferably a 0.5 to 5% solution, more preferably a 1 to 2% solution. A 1% solution means that, based on 100% by weight of the solution, 1% by weight of the at least one polymer is contained.

According to the invention, the polymer matrix may comprise and in particular consist of a polymer. However, it is likewise possible according to the invention for a mixture of two or more polymers to be used for producing the flowable solution in step a) of the process according to the invention, so that the polymeric matrix comprises or consists of a plurality of polymers. In this case, the at least one polymer may be at least one natural and / or at least one synthetic polymer. Preferably, the polymer comprises at least one natural polymer, more preferably it comprises a natural polymer and most preferably the polymer is a natural polymer. The natural polymer may be, for example, carrageenan, alginate, pectin, guar, gelatin and / or gelan gum.

Alginate is a naturally occurring salt of alginic acid and is found in all brown algae (Phaeophycea) as a cell component. Alginates are acidic carboxy group-containing polysaccharides having a relative molecular weight M _r of about 200,000 and consisting of D-mannuronic acid and L-guluronic acid in different proportions linked to 1,4-glycosidic bonds. The sodium, potassium, ammonium and magnesium alginates are water-soluble. The viscosity of alginate solutions depends inter alia on the molecular weight and on the counterion. For example, calcium alginates form thermo-reversible gels at certain proportions. Sodium alginates give very viscous solutions with water and can interact with divalent metal ions such as Ca ²⁺ or trivalent Metal ions are crosslinked. Ingredients, which are also contained in the aqueous sodium alginate solution, are thus enclosed in an alginate matrix.

Carrageenan is an extract of the red algae (Chrondrus crispis and Gigartina stellata) that are part of the floidae. In the presence of K ⁺ ions or Ca ²⁺ ions, carrageenan crosslinks.

Gellan gum is a branched anionic microbial heteroexopolysaccharide having a tetrasaccharide repeat unit consisting of the monomers glucose, glucuronic acid and rhamnose, wherein each repeat unit is esterified with an L-glyceate and every other repeat unit is esterified with an acetate. Gellan gum cross-links in the presence of K'-ions, Na ⁺ -ions, Ca ²⁺ -ions or Mg ²⁺ -ions.

Pectins are plant polysaccharides, more specifically polyuronides, which consist essentially of α-1,4-glycosidically linked D-galactoronic acid units. In addition to α-1,4-compounds is usually also a small proportion of β-1,4-glycosidic bonds, via which the galactoronic acid monomers are linked together.

Guar, or guar gum is a polysaccharide, which is obtained from the guar bean.

Gelatine is a mixture of tasteless animal protein. The main component is denatured or hydrolyzed collagen, which is produced from the connective tissue of various animal species, especially pigs and cattle. Since gelatin lacks the essential amino acid trytophan, it is not considered a full-fledged protein. Gelatin swells in water and dissolves when heated at about 50 ° C.

More preferably, the at least one polymer is a hydrocolloid. Hydrocolloids for the purposes of the present invention are polysaccharides and / or proteins which dissolve in water as colloids and show a high ability for gel formation. For example, hydrocolloids are selected from cornstarch, cellulose, pectins, gum arabic, galactomanans such as guar gum, carob bean carob, aggar, carrageenan, alginate, gelatin, caseinate, xanthan or dextran.

More preferably, the at least one polymer is selected from alginate, agar, carrageenan, pectin and / or guar, with carrageenan and / or alginate being even more preferred.

To provide a flowable solution comprising the at least one polymer, water is preferably used as the solvent. Suitable conditions under which a corresponding solution can be prepared are known to the person skilled in the art. Flowable in the sense In the present application means that the solution is processable in conventional processes and can be brought into contact with the suspension of the active ingredient and in particular mixed with this.

The inventive method comprises in step b) providing a suspension of the active ingredient. Polymeric matrix and active ingredient preferably have mutually different properties. In the capsule, the drug is embedded in the polymeric network of the matrix.

The active ingredient is provided in the process according to the invention in a suspension. For this purpose, the active ingredient is introduced into a non-solvent, wherein the non-solvent is miscible with the solvent of the polymer. Since the at least one polymer is usually dissolved in water, the non-solvent of the active ingredient is especially a water-miscible liquid and is preferably selected from propylene glycol, glycerol, ethanol and / or isopropanol.

If the active ingredient is introduced into a suitable non-solvent, a suspension is obtained. A suspension is a heterogeneous mixture of a liquid (the non-solvent) and finely divided solids, namely the active ingredient. Non-solvent in the sense of the present invention means that this is a liquid (at room temperature) in which the at least one active ingredient only to 5 wt .-% or less, in particular to 3 wt .-% or less, in particular to 1% by weight or less at room temperature (20 ° C) is soluble.

The proportion of the active ingredient in the suspension is preferably 10% a.i. (active ingredient) or more, especially 10% a.i. up to 40% a.i. and more preferably 12% a.i. up to 20% a.i. in each case based on the total composition of the suspension. A.i. in the sense of the present invention means the proportion of active substance (a.s.) which is present in the suspension. The proportion of any remaining ingredients is not taken into account. If the proportion is less than 10% a.i., the proportion of active ingredient obtained in the end product is low. If the share is more than 40% a.i. For example, the viscosity of the suspension / solution may become too high so that steps c) and d) of the process can no longer be carried out without a time delay. A share of 20% a.i. has proven to be easy to process with good efficacy in the final product.

According to the invention, the capsule may comprise one or more active substances. Preferably, it contains an active ingredient. The at least one active ingredient may be polymeric or particulate. Examples of corresponding polymeric active substances are soil-repellent polymers (in particular anionic or else nonionic terephthalates), grayness inhibitors (in particular cellulose derivatives),

Reinforcers of the primary washing power (in particular PEI and / or PVP and their derivatives), softeners (for example modified siloxanes), anti-crease agents (for example siloxanes) and enzymes (in particular cellulase, amylase and lipases). Particulate active substances are, for example, microcapsules, microparticles (for example bentonite for softening) or nanoparticles.

Especially in the case of swelling active ingredients which swell on contact with water, capsules can not be prepared by the processes described in the prior art. If, in this case, polymer and active ingredient are dissolved or dispersed in water, the active ingredient swells and a mixture is formed which can no longer be processed into capsules.

The inventive method now allows that swelling agents can be introduced into a capsule. Corresponding capsules can be introduced into liquid washing or cleaning agents, so that the method according to the invention makes it possible for the first time to provide swelling active ingredients in capsules for liquid detergents or cleaners. Particularly in the case of polymeric and especially swelling active substances, it is advantageous if the proportion of the active ingredient in the suspension is 40% a.i. or less, especially 30% a.i. or less, especially 20% a.i. or less. In the case of polymeric active ingredients in particular, if the concentrations are too high, the polymer wad may collapse, which then does not expand again even during a subsequent dilution. This reduces the effectiveness.

worin

• a und c unabhängig voneinander jeweils für eine Zahl von 1 bis 200 steht,
• R¹ ,R², R⁵ und R⁶ unabhängig voneinander jeweils für Wasserstoff oder eine C₁- oder C₂-C₁₈-n-Alkylgruppe oder C₃- oder C₄-C₁₈-iso-Alkylgruppe steht,
• R⁷ für eine lineare oder verzweigte C₁- oderC₂-C₃₀-Alkylgruppe oder für eine lineare oder verzweigte C₂- oder C₃-C₃₀-Alkenylgruppe, für eine Cycloalkylgruppe mit 5 bis 9 Kohlenstoffatomen, für eine C₆-C₃₀-Arylgruppe oder für eine C₆-C₃₀-Arylalkylgruppe steht.

In a preferred embodiment, the active substance is therefore a swelling active ingredient, in particular at least one soil repellent polymer and / or at least one grayness inhibitor such as, for example, a cellulose derivative, such as methylcellulose, carboxymethylcelullose or hydroxypropylmethylcelullose. Soil repellent polymers reduce the re-soiling of textiles after washing. Preferably, these have a phthalate group. The polymer is preferably a polyester containing at least one structural unit of the formula (I) and at least one structural unit of the formula (II)

wherein

• a and c independently of one another each represent a number from 1 to 200,
• R ¹ , R ² , R ⁵ and R ⁶ independently of one another each represent hydrogen or a C ₁ - or C ₂ -C ₁₈ -n-alkyl group or C ₃ - or C ₄ -C ₁₈ -iso-alkyl group,
• R ^{7 is} a linear or branched C ₁ - or C ₂ -C ₃₀ -alkyl group or a linear or branched C ₂ - or C ₃ -C ₃₀ -alkenyl group, for a cycloalkyl group having 5 to 9 carbon atoms, a C ₆ -C ₃₀ -Arylgruppe or a C ₆ -C ₃₀ -Arylalkylgruppe stands.

worin

• a, b und c unabhängig voneinander jeweils für eine Zahl von 1 bis 200 steht,
• 1/n Mⁿ⁺ für ein Äquivalent eines Kations mit der Ladungszahl n steht mit n = 1, 2 oder 3,
• R¹, R², R³, R⁴, R⁵ und R⁶ unabhängig voneinander jeweils für Wasserstoff oder eine C₁-oder C₂-C₁₈-n-Alkylgruppe oder C₃- oder C₄-C₁₈-iso-Alkylgruppe steht,
• R⁷ für eine lineare oder verzweigte C₁- oder C₂-C₃₀-Alkylgruppe oder für eine lineare oder verzweigte C₂- oder C₃-C₃₀-Alkenylgruppe, für eine Cycloalkylgruppe mit 5 bis 9 Kohlenstoffatomen, für eine C₆-C₃₀-Arylgruppe oder für eine C₆-C₃₀-Arylalkylgruppe steht. Dieser bevorzugte Polyester wird im Folgenden als anionischer Polyester bezeichnet.

The soil repellent polymer is very particularly preferably at least one anionic polyester containing at least one structural unit of the formula (I), at least one structural unit of the formula (II) and at least one structural unit of the formula (III)

wherein

• a, b and c independently of one another each represent a number from 1 to 200,
• 1 / n M ^{n +} for one equivalent of a cation with the number of charges n is n = 1, 2 or 3,
• R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently hydrogen or a C ₁ or C ₂ -C ₁₈ -n-alkyl group or C ₃ - or C ₄ -C ₁₈ -iso- Alkyl group is,
• R ^{7 is} a linear or branched C ₁ - or C ₂ -C ₃₀ -alkyl group or a linear or branched C ₂ - or C ₃ -C ₃₀ -alkenyl group, a cycloalkyl group having 5 to 9 carbon atoms, a C ₆ - C ₃₀ aryl group or a C ₆ -C ₃₀ arylalkyl group. This preferred polyester is hereinafter referred to as anionic polyester.

A chemical bond identified by a * in formulas (I), (II), (III) means a free valency of the structural element concerned, forming an ester linkage in the polymer backbone of the polyester, for example either with one of said structural elements Formulas (I) or the formula (III) or with another at least bivalent structural element. To form a polymer terminus, said valencies of the formula (I) or (III) bind to the structural element of the formula (II) or to another monovalent structural element to form an ester linkage.

The (preferably anionic) polyesters according to the invention are copolyesters which can be formed at least from monomers which, after a polymerization reaction, give corresponding structural units of the formulas (I) and (II) and preferably (III) at least in the polymer backbone. Such polyesters can be obtained, for example, by polycondensation of dialkyl terephthalates (and preferably dialkyl 5-sulfoisophthalates and alkylene glycols and optionally polyalkylene glycols (a, b and / or c> 1) and polyalkylene glycols which are end-capped on one side.) The synthesis of the preferred, anionic, polyesters according to the invention can be carried out according to known methods Processes are carried out, for example, by first heating the abovementioned components with the addition of a catalyst at normal pressure and then building up the required molecular weights in vacuo by distilling off superstoichiometric amounts of the glycols used. Dibutyltin oxide, alkali or alkaline earth metal alcoholates or antimony trioxide / calcium acetate EP 442 101 directed.
Said structural units may be present either in the block or randomly distributed in the polyester molecule of said anionic polyester.

• zwischen 1 und 25, insbesondere zwischen 1 bis 10, besonders bevorzugt zwischen 1 und 5, Struktureinheiten der Formel (I) und
• zwischen 0,05 und 15, insbesondere zwischen 0,1 und 10 und besonders bevorzugt zwischen 0,25 und 3, Struktureinheiten des Formel (II) und
• wenn anionisch besonders bevorzugt zwischen 1 und 30, insbesondere zwischen 2 und 15, besonders bevorzugt zwischen 3 und 10, Struktureinheiten der Formel (III).

Again, preferably, particularly preferably anionic, polyester contains in each case by number average

• between 1 and 25, in particular between 1 and 10, particularly preferred between 1 and 5, structural units of the formula (I) and
• between 0.05 and 15, in particular between 0.1 and 10 and particularly preferably between 0.25 and 3, structural units of the formula (II) and
• when anionically more preferably between 1 and 30, in particular between 2 and 15, particularly preferably between 3 and 10, structural units of the formula (III).

The, preferably anionic, polyesters containing the structural units (I), (II) and preferably (III) (and optionally (IV) vide supra), preferably have number average molecular weights in the range of 700 to 50,000 g / mol, the number average molecular weight can be determined by size exclusion chromatography in aqueous solution using calibration using narrowly distributed polyacrylic acid Na salt standards. The number-average molecular weights are preferably in the range from 800 to 25,000 g / mol, in particular from 1,000 to 15,000 g / mol, particularly preferably from 1,200 to 12,000 g / mol.

It is preferred according to the invention if 1 / n Mn + according to formula (III) for Li ⁺ , Na ⁺ , K ⁺ , 1/2 Mg ²⁺ , 1/2 Ca ²⁺ , 1/3 Al ³⁺ , NH ₄ ⁺ , Monoalkyl, dialkyl, trialkyl or tetraalkylammonium, wherein the alkyl radicals of the ammonium ions are C ₁ -C ₂₂ -alkyl or C ₂ -C ₁₀ -hydroxyalkyl radicals or any mixtures thereof.

• R¹,R²,R³,R⁴,R⁵ und R⁶ unabhängig voneinander jeweils für Wasserstoff oder Methyl,
• R⁷ für Methyl, und/oder
• a, b und c unabhängig voneinander jeweils für eine Zahl von 1 bis 200, insbesondere 1 bis 20, besonders bevorzugt 1 bis 5, außerordentlich bevorzugt a und b = 1, bedeuten und/oder c eine Zahl von 2 bis 10 ist.

Preference is given to anionic polyesters in which correspondingly in formulas (I), (II) and (III)

• R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently hydrogen or methyl,
• R ^{7 is} methyl, and / or
• a, b and c independently of one another each represent a number from 1 to 200, in particular 1 to 20, particularly preferably 1 to 5, very preferably a and b = 1, and / or c is a number from 2 to 10.

• zwischen 1 und 25, insbesondere zwischen 1 bis 10, besonders bevorzugt zwischen 1 und 5, Struktureinheiten der Formel (I) und
• zwischen 0,05 und 15, insbesondere zwischen 0,1 und 10 und besonders bevorzugt zwischen 0,25 und 3, Struktureinheiten des Formel (II) und
• besonders bevorzugt zusätzlich zwischen 1 und 30, insbesondere zwischen 2 und 15, besonders bevorzugt zwischen 3 und 10, Struktureinheiten der Formel (III).

Again, preferably, particularly preferably anionic, polyester contains in each case by number average

• between 1 and 25, in particular between 1 and 10, particularly preferred between 1 and 5, structural units of the formula (I) and
• between 0.05 and 15, in particular between 0.1 and 10 and particularly preferably between 0.25 and 3, structural units of the formula (II) and
• more preferably additionally between 1 and 30, in particular between 2 and 15, particularly preferred between 3 and 10, structural units of the formula (III).

• R¹,R²,R³,R⁴,R⁵ und R⁶ unabhängig voneinander jeweils für Wasserstoff oder Methyl,
• R⁷ für Methyl, und
• a, b und c unabhängig voneinander jeweils für eine Zahl von 1 oder 2 bis 200, insbesondere 1 oder 2 bis 20, besonders bevorzugt 1 oder 2 bis 5, außerordentlich bevorzugt a und b = 1, bedeuten und
• c eine Zahl von 2 bis 10 ist,
  enthalten, wobei die in den suspendierten Feststoffpartikeln enthaltene Gesamtmenge des besagten anionischen Polyesters im Zahlenmittel
  zwischen 1 und 25, insbesondere zwischen 1 bis 10, besonders bevorzugt zwischen 1 und 5, Struktureinheiten der Formel (I)
  zwischen 0,05 und 15, insbesondere zwischen 0,1 und 10 und besonders bevorzugt zwischen 0,25 und 3, Struktureinheiten des Formel (II)
  zwischen 1 und 30, insbesondere zwischen 2 und 15, besonders bevorzugt zwischen 3 und 10, Struktureinheiten der Formel (III).

Very particular preference is given to anionic polyesters in which correspondingly in formulas (I), (II) and (III)

• R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently hydrogen or methyl,
• R ^{7 is} methyl, and
• a, b and c independently of one another each represent a number from 1 or 2 to 200, in particular 1 or 2 to 20, particularly preferably 1 or 2 to 5, very preferably a and b = 1, and
• c is a number from 2 to 10,
  contain, wherein the total amount of the said anionic polyester contained in the suspended solid particles in the number average
  between 1 and 25, in particular between 1 and 10, particularly preferred between 1 and 5, structural units of the formula (I)
  between 0.05 and 15, in particular between 0.1 and 10 and particularly preferred between 0.25 and 3, structural units of the formula (II)
  between 1 and 30, in particular between 2 and 15, particularly preferably between 3 and 10, structural units of the formula (III).

Such polyesters can be obtained, for example, by polycondensation of terephthalic acid dialkyl ester, 5-sulfoisophthalic acid dialkyl ester, alkylene glycols, optionally polyalkylene glycols (at a, b and / or c> 1) and polyalkylene glycols end-capped on one side (corresponding to the unit of the formula II).

As the unit of the formula (I) is an ester of terephthalic acid with one or more difunctional, aliphatic alcohols in question, preferably used here are ethylene glycol (R ₁ and R _{2 are} each H) and / or 1,2-propylene glycol (R ₁ = H and R ₂ = -CH ₃ or vice versa) and / or shorter-chain polyethylene glycols and / or poly [ethylene glycol-copropylene glycol] having number-average molecular weights of 100 to 2000 g / mol.

Poly (ethylene glycol-co-propylene glycol) monomethyl ethers with number average molecular weights of 100 to 2000 g / mol and polyethylene glycol monomethyl ethers of the general formula CH ₃ -O- (C ₂ H ₄ O) _n -H with n = 1 to 99, in particular 1 to 20 and more preferably 2 to 10. Since the theoretical quantitative quantitative conversion to be achieved maximum average molecular weight of a polyester structure is specified by using such unilaterally closed ether, is considered as the preferred amount of Structural unit (II) that necessary to achieve preferred average molecular weights (vide supra).

As the unit of the formula (III), an ester of 5-sulfoisophthalic acid with one or more difunctional aliphatic alcohols is suitable, in which case the abovementioned ones are preferably used.

In a special embodiment of the invention, the, preferably anionic,) polyester additionally contains at least one structural unit of the formula IV,

- [polyfunctional unit] _g (IV)

in the
g is a number from 0 to 5,
Polyfunctional unit for a unit with 3 to 6 free valencies, which can bind to the polymer structure via ester groups.

Apart from linear polyesters which result from the structural units (I), (II) (and preferably (III)), the use of crosslinked or branched polyester structures is also according to the invention. This is expressed by the presence of a crosslinking polyfunctional structural unit (IV) having at least three to a maximum of 6 functional groups capable of esterification reaction. As functional groups, for example, acid, alcohol, ester, anhydride or Be named epoxy groups. Different functionalities in one molecule are also possible. As examples, citric acid, malic acid, tartaric acid and gallic acid, particularly preferably 2,2-dihydroxymethylpropionic acid, can be used for this purpose. Furthermore, polyhydric alcohols such as pentaerythrol, glycerol, sorbitol and / or trimethylolpropane can be used. These may also be polybasic aliphatic or aromatic carboxylic acids, such as benzene-1,2,3-tricarboxylic acid (hemimellitic acid), benzene-1,2,4-tricarboxylic acid (trimellitic acid), or benzene-1,3,5-tricarboxylic acid ( Trimesithsäure) act. The proportion by weight of crosslinking monomers, based on the total mass of the anionic polyester, can be, for example, up to 10% by weight, in particular up to 5% by weight and particularly preferably up to 3% by weight.

According to the invention, preference is given to using solid (particularly preferably anionic) polyesters which have softening points above 40.degree. C.; they preferably have a softening point between 50 and 200 ° C, more preferably between 80 ° C and 150 ° C, and most preferably between 100 ° C and 120 ° C.

Furthermore, the at least one active ingredient may comprise at least one graying inhibitor. Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the graying of the fibers. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ethercarboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, soluble starch preparations and other than the above-mentioned starch products can be used, for example partially hydrolyzed starch. Na-carboxymethylcellulose, methylcellulose, methylhydroxyethylcellulose and mixtures thereof are preferably used.

The process according to the invention thus makes it possible for the first time to prepare matrix capsules loaded with an active ingredient, the active substance having swelling properties in the presence of water. Thus, it is possible that corresponding active ingredients can be stably incorporated into liquid detergents or cleaners. In addition, the production of particularly highly loaded matrix capsules is possible. In the capsules produced by the method according to the invention, it is possible to obtain a high mass ratio of matrix to active ingredient. The mass ratio of matrix to active substance in the capsule is in particular 1: 1 to 1:60, preferably 1: 3 to 1:50 and particularly preferably 1: 5 to 1:40. The mass ratio according to the invention relates to the dry matter of the matrix and the active ingredient. The proportion by weight of any solvents contained is not considered.

In addition to the at least one active ingredient, the suspension from step b) may also comprise at least one further ingredient which is in particular selected from plasticizer, plasticizer, enzyme, enzyme stabilizer, complexing agent for metals, for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids, color transfer inhibitor, for example polyvinylpyrrolidone or polyvinylpyridine N-oxide, foam inhibitor, for example organopolysiloxanes or paraffins, optical brighteners, for example stilbene disulfonic acid derivatives, fragrances or density control agents, or mixtures of these.

Optionally additionally contained enzymes are preferably selected from the group comprising protease, amylase, pullulanase, mannanase, lipase, cellulase, hemicellulase, oxidase, peroxidase, pectate lyase or mixtures thereof. First and foremost, proteases derived from microorganisms, such as bacteria or fungi, come into question. It can be obtained in a known manner by fermentation processes from suitable microorganisms. Proteases are commercially available, for example, under the names BLAP®, Savinase®, Esperase®, Maxatase®, Optimase®, Alcalase®, Durazym® or Maxapem®.

The lipase which can be used can be obtained from Humicola lanuginosa, from Bacillus species, from Pseudomonas species, from Fusarium species, from Rhizopus species or from Aspergillus species. Suitable lipases are commercially available, for example, under the names Lipolase®, Lipozym®, Lipomax®, AmanoQLipase, Toyo-Jozo® lipase, Meito® lipase and Diosynth® lipase. Suitable amylases are commercially available, for example, under the names Maxamyl® and Termamyl®.

The usable cellulase may be a recoverable from bacteria or fungi enzyme, which has a pH optimum, preferably in the weakly acidic to slightly alkaline range of 6 to 9.5.

Suitable foam inhibitors include long-chain soaps, especially behenic soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which moreover can contain microfine, optionally silanated or otherwise hydrophobicized silica. For use in accordance with the invention suspended, said solid particles such foam inhibitors are preferably bound to granular, water-soluble carrier substances.

According to the invention, the flowable solution and the suspension of the at least one active substance are brought into contact with one another. Preferably, the two liquids are mixed together. This can be done, for example, in a static or dynamic mixer done with low intrinsic volume. This works preferably continuously. The mixing should take place as quickly as possible. By bringing the solution into contact with the suspension of the at least one active substance, water molecules also come into contact with the active substance. If this is a swelling agent, it may also swell in this step. Therefore, it is necessary that the contacting and the formation of droplets as well as the subsequent crosslinking of the polymer takes place quickly, ie immediately after one another without a time delay. This is made possible for example by a low intrinsic volume of a static or dynamic mixer.

After contacting, preferably mixing, the crosslinking of the polymer takes place, for example in a crosslinking bath. As already stated, this should be done without delay after contacting. Thus, the production of highly loaded matrix capsules is possible, wherein the active substance may also comprise swelling active ingredients.

The crosslinking of the polymer can be carried out, for example, in the presence of cations, in particular the polymer is crosslinked in the presence of at least one salt of an alkali and / or alkaline earth metal. In particular, a calcium salt and / or a potassium salt are used to crosslink the polymer.

In another embodiment, the present invention relates to polymeric matrix and drug capsules prepared by the method described above. In particular, the capsules are those which have a mass ratio of matrix to active substance of 1: 1 to 1:60, in particular 1: 3 to 1:50, particularly preferably 1: 5 to 1:40. The mass ratio according to the invention relates to the dry matter of the matrix and the active ingredient. The proportion by weight of any solvents contained is not considered.

Furthermore, the present invention relates to the use of such a capsule in a liquid washing or cleaning agent, as well as a liquid detergent or cleaning agent, which comprises the capsules, which were prepared by the process according to the invention.

A corresponding liquid detergent or cleaning agent according to the invention contains polymeric active ingredients in an aesthetic form which the consumer can understand. It is characterized by an aesthetic product design, since the active ingredients are in the form of visually appealing beads. According to the invention, it is therefore also possible that the capsules comprise a dye in addition to the polymer and active ingredient, as a result of which the capsules receive an optical color impression which is visible to the human eye.

If desired, can be applied to the surface of the capsules dyes, which can be dyed in different colors. It is also possible to introduce at least one dye into the polymer or the suspension of the at least one active ingredient so that the dye is located inside the capsule. In both cases, the invention speaks of a coloring or coloring of the capsules.

In one embodiment of the invention, the capsules are colored with a non-white color. Preferred dyes include Acid Red 18 (CI 16255), Acid Red 26, Acid Red 27, Acid Red 33, Acid Red 51, Acid Red 87, Acid Red 88, Acid Red 92, Acid Red 95, Acid Red 249 (CI 18134), Acid Red 52 (CI 45100), Acid Violet 126, Acid Violet 48, Acid Violet 54, Acid Yellow 1, Acid Yellow 3 (CI 47005), Acid Yellow 11, Acid Yellow 23 (CI 19140), Acid Yellow 3 , Direct Blue 199 (CI 74190), Direct Yellow 28 (CI 19555), Food Blue 2 (CI 42090), Food Blue 5: 2 (CI 42051: 2), Food Red 7 (01 16255), Food Yellow 13 (CI 47005), Food Yellow 3 (CI 15985), Food Yellow 4 (CI 19140), Reactive Green 12, Solvent Green 7 (CI 59040). Particularly preferred dyes are water-soluble acid dyes, for example, Food Yellow 13 (Acid Yellow 3, CI 47005), Food Yellow 4 (Acid Yellow 23, CI 19140), Food Red 7 (Acid Red 18, CI 16255), Food Blue 2 (Acid Blue 9, CI 42090), Food Blue 5 (Acid Blue 3, CI 42051), Acid Red 249 (CI 18134), Acid Red 52 (CI 45100), Acid Violet 126, Acid Violet 48, Acid Blue 80 (01 61585), Acid Blue 182, Acid Blue 182, Acid Green 25 (CI 61570), Acid Green 81. Also preferably used are water-soluble direct dyes, for example Direct Yellow 28 (CI 19555), Direct Blue 199 (CI 74190) and water-soluble reactive dyes For example, Reactive Green 12, and the dyes Food Yellow 3 (CI 15985), Acid Yellow 184. Also preferably used are aqueous dispersions of the following pigment dyes, Pigment Black 7 (CI 77266), Pigment Blue 15 (CI 74160), Pigment Blue 15: 1 (CI 74160), Pigment Blue 15: 3 (CI 74160), Pigment Green 7 (CI 74260), Pigment Orange 5, Pigment Re Pigment Red 184 (CI 12487), Pigment Red 188 (CI 12467), Pigment Red 4 (CI 12085), Pigment Red 5 (CI 12490), Pigment Red 9, Pigment Violet 23 (CI 51319), Pigment Yellow 1 (CI 28 11680), Pigment Yellow 13 (CI 21100), Pigment Yellow 154, Pigment Yellow 3 (cf. CI 11710), Pigment Yellow 74, Pigment Yellow 83 (CI 21108), Pigment Yellow 97. In preferred embodiments, the following pigment dyes are used in the form of dispersions: Pigment Yellow 1 (CI 11680), Pigment Yellow 3 (CI 11710), Pigment Red 112 (CI 12370), Pigment Red 5 (CI 12490), Pigment Red 181 (CI 73360), Pigment Violet 23 (CI 51319), Pigment Blue 15: 1 (CI 74160), Pigment Green 7 (CI 74260), Pigment Black 7 (CI 77266). In likewise preferred embodiments, water-soluble polymer dyes, for example Liquitint RTM, Liquitint Blue HP.RTM., Liquitint Blue 65.RTM., Liquitint Patent Blue.RTM., Liquitint Royal Blue.RTM., Liquitint Experimental Yellow 8949-43.RTM., Liquitint Green HMC.RTM., Liquitint Yellow II.RTM. and mixtures thereof.

The capsules preferably have a diameter in the range from 0.3 mm to 5 mm, in particular from 0.5 mm to 3 mm, particularly preferably from 1 mm to 2 mm. In this size range, capsules are visible to the human eye, but are perceived as adjuvants and not as dominating or interfering, but rather as aesthetically pleasing. The specified diameter is the average particle diameter X _50.3 . The mean particle diameter X _50.3 is the volume mean of the particles (measured after storage of the capsules in the climatic chamber for 24 hours at 30 ° C. and 50% relative atmospheric humidity).

The liquid washing or cleaning agent according to the invention preferably has a yield point. As a result, the capsules according to the invention can be uniformly and stably suspended therein. By means of the method according to the invention, it is possible to introduce active substances into liquid washing or cleaning agents which are otherwise only suitable for solid powdery detergents or cleaners.

In the rheology, the yield point is understood as the shear stress (in Pa) below which a specimen exclusively or at least largely elastically deforms, and above which an irreversible, time-dependent, plastic deformation, ie, a flow, takes place. Such a yield value is usually determined by measurement with a rheometer at room temperature, ie a temperature of 20 ° C to 25 ° C, in particular of 25 ° C. Absolutely measuring rheometers, such as the AR 1000-N or AR G2 rheometer from TA Instruments, enable the determination of measurement values independent and reliable, absolute measured values.

The yield point of the liquid detergent or cleaning agent according to the invention, for example, with a rotary rheometer from TA-Instruments, type AR G2 (shear stress controlled rheometer, cone-plate measuring system with 40 mm diameter, 2 ° cone angle, 20 ° C) are measured. This is a so-called shear stress controlled rheometer. Here, the samples in the rheometer with a time-increasing shear stress σ (t) are applied. For example, the shear stress can be increased from the lowest possible value (for example, 0.01 Pa) to, for example, 100 Pa in the course of 30 minutes. As a function of this shear stress σ , the deformation γ of the sample is measured. The deformation is plotted against the shear stress in a log-log plot (log γ against log σ ). If the investigated sample has a yield point, it can be recognized by a sudden change in the slope of the curve. Below a certain shear stress, one finds a purely elastic deformation. The slope of the curve γ ( σ ) (log-log plot) in this range is ideally one. Above this shear stress begins to flow viscous and the slope of the curve is suddenly higher. The shear stress at which the bending of the curve takes place, ie the transition from the elastic to a plastic deformation, marks the yield point. A convenient determination of the yield stress (= bend of the curve) is possible by applying tangents to the two curve parts. Samples without yield point do not show a characteristic kink in the function γ ( σ ).

The composition according to the invention preferably has a yield point in the range from 0.01 Pa to 10 Pa, preferably from 0.1 Pa to 5 Pa, particularly preferably from 0.3 Pa to 3 Pa.

According to the invention, the liquid washing or cleaning agent comprises at least one surfactant and at least one solvent. The liquid detergent or cleaning agent may thus comprise one or more surfactants. These surfactants are selected from the group consisting of anionic, cationic, zwitterionic, nonionic surfactants and mixtures thereof. If the composition comprises a plurality of surfactants, these may be, for example, several different nonionic surfactants. However, it is also possible that the composition comprises, for example, both nonionic and anionic surfactants. This applies analogously to the other surfactants. Preferably, the base formulation comprises at least one anionic surfactant and at least one nonionic surfactant.

If the liquid washing or cleaning agent comprises an anionic surfactant, this is preferably selected from the group consisting of C _9-13- alkylbenzenesulfonates, olefinsulfonates, C _12-18 -alkanesulfonates, ester sulfonates, alk (en) ylsulfates, fatty alcohol ether sulfates and mixtures thereof. It has been found that these sulfonate and sulfate surfactants are particularly suitable for the preparation of stable liquid detergent or cleaning agent with yield point. Liquid washing or cleaning compositions which comprise as anionic surfactant C _9-13- alkylbenzenesulfonates and fatty alcohol ether sulfates have particularly good dispersing properties. Preferred surfactants of the sulfonate type are C _9-13 -alkylbenzenesulfonates, olefinsulfonates, that is to say mixtures of alkene and hydroxyalkanesulfonates and also disulfonates, as are obtained, for example, from C _12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous Sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained. Also suitable are C _12-18 alkanesulfonates and the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. From washing technical Of interest are the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates preferred. 2,3-alkyl sulfates are also suitable anionic surfactants.

Also, fatty alcohol ether sulfates, such as the sulfuric acid monoesters of straight-chain or branched C _7-21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11- alcohols having on average 3.5 mol of ethylene oxide (EO) or C _{12 -18} fatty alcohols with 1 to 4 EO are suitable.

It is preferred that the liquid washing or cleaning agent according to the invention contains a mixture of sulfonate and sulfate surfactants. In a particularly preferred embodiment, the liquid composition C _9-13 alkylbenzenesulfonates and fatty alcohol ether sulfates as anionic surfactant.

In addition to the anionic surfactant, the liquid washing or cleaning agent may also contain soaps. Suitable are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.

The anionic surfactants and the soaps may be in the form of their sodium, potassium or magnesium or ammonium salts. Preferably, the anionic surfactants are in the form of their sodium salts. Further preferred counterions for the anionic surfactants are also the protonated forms of choline, triethylamine, monoethanolamine or methylethylamine.

The liquid washing or cleaning agent may also comprise at least one nonionic surfactant in addition to the anionic surfactant. The nonionic surfactant includes alkoxylated fatty alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl polyglucosides, and mixtures thereof.

The nonionic surfactant used is preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 4 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates having linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example coconut, palm, tallow or oleyl alcohol, and on average 5 to 8 EO per mole of alcohol are preferred. Among the preferred ethoxylated alcohols include for example C _12-14 alcohols with 4 EO or 7 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 5 EO or 7 EO and mixtures of these. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention. Also suitable are also a mixture of a (more) branched ethoxylated fatty alcohol and an unbranched ethoxylated fatty alcohol, such as a mixture of a C _16-18 fatty alcohol with 7 EO and 2-propylheptanol with 7 EO. The washing or cleaning agent particularly preferably contains a C _12-18 fatty alcohol with 7 EO or a C _13-15 oxo alcohol with 7 EO as nonionic surfactant.

The liquid detergent or cleaning agent further comprises one or more solvents. These may be water and / or non-aqueous solvents. Preferably, it contains water as the main solvent, but may further include non-aqueous solvents. Suitable non-aqueous solvents include monohydric or polyhydric alcohols, alkanolamines or glycol ethers. Preferably, the solvents are selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, diglycol, propyldiglycol, butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, Diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, di-n-octyl ether and mixtures thereof Solvent.

In addition to the at least one surfactant and the at least one solvent, the liquid washing or cleaning agent may further comprise builders and / or alkaline substances. As builders, for example, polymeric polycarboxylates are suitable. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those having a molecular weight of 600 to 750,000 g / mol.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 1,000 to 15,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1,000 to 10,000 g / mol, and particularly preferably from 1,000 to 5,000 g / mol, may again be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. To improve the water solubility, the polymers may also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.

As builders which may be present in the washing or cleaning agent according to the invention, particular mention may also be made of silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.

Organic builders which may furthermore be present in the liquid detergent or cleaning agent are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), methylglycinediacetic acid (MGDA) and derivatives thereof and mixtures thereof. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.

However, preference is given to using soluble builders, such as, for example, citric acid, or acrylic polymers having a molar mass of from 1,000 to 5,000 g / mol in the basic formulation.

For the purposes of the present invention, alkaline substances or wash alkalis are chemicals for raising and stabilizing the pH of the composition.

Furthermore, the washing or cleaning agent according to the invention comprises one or more co-surfactants and / or one or more electrolytes. The co-surfactant or the cosurfactants change the micellar structure of the surfactants. By one or more electrolytes, this effect can be strengthened. This results in a lamellar structure of the surfactants. Corresponding structured detergents or cleaning agents with yield point are in the prior art, for example in WO 2013/064357 A1 described. The content of this application is fully incorporated by reference.

Co-surfactants for the purposes of the present invention are amphiphilic molecules with a small, hydrophilic head group. In a binary system with water, these co-surfactants are often only weakly or not at all soluble. Accordingly, they do not form micelles there either. In the presence of surfactants, the co-surfactants are incorporated into their associates and thereby change the Morphology of these associates. The spherical micelles become rod-shaped and / or disc-shaped micelles. With a sufficiently high total surfactant content, lamellar phases or structures are formed.

The cosurfactant is preferably selected from the group consisting of alkoxylated C ₈ -C ₁₈ fatty alcohols having a degree of alkoxylation ≦ 3, aliphatic C ₆ -C ₁₄ -alcohols, aromatic C ₆ -C ₁₄ -alcohols, aliphatic C ₆ -C ₁₂ dialcohols, monoglycerides of C ₁₂ -C ₁₈ fatty acids, diglycerol ethers of C _8- C ₁₈ fatty alcohols and mixtures thereof. Other suitable cosurfactants are 1-hexanol, 1-heptanol, 1-octanol, 1,2-octanediol, stearic monoglycerol and mixtures thereof.

Also suitable are fragrance alcohols such as geraniol, nerol, citronellol, linalool, rhodinol and other terpene alcohols or fragrance aldehydes such as lilial or decanal as co-surfactants.

Preferred cosurfactants are C ₁₂ -C ₁₈ fatty alcohols having a degree of alkoxylation ≦ 3. These cosurfactants are particularly well incorporated into the preferred anionic and nonionic surfactant associates.

Suitable alkoxylated C ₁₂ -C ₁₈ fatty alcohols having a degree of alkoxylation ≦ 3 include, for example, iC ₁₃ H ₂₇ O (CH ₂ CH ₂ O) ₂ H, iC ₁₃ H ₂₇ O (CH ₂ CH ₂ O) ₃ H, C _12-14 -Alcohol with 2 EO, C _12-14 -alcohol with 3 EO, C _13-15 -alcohol with 3 EO, C _12-18 -alcohols with 2 EO and C _12-18 -alcohols with 3 EO.

An electrolyte in the sense of the present invention is an inorganic salt. Preferred inorganic salts include sodium chloride, potassium chloride, sodium sulfate, sodium carbonate, potassium sulfate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, calcium chloride, magnesium chloride, and mixtures thereof. Particularly stable compositions are obtained using sodium chloride or mixtures of sodium chloride and potassium sulfate.

The addition of the inorganic salt promotes the formation of lamellar structures. In addition, the inorganic salt has an influence on the viscosity, so that the viscosity of the liquid composition can be adjusted by means of the inorganic salt.

The capsules prepared according to the invention can be stably dispersed in the liquid detergents or cleaners. Stable means that the agents are stable at room temperature and at 40 ° C for a period of at least 4 weeks, and preferably of at least 6 weeks, without the medium creaming or sedimenting.

Claims (16)

Process for the preparation of capsules of a polymeric matrix and at least one active ingredient, comprising the following steps: a) providing a flowable solution of at least one polymer, b) providing a suspension of the at least one active substance, c) bringing the solution from step a) into contact with the suspension from step b) and d) crosslinking of the polymer. A method according to claim 1, characterized in that the polymer comprises a natural polymer, in particular consists thereof. A method according to claim 2, characterized in that the natural polymer is selected from carageenan, alginate, pectin, guar, gelatin and / or gellan gum. Method according to one of claims 1 to 3, characterized in that the active ingredient is a polymeric agent. Method according to one of claims 1 to 4, characterized in that the at least one active ingredient is selected from soil repellent polymers, siloxane derivatives, cellulose and derivatives thereof, washing power-enhancing polymeric active substances, particulate active ingredients, especially those in microparticulate form. Method according to one of claims 1 to 5, characterized in that the active ingredient comprises a soil repellent polymer, in particular a soil repellent polymer. Method according to one of claims 1 to 6, characterized in that the at least one active ingredient is a polyester containing at least one structural unit of the formula (I) and at least one structural unit of the formula (II)

wherein a and c independently of one another each represent a number from 1 to 200, R ¹ , R ² , R ⁵ and R ⁶ independently of one another each represent hydrogen or a C ₁ - or C ₂ -C ₁₈ -n-alkyl group or C ₃ - or C ₄ -C ₁₈ -iso-alkyl group, R ^{7 is} a linear or branched C ₁ - or C ₂ -C ₃₀ -alkyl group or a linear or branched C ₂ - or C ₃ -C ₃₀ -alkenyl group, a cycloalkyl group having 5 to 9 carbon atoms, a C ₆ - C ₃₀ aryl group or a C ₆ -C ₃₀ arylalkyl group comprises. A method according to claim 7, characterized in that the polyester is anionic and additionally contains at least one structural unit of the formula (III)

wherein b is a number from 1 to 200, 1 / n M ^{n +} for one equivalent of a cation with the number of charges n is n = 1, 2 or 3, R ³ and R ⁴ are each independently hydrogen or a C ₁ - or C ₂ -C ₁₈ -n-alkyl group or C ₃ - or C ₄ -C ₁₈ -iso-alkyl group. A method according to claim 7 or 8, characterized in that in the formulas (I), (II) and (III) of the polyester R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently hydrogen or Methyl and / or R ⁷ in formula (II) is methyl. A method according to any one of claims 1 to 9, characterized in that contacting comprises mixing the mixture and the suspension in a static or dynamic mixer. Method according to one of claims 1 to 10, characterized in that the crosslinking of the polymer takes place in the presence of at least one salt of an alkali and / or alkaline earth metal. Method according to one of claims 1 to 11, characterized in that the crosslinking of the polymer takes place in the presence of at least one calcium salt and / or a potassium salt. Capsules of a polymeric matrix and an active ingredient prepared by the process according to any one of claims 1 to 12. Capsule according to Claim 13, in which the mass ratio of matrix to active substance is 1: 1 to 1:60, in particular 1: 3 to 1:50, especially 1: 5 to 1:40. Use of a capsule according to claim 13 or 14 in a liquid washing or cleaning agent. Liquid washing or cleaning agent comprising capsules according to claim 13 or 14.