WO2001004255A1 - Capsule for the controlled release of active substances - Google Patents

Abstract

The invention relates to a capsule with a controlled release system that releases an active substance at a desired point in time and that is used in machine washing and cleaning processes and releases the active substance at a desired point of the washing process. The wall of the capsule is provided with an opening for releasing the compounds that are contained in the capsule. The inventive capsule contains (A) a substance that is suitable to destroy the wall of the capsule by reacting with the material of the capsule and/or by reacting with another substance, (B) a gas that does not react with the ingredients contained in the capsule under storage conditions, (C) an active substance.

Description

 Capsule for the controlled release of active substances

The present invention relates to a capsule for the controlled release of active substances, in particular it relates to the use of this capsule in detergents and cleaning agents, surfactant compositions and in pharmaceutical and cosmetic preparations.

Capsules for the controlled release of active substances are known from a large number of applications. In the pharmaceutical field there are systems with so-called delayed release, i.e. the active ingredients are released after a predetermined period after oral intake. With the so-called controlled release, the dosage of the release of the active substances takes place in a predetermined organ. A generally used system is the release of the active substances in the intestine, in which the capsules consist of an enteric material that is soluble in the intestine. The capsules dissolve in the intestine and the active ingredient is released there.

Another area of application for the use of encapsulated active ingredients are detergents and cleaning agents. Finished agents often contain sensitive substances that can be destroyed by other components under storage conditions. These substances can be incorporated into the agents in encapsulated form. The encapsulated materials are usually surrounded by a water-soluble shell which is dissolved by the wash water, the release then taking place.

The dissolving process begins immediately in the known capsules, so that the rate of release of the active ingredients depends on the rate of dissolution of the capsule material. If the components are to be added only in a certain part of the washing process, ie a certain washing cycle, these components are usually metered in via appropriate devices which are arranged in the washing machines. Household washing machines contain, for example, storage containers for the prewash, the main wash and the rinse cycle. One dishwasher contains storage containers for the detergent and another for the rinse aid.

Capsules that can take advantage of the different pH environments in the body, as in the pharmaceutical sector, are scarce in the field of detergents and cleaning agents. As a rule, there are very similar pH levels in the individual wash cycles. These also show similar temperature fluctuations in the heating and cooling phases. No system is known from the prior art which enables a controlled release of the active substance in a later washing or rinsing cycle.

The object of the present invention was to provide a capsule with a controlled release system which contains an active substance at a desired time, i.e. released at a predetermined location after delivery. The invention was particularly based on the object of providing a capsule which can be used in machine washing and cleaning processes and which releases the active substance at a predetermined time in the washing process.

The present invention accordingly relates to a capsule for the controlled release of active substance

(A) a substance which is suitable for destroying the capsule wall by chemical reaction with the capsule material and / or with another substance,

(B) a gas that does not react with the other components contained in the capsule under storage conditions, and

(C) active substance, the capsule shell having an opening for the outlet of one of the components contained therein. The capsule according to the invention is suitable for a large number of applications in the pharmaceutical and cosmetic field and also for use in machine washing and cleaning agents, in particular in agents for textile washing and for machine washing of dishes.

In the context of the present invention, the term “capsule” is not limited to containers that have the shape of the capsules known from pharmacy. Rather, the term “capsule” in the context of the present invention stands for containers whose walls are stable enough to to withstand the volume expansion and subsequent contraction to such an extent that the outer medium can pass into the interior of the container. In addition to the processes known from the pharmaceutical capsules cylindrical with hemispherical ends also other geometries are, of course, be realized according to the invention, in particular, for example, pouches made of rigid films, spherical, cubic or etc teraederf ^'-shaped packaging ..

By a suitable combination of the materials of the capsule wall and the ingredients, customized capsules according to the invention can be produced. Here, the active substance and the capsule material can, for example, also be selected such that the active substance destroys the material of the capsule. In this special case, substance A and substance C would be identical.

It is not necessary for the entire capsule wall to be destroyed in order to release the active substance from the capsule. Rather, it is sufficient for the content to escape from the capsule that substance A destroys parts of the capsule wall, as a result of which substance C (which can be identical to A) can escape from the capsule.

The opening present in the capsule shell according to the invention, which effects the release mechanism described below, can initially be closed. It is then only necessary for the part which closes the opening to dissolve under the ambient conditions of the application or to open the opening in some other way so that the effect can take place. The release mechanism of the capsule according to the invention is essentially temperature-dependent and takes advantage of the volume expansion of gases as the temperature rises. The capsule according to the invention is particularly suitable for use in an aqueous environment which is heated during use and then cooled again. If the capsule according to the invention is added to an aqueous environment at room temperature, which is then heated, the gas volume in the capsule expands and a small amount of the components A, B and / or C contained therein escapes through the opening in the capsule wall. If the system cools down again after the warm-up process has been completed, or if cold water is supplied to the outside of the capsule, the gas contracts in volume. Simultaneously with the volume contraction, substance is absorbed from the outside, in an aqueous environment, through the opening in the capsule wall. The entering water dissolves or reacts with component A, whereby a medium develops within the capsule, which leads to the destruction or dissolution of the capsule wall. The active substance C is released simultaneously or after the capsule wall has been destroyed.

The shape of the capsule can be any, but it has proven to be advantageous if the capsule is slightly elongated. The solid ingredients collect in an elongated form in the lower part and are then located below the water level when used in an aqueous environment. In such an embodiment, the opening in the capsule wall should also be below the water level.

The wall of the capsule according to the invention should be such that it is initially inert and insoluble to the external medium into which the capsule is introduced during use (for example water) and to the components A, B and C contained in the capsule , but soluble at high and / or low pH values and at least partially destroyed by mechanical forces such as stirring, pressure or abrasion. Examples of suitable materials are polymers which are soluble or dispersible in the alkaline or acidic range. Examples of suitable polymers are modified polysaccharides such as carrageenan, guar, pectin, xantane, partially hydrolyzed cellulose, cellulose acetate, hydroxyethyl, hydroxypropyl and hydroxybutyl cellulose, methyl cellulose and the like. Furthermore, proteins and modified Proteins, called gelatin. Other suitable polymers are acrylates and acrylate polymers. These materials are described below.

To fulfill the above Requirements for the capsule wall may require combinations of different wall materials or a multi-layer structure of the wall made of different wall materials to be used.

The capsule wall has an opening for the exit of components contained in the capsule. This opening should be of a size such that at least one of the components contained in the capsule can escape during the volume expansion in order to avoid bursting of the capsule as a result of the excess pressure which forms. The size of this opening is preferably less than 1 mm, in particular less than 0.5 mm. Component A is selected so that after the entry of external medium into the capsule there is a dissolution or destruction of the capsule wall, for example by formation of an aqueous solution with a pH value that is aggressive for the capsule wall or by the fact that component A contains Water reacts to form a gas, which creates an excess pressure in the capsule, which ultimately leads to its destruction and release of the active substance.

In a preferred embodiment of the present invention, component A is a solid acid and a material of the capsule wall is an acid-soluble polymer. As solid or crystalline acids, preference is given to those which do not give off water of crystallization at the process temperatures, for. B. amidosulfonic acid, citric acid and Na, KHSO. For example, boric acid and other alkali metal bisulfates, alkali metal dihydrogen phosphates and other inorganic salts can also be used as acidifying agents. However, organic acidifying agents are preferably used, citric acid being a particularly preferred acidifying agent. However, the other solid mono-, oligo- and polycarboxylic acids can also be used in particular. Tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are preferred from this group. Organic sulfonic acids such as amidosulfonic acid can also be used. Commercially available and is also preferably used as an acidifying agent in the context of the present invention Sokalan DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (max. 33% by weight).

In a further embodiment, component A is a substance which reacts alkaline under reaction with water and the material of the capsule wall is a polymer which is soluble in alkaline. Examples of solid substances which have an alkaline reaction in aqueous solution are, for example, hydroxides, carbonates, hydrogen carbonates and / or silicates, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, alkali silicates, alkali metal silicates and mixtures of the aforementioned substances being preferred. For the purposes of this invention, the potassium and in particular the sodium salts are preferred among the alkali metal salts, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate.

In a further embodiment of the present invention, as already mentioned above, the release takes place through gas formation in the interior of the capsule and subsequent destruction as a result of the excess pressure. In this embodiment, component A is a substance or a mixture of substances which reacts with the penetrating water to form gas. Possible substances are, for example, a combination of carbonates, such as alkali carbonates and hydrogen carbonates, and a solid acid, for example citric acid, succinic acid, or one or more of the above-mentioned acidifying agents or cobaltamine complexes in combination with resorcinol, an example of a suitable cobaltamine complex [ Co (NH ₃ ) ₅ Cl] Cl ₂ can be called.

A third possible release mechanism for the active substance C is the use of swelling agents as component A. As suitable swelling agents, cellulose and cellulose derivatives can be mentioned which swell when water enters the capsule and lead to destruction and thus release of the active substance. Swelling agents, which are also referred to as "explosives" due to their effect, increase their volume when water enters, whereby on the one hand the intrinsic volume increases (swelling), on the other hand a pressure can be generated by the release of gases, which burst the capsule and in lets smaller particles disintegrate. Well-known swelling agents are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modern differentiated natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.

In the context of the present invention, preferred swelling agents are those based on cellulose. Pure cellulose has the formal gross composition (C ₆ HιoO ₅ ) _n and, formally speaking, is a ß-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. In the context of the present invention, cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions can also be used as swelling agents based on cellulose. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxyl hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based swelling agent. Pure cellulose which is free from cellulose derivatives is particularly preferably used as the cellulose-based swelling agent.

The cellulose used as the swelling agent is preferably not incorporated into the capsule in a finely divided form, but is instead converted into a coarser form before being filled in, for example granulated or compacted. The particle sizes of such disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 μm and in particular at least 90% by weight between 400 and 1200 μm.

Microcrystalline cellulose can be used as a further swelling agent based on cellulose or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions that only the amorphous attack and completely dissolve the phen areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged. Subsequent disaggregation of the microfine celluloses produced by the hydrolysis gives the microcrystalline celluloses, which have primary particle sizes of approximately 5 μm and can be compacted, for example, into granules with an average particle size of 200 μm.

Another possible release mechanism for the active substance C is the use of enzymes as component A. These can be coated, for example, whereby the coating dissolves into the interior of the capsule after a small amount of water has entered, after which the enzymes break down the capsule material and thus release the active substance C. Depending on the capsule material, all common enzymes such as proteases, amylases, cellulases etc. can be used as suitable enzymes, which may also have a function in the washing or cleaning cycle. These enzymes are described in detail below.

Any substances for which controlled release is desired can be used as active substance C. Any active ingredient can be used in the field of pharmaceuticals.

In the washing and cleaning agents, in particular those substances are incorporated in capsule form which are not stable under normal conditions and / or which are to be used in a later stage of the washing process. Examples of active substances which are incorporated into detergents and cleaning agents in the form of capsules, e.g. Rinse aid surfactants, textile treatment agents (fabric softeners), enzymes, bleaching agents, bleaching catalysts, bleach activators, optical brighteners, dyes, fragrances, corrosion inhibitors, etc.

The above-mentioned rinse aid surfactants, which are used in particular in the automatic cleaning of dishes and the textile treatment agents, such as fabric softener components, which are used in textile washing, are components which are only used in machine washing and cleaning processes in one process step after the ordinary washing process can be added. Suitable as rinse aid surfactants are all nonionic surfactants, but in particular fatty alcohol polyethylene glycol ether, fatty alcohol polyethylene / polypropylene glycol ether, mixed ether and / or hydroxyalkyl polyethylene glycol ether.

Examples of fatty alcohol polyethylene glycol ethers are those with the formula (I)

in which R ^{1 is} a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and nl is a number from 1 to 5.

The substances mentioned are known commercial products. Typical examples are adducts of on average 2 or 4 moles of ethylene oxide with technical C12 / 14 coconut fatty alcohol (Dehydol ^® LS-2 and LS-4, Fa. Henkel KGaA) or adducts of on average 4 Moles of ethylene oxide to Cι _/ i ₅ -oxoalcohols (Dobanol ^® 45-4, Shell). The products can have a conventional or even narrowed homolog distribution.

Fatty alcohol polyethylene / polypropylene glycol ethers are to be understood as meaning nonionic surfactants of the formula (II)

CH ₃

R ⁴ O- (CH ₂ CH ₂ O) _n2 (CH ₂ CHO) _rn2 H (II)

in which R ^{2 is} a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms, n2 is a number from 1 to 5 and m2 is a number from 1 to 4. These substances are known commercial products. A typical example is an adduct of an average of 5 moles ethylene oxide and 4 moles of propylene oxide with technical Cι _2/4 ι coconut oil fatty alcohol (Dehydol ^® LS-54, Messrs. Henkel KGaA).

Mixed ethers are to be understood as meaning end-capped fatty alcohol polyglycol ethers with the formula (III)

CH ₃

R ⁵ O- (CH ₂ CH ₂ O) _n3 (CH ₂ CHO) _m3 -R ⁶ (III)

in which R ³ for a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms, n3 for numbers from 1 to 10, m2 for 0 or numbers from 1 to 4 and R ⁴ for an alkyl radical 1 to 4 carbon atoms or a benzyl radical.

Typical examples are mixed ethers of the formula (III) in which R ^{3 stands} for an industrial C 12/14 cocoalkyl radical, n3 for 5 or 10, m3 for 0 and R ⁴ for a butyl group (Dehypon ^® LS-54 or LS-104, from Henkel KGaA). The use of mixed ethers capped with butyl or benzyl groups is particularly preferred for technical reasons.

Hydroxyalkyl polyethylene glycol ethers are compounds with the general formula (IV)

OH R ³

R ⁵ -CH-CH- (OCH ₂ CH ₂ O) _n4 -OR ² (IV)

in which R ^{5 represents} hydrogen or a straight-chain alkyl radical having 1 to 16 carbon atoms,

R ^{6 is} a straight-chain or branched alkyl radical having 4 to 8 carbon atoms,

R represents hydrogen or an alkyl radical having 1 to 16 carbon atoms and n4 stands for a number from 7 to 30, with the proviso that the total number of C atoms contained in R ⁵ and R ⁷ is 6 to 16.

Examples of textile treatment agents are, in particular, cationic surfactants. All customary surface-active substances can be considered as cationic surfactants, cationic surfactants having a textile-softening effect being clearly preferred.

Such cationic active substances with a textile-softening effect are selected with particular preference from those which can be described by one or more of the formulas V, VI or VII:

R ¹

R ¹ -N ⁽⁺⁾ - (CH ₂ ) _n -TR ² (V)

(CH ₂ ) _n -TR ²

R ¹

R ¹ -N ⁽⁺⁾ - (CH ₂ ) _n -CH-CH ₂ (VI)

R 'T T

R ² R ²

R ¹

R ³ -N ⁽⁺⁾ - (CH ₂ ) _n -TR ² (VII)

R ⁴ wherein each group R is selected independently of one another from C ₆ alkyl, alkenyl or hydroxyalkyl groups; each R ^{2 group is} independently selected from C _8-28 alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5.

Enzymes can be incorporated into the capsules in the form of liquid or solid enzyme preparations. Suitable enzymes are in particular those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils. Oxidoreductases can also be used to bleach or inhibit color transfer. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases. Cellobiohydrolases, endoglucanases and glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Because there are different Differentiate cellulase types by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

Capsules, which are to be used in detergents for machine dishwashing, naturally use other enzymes to take account of the different substrates and contaminations treated. In particular, those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned are suitable. All of these hydrolases contribute to the removal of stains such as stains containing protein, fat or starch. Oxido reductases can also be used for bleaching. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Here are enzyme mixtures, for example of protease and amylase or protease and lipase or lipolytic enzymes or of protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes, but especially protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases.

The enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition.

The enzymes are usually produced in a granulated and encapsulated form and added to the detergent and cleaning agent in this form. These granulated and encapsulated enzymes would dissolve in water-containing liquid cleaning agents, which is why the use of liquid enzyme concentrates is generally preferred here. Such liquid enzyme concentrates are either based homogeneously on a propylene glycol / water basis or heterogeneously as a slurry, or they are in a microencapsulated structure. The use of liquid enzyme products is also possible in the capsules according to the invention.

Preferred liquid proteases are Savinase ^® L, Durazym ^® L, Esperase ^® L, and Ever- lase ^® from. Novo Nordisk, Optimase.RTM ^® L, Purafect ^® L, Purafect ^® OX L, Properase.RTM ^® L from. Genencor International, and BLAP ^® L from Biozym Ges.mbH

Preferred amylases are Termamyl ^® L, Duramyl ^® L, and BAN ^® from. Novo Nordisk, Maxamyl ^® WL and Purafect ^® HP On L from. Genencor International. Preferred lipases are Lipolase ^® L, Lipolase ^® ultra L and Lipoprime ^® L from. Novo Nordisk and Lipomax® ^® L from. Genencor International.

As slurries or microencapsulated liquid products e.g. Products such as the Novo Nordisk products labeled SL or LCC are used. The commercial liquid enzyme preparations mentioned contain, for example, 20 to 90% by weight of propylene glycol or mixtures of propylene glycol and water. Capsules preferred in the context of the present invention are characterized in that they contain one or more liquid amylase preparations and / or one or more liquid protease preparations.

Substances from the groups of bleaching agents and bleach activators or bleaching catalysts are also suitable as ingredients for the capsules according to the invention. Sodium percarbonate is of particular importance among the compounds which serve as bleaching agents and produce H ₂ O ₂ in water. Other usable bleaching agents are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and HO ₂ -supplying acidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. Capsules according to the invention for use in cleaning agents can also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) peroxybenzoic acid and their ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phfhalimidoperoxcaproic acid [phthaloiminoperoxyhexanoic acid (phthaloiminoperoxyhexanoic acid) - peroxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1, 9-diperoxyazelaic acid, diperocysebacic acid, diperoxybrassyl acid, 4-diperoxybutanoic acid, diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Chlorine or bromine-releasing substances can also be used as bleaching agents in the capsules according to the invention, which are used in cleaning agents for automatic dishwashing. Suitable materials which release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

Bleach activators which support the action of the bleaching agents can also be ingredients in the capsules according to the invention. Known bleach activators are compounds which contain one or more N- or O-acyl groups, such as substances from the class of anhydrides, esters, imides and acylated imidazoles or oximes. Examples are tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, l, 5-diacetyl-2,2-dioxo-hexahydro-l, 3,5-triazm DADHT and isatoic anhydride ISA.

Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multi-acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), are preferred, acylated triazine derivatives, in particular l, 5-diacetyl-2,4-dioxohexahydro-l, 3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates , in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methylmoly holinium Acetonitrile methyl sulfate (MMA), and the enol esters known from German patent applications DE 196 16 693 and DE 196 16 767, as well as acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose Octaacetyllactose and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam. Hydrophilically substituted acylacetals and acyllactams are also preferably used. Combinations of conventional bleach activators can also be used. The bleach activators are usually used in capsules for automatic dishwashing detergents in amounts of 0.1 to 20% by weight, preferably 0.25 to 15% by weight and in particular 1 to 10% by weight, based in each case on the total detergent , used.

In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be incorporated into the capsules. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.

Bleach activators from the group of multi-acylated alkylenediamines, in particular tetraacetylethylene diamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n-) or iso-NOB or , n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), preferably in amounts of up to 10% by weight, in particular 0.1% by weight up to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 to 6% by weight, based on the total agent.

Bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group consisting of manganese and / or cobalt salts and / or complexes, particularly preferably cobalt (ammin) - Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of manganese sulfate are used in conventional amounts, preferably in an amount of up to 5% by weight, in particular 0.0025% by weight .-% to 1 wt .-% and particularly preferably from 0.01 wt .-% to 0.25 wt .-%, each based on the total agent used. But in special cases, more bleach activator can be used.

When used in detergents and cleaning agents to protect the items to be washed or the machine, the capsules according to the invention can contain corrosion inhibitors, silver protection agents in particular being particularly important in the field of automatic dishwashing. The known substances of the prior art can be used. In general, silver protection agents selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. In addition, active chlorine-containing agents are often found in cleaner formulations, which can significantly reduce the corroding of the silver surface. In chlorine-free cleaners, especially oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these classes of compounds. Salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used. Preferred here are the transition metal salts which are selected from the group consisting of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate. Zinc compounds can also be used to prevent corrosion on the wash ware. In detergent tablets preferred in the context of the present invention, the capsule contains silver protective agents from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes, particularly preferably benzotriazole and / or alkylami - Notriazole, in amounts of 0.01 to 5 wt .-%, preferably from 0.05 to 4 wt .-% and in particular from 0.5 to 3 wt .-%, each based on the weight of the total agent, the which contains capsules.

In order to improve the aesthetic impression of the capsules or of the agents which contain the capsules, the capsules can be wholly or partly colored with suitable dyes or contain dyes. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and are not sensitive to the other ingredients of the compositions and to light, and have no pronounced substantivity towards the treated substrates, such as textile fibers or dishes, in order not to stain them.

Preferred for use in capsules according to the invention for textile washing or for incorporation in textile detergents are all colorants which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners. It has proven to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. For example, anionic colorants, for example anionic nitroso dyes, are suitable. One possible dye is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020). Which as a commercial product ^® for example as Basacid Green 970 from BASF, Ludwigshafen, and mixtures thereof with suitable blue dyes. Other colorants include Pigmosol ^® Blue 6900 (CI 74160), Pigmosol ^® Green 8730 (CI 74260), Basonyl ^® Red 545 FL (CI 45170), Sandolan ^® Rhodamine EB400 (CI 45100), Basacid ^® Yellow 094 (CI 47005), Sicovit ^® Patentblau 85 E 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acidblue 183), Pigment Blue 15 (CI 74160), Supranol ^®

Blue GLW (CAS 12219-32-8, CI Acidblue 221)), Nylosan ^® Yellow N-7GL SGR (CAS 6 611881144--5577--11 ,, CCII AAcciiddyyeellklow 218) and / or Sandolan ^® Blue (CI Acid Blue 182 , CAS 12219-26-0). When choosing the colorant, care must be taken to ensure that the colorants do not have too strong an affinity for the textile surfaces and especially for synthetic fibers. At the same time, when choosing suitable colorants, it must also be taken into account that colorants have different stabilities against oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaning agents varies. For highly soluble dyes, for example, the above-mentioned Basacid Green or the above-mentioned Sandolan Blue ^®, are typically selected dye concentrations in the range of some 10 ^"2 to ^{10" 3} wt .-%. In the due to their brilliance, particularly preferred, but are less readily water-soluble pigment dyes, for example the above-mentioned Pigmosol ^® ATTO-dyes, the appropriate concentration of the colorant is in washing or cleaning agents, however, typically a few 10 ^"3 to ^{10" 4} wt .-% ,

The capsules according to the invention can contain one or more optical brighteners. These fabrics, which are also called "whiteners", are used in modern laundry detergents because even freshly washed and bleached white laundry has a slight yellow tinge. Optical brighteners are organic dyes that convert part of the invisible UV radiation from sunlight into longer-wave blue light. The emission of this blue light complements the "gap" in the light reflected by the textile, so that a textile treated with an optical brightener appears whiter and brighter to the eye. Since the action mechanism of brighteners presupposes that they are drawn onto the fibers, a distinction is made depending on the "dyed" fibers, for example brighteners for cotton, polyamide or polyester fibers. The commercial brighteners suitable for incorporation in detergents essentially belong to five structural groups: the stilbene, the diphenylstilbene, the coumarin-quinoline, the diphenylpyrazoline group and the group of the combination of benzoxazole or benzimidazole with conjugated systems. An overview of common brighteners can be found, for example, in G. Jakobi, A. Löhr "Detergents and Textile Washing", VCH-Verlag, Weinheim, 1987, pages 94 to 100. Suitable are, for example, salts of 4,4'-bis [(4-anilino-6-moφholino-s-triazin-2-yl) amino] -stilbene-2,2'- disulfonic acid or similarly structured compounds which carry a diethanolammo group, a methylamino group, an anilino group or a 2-mefhoxyefhylamino group instead of the morpholino group. Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.

Fragrances are added to the capsules according to the invention in order to improve the aesthetic impression of the products and, in addition to the performance of the product, to provide the consumer with a visually and sensorially "typical and distinctive" product. The aspect of long-lasting scenting of textiles or the delayed fragrance release, which covers the unpleasant "alkali smell" when opening dishwashers, is also important here. Perfume oils or fragrances can be individual fragrance compounds, for example synthetic products of the ester, ether, Aldehydes, ketones, alcohols and hydrocarbons are used. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert.-butylcyclohexyl acetate, linalyl acetate, dimethylbenzyl-carbinyl acetate, phenylethyl-ethyl acetate, linalyl benzoate, benzyl formyl ethylyl ethylphenyl ethylethyl ethyl ethyl ethyl ethyl methyl ethyl pyl nate, styrallyl propionate and benzyl salicylate The ethers include, for example, benzylethyl ether, and the aldehydes include, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeononal Ketones eg the Jonone, oc-isomethyl ion on and methyl cedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lentil flower oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil. The fragrance content of the capsules according to the invention or of the compositions containing the capsules is usually up to 2% by weight of the total formulation. The fragrances can be incorporated directly into the capsules or agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release. Cyclodextrins, for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.

In addition, the capsules can also contain components which have a positive influence on the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component. The preferred oil- and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

Foam inhibitors that can be contained in the capsules according to the invention are, for example, soaps, paraffins or silicone oils, which can optionally be applied to carrier materials.

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed. Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acid. ren of the starch or the cellulose or salts of acidic sulfuric acid esters of the cellulose or the starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof in amounts of 0.1 to 5% by weight, based on the composition, are preferably used

Since textile fabrics, in particular rayon, rayon, cotton and their mixtures, can be wrinkled because the individual fibers prevent bending and kinking. If squeezing and squeezing across the grain are sensitive, the capsules can contain synthetic anti-crease agents. These include, for example, synthetic products based on fatty acids, fatty acid esters. Fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.

To combat microorganisms, the capsules according to the invention can contain antimicrobial active ingredients. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungiostatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarlylsulfonates, halogenophenols and phenol mercuric acetate, although these compounds can be dispensed with entirely.

The capsules can contain antioxidants in order to prevent undesirable changes to the agents and / or the treated textiles or substrates caused by the action of oxygen and other oxidative processes. This class of compounds includes, for example, substituted phenols, hydroquinones, pyrocatechols and aromatic amines as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates. Increased wearing comfort can result from the additional use of antistatic agents, which are additionally added to the capsules according to the invention. Antistatic agents increase the surface conductivity and thus enable the flow of charges that have formed to improve. External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be divided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. External antistatic agents are described, for example, in patent applications FR 1,156,513, GB 873 214 and GB 839 407. The lauryl (or stearyl) dimethylbenzylammonium chlorides disclosed here are suitable as antistatic agents for textiles or as an additive to detergents, an additional finishing effect being achieved.

To improve the water absorption capacity, the rewettability of the treated textiles and to facilitate the ironing of the treated textiles, for example silicone derivatives can be used in the capsules according to the invention which are used for laundry treatment. These additionally improve the rinsing behavior of the agents due to their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated. Preferred silicones are poly-dimethylsiloxanes, which can optionally be derivatized and then are amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds. The viscosities of the preferred silicones at 25 ° C. are in the range between 100 and 100,000 centistokes, the silicones being used in amounts between 0.2 and 5% by weight, based on the total agent.

Finally, the capsules for textile detergents according to the invention can also contain UV absorbers, which absorb onto the treated textiles and improve the light resistance of the fibers. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position. Also substituted are benzotriazoles, in the 3-position phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanoic acid.

Of course, other ingredients of detergents and cleaning agents, such as builders, cobuilders, other surfactants, in particular anionic surfactants, etc., can also be incorporated into the capsules according to the invention. Incoφoration of any pharmaceutical or cosmetic active ingredients is also possible without any problems, so that the advantages of controlled release can be used in a wide variety of fields of application with the aid of the capsules according to the invention.

Any gas which is compatible with the other components present in the capsule can be used as component B. Examples are air, N ₂ , O ₂ , noble gases and noble gas mixtures, and CO2.

The capsule according to the invention can be produced in different ways. One possibility is that prefabricated capsule parts made of the above-mentioned materials are filled with components A and C and the capsule parts are then put together. Prefabricated capsule parts are commercially available as so-called plug capsules. The amount of gas component B is determined by the amount of components A and C filled. If the capsule parts are filled in air, the gas component is air. In the event that a gas component other than air is to be used, the filling is generally carried out in an appropriate gas atmosphere.

After the capsule has been closed, the capsule is provided with the opening, this is usually done by means of a pointed object with a corresponding diameter. Alternatively, pre-perforated capsule shells can also be used.

Another method of manufacture is the manufacture of soft capsules. This takes place on an industrial scale in the so-called "Scherer" process. Here, two tapes made of the capsule wall materials (eg gelatin tapes) are combined in opposing shaping rolls, the capsule being shaped and filled at the same time Capsule opening can take place during capsule shaping / filling, or also in a subsequent process step.

As mentioned above, in order to achieve the properties of the capsule wall mentioned, it may be expedient or necessary to apply one or more layers of further wall materials to the capsules. This can be done, for example, by immersion, film coating or the fluidized bed process.

Microcapsules according to the invention can also be produced which enable the release mechanism. Here, the usual manufacturing processes can be used, followed by the attachment of one or more microholes.

As already mentioned, polymers are particularly suitable as capsule materials. The materials mentioned above such as carrageenan, guar, pectin, xanthan, cellulose and their derivatives as well as gelatin are described below.

Carrageenan is an extract from North Atlantic red algae, which is one of the florid plants, and is named after the Irish coastal town of Carragheen. The carrageenan precipitated from the hot water extract of the algae is a colorless to sand-colored powder with molecular weights of 100000-800000 and a sulfate content of approx. 25%, which is very easily soluble in warm water. There are three main components in carrageenan: The yellow-forming / fraction consists of D-galactose-4-sulfate and 3,6-anhydro-aD-galactose, which are alternately glycosidically linked in the 1,3- and 1,4-positions (agar in contrast, contains 3,6-anhydro-aL-galactose). The non-gelling 1 fraction is composed of 1,3-glycosidically linked D-galactose-2-sulfate and 1,4-linked D-galactose-2,6-disulfate residues and is readily soluble in cold water. The i-carrageenan composed of D-galactose-4-sulfate in 1,3-bond and 3,6-anhydro-aD-galactose-2-sulfate in 1,4-bond is both water-soluble and gel-forming. Other types of carrageenan are also designated with Greek letters: α, ß, γ, μ, v, ξ, π, ω, χ. The type of cations present (K, NH, Na, Mg, Ca) also influences the solubility of the carrageenans. semi-synthetic Products which contain only one type of ion and which can also be used as capsule materials in the context of the present invention are also called carrag (h) eenate.

The guar, also called guar flour, which can be used as a capsule material in the context of the present invention is an off-white powder which is obtained by grinding the endosperm of those originally endemic in the Indian and Pakistani regions, but now also in other countries, e.g. in the southern United States, cultivated guar beans (Cyamopsis tetragonobolus) belonging to the legume family. The main constituent of the guar is up to approx. 85% by weight of the dry substance guaran (guar gum, cyamopsis gum); Minor components are proteins, lipids and cellulose. Guaran itself is a polygalactomannan, i.e. a polysaccharide, the linear chain of which is composed of unsubstituted (see formula VIII) and substituted in the C6 position with a galactose residue (see formula (IX) mannose units in a b-D (I-> 4) linkage.

galactose

Manno

VIII IX

The ratio of VIILIX is approximately 2: 1; contrary to the original assumptions, the IX units are not strictly alternating, but are arranged in pairs or triplets in the polygalactomannan molecule. Information on the molar mass of guaran varies significantly with values of approx. 2.2-10 ⁵ -2.2-10 ⁶ g / mol depending on the degree of purity of the polysaccharide - the high value was determined on a highly purified product - and corresponds to approx. 1350 -13500 sugar units / macromolecule. Guaran is insoluble in most organic solvents. The pectins, which can also be used as capsule material, are high-molecular glycosidic plant substances that are very common in fruits, roots and leaves. The pectins consist essentially of chains of 1,4-α-glycoside. connected galacturonic acid units, the acid groups of which are 20-80% esterified with methanol, a distinction being made between highly esterified (> 50%) and low-esterified pectins (<50%). The pectins have a sheet structure and are thus in the middle of starch and cellulose molecules. Your macromolecules still contain some glucose, galactose, xylose and arabinose and have weakly acidic properties.

Fruit pectin contains 95%, beet pectin up to 85% galacturonic acid. The molar masses of the various pectins vary between 10,000 and 500,000. The structural properties are also strongly dependent on the degree of polymerization; so form e.g. the fruit pectins in the dried state asbestos-like fibers, the flax pectins, on the other hand, fine, granular powder.

The pectins are produced by extraction with dilute acids, mainly from the inner parts of citrus fruit peel, leftovers or sugar beet pulp.

Xanthan can also be used as a capsule material according to the invention. Xanthan is a microbial anionic heteropolysaccharide that is produced by Xanthomonas campestris and some other species under aerobic conditions and has a molecular weight of 2 to 15 million Daltons. Xanthan is formed from a chain with ß-1,4-bound glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan. Xanthan can be described by the following formula:

Basic unit of xanthan

The celluloses and their derivatives have already been described above as capsule ingredients. Of course, the capsules can also be made from such materials. In addition to cellulose and cellulose derivatives, (modified) dextrins, starch and starch derivatives can also be used as capsule materials.

Suitable nonionic organic capsule materials are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 as well as international patent applications WO 92 / 18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608. An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Starch can also be used as the capsule material for the capsules according to the invention. Starch is a homoglycan, with the glucose units linked α-glycosidically. Starch is made up of two components of different molecular weights: approx. 20-30% straight-chain amylose (MW. Approx. 50,000-150,000) and 70-80% branched chain amylopectin (MW. Approx. 300,000-2,000,000), alongside still contain small amounts of lipids, phosphoric acid and cations. While the amylose forms long, helical, intertwined chains with about 300-1200 glucose molecules as a result of the binding in the 1,4-position, the chain in the amylopectin branches after an average of 25 glucose units through 1,6-binding to form a knot-like structure with about 1500-12000 molecules of glucose. In addition to pure starch, for the production of capsules within the scope of the present invention there are also starch derivatives which can be obtained from starch by polymer-analogous reactions. Such chemically modified starches include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Starches in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as starch derivatives. The group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and starches and amino starches. Among the proteins and modified proteins, gelatin is of outstanding importance as a capsule material. Gelatin is a polypeptide (molecular weight: approx. 15,000-> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions. The amino acid composition of the gelatin largely corresponds to that of the collagen from which it was obtained and varies depending on its provenance. The use of gelatin as a water-soluble coating material is extremely widespread, especially in the pharmaceutical industry in the form of hard or soft gelatin capsules.

Other polymers which can be used as capsule materials are synthetic polymers which are preferably water-swellable and / or water-soluble. These come in particular from the groups of

a) water-soluble nonionic polymers from the group of

al) polyvinylpyrrolidones, a2) vinylpyrrolidone / vinyl ester copolymers, a3) cellulose ethers a4) (modified) polyvinyl alcohols

b) water-soluble amphoteric polymers from the group of

b 1) alkyl acrylamide / acrylic acid copolymers b2) alkyl acrylamide / methacrylic acid copolymers b3) alkyl acrylamide / methyl methacrylic acid copolymers b4) alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b5) alkyl acrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid -

Copolymers b6) alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid

copolymers b7) alkyl acrylamide / alkyl methacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers b8) copolymers of b8i) unsaturated carboxylic acids b8ii) cationically derivatized unsaturated carboxylic acids b8iii) optionally further ionic or nonionic monomers

c) water-soluble zwitterionic polymers from the group of

cl) acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali and ammonium salts c2) acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali and ammonium salts c3) methacroylethylbetaine / methacrylate copolymers

d) water-soluble anionic polymers from the group of

dl) vinyl acetate / crotonic acid copolymers d2) vinyl pyrrolidone / vinyl acrylate copolymers d3) acrylic acid / ethyl acrylate / N-tert-butyl acrylamide teφolymers d4) graft polymers from vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture, copolymerized with crotonic acid, acrylic acid

Methacrylic acid with polyalkylene oxides and / or polyalkylene glycols d5) grafted and crosslinked copolymers from the copolymerization of d5i) at least one monomer of the non-ionic type, d5ii) at least one monomer of the ionic type, d5iii) of polyethylene glycol and d5iv) a crosslinked d6) by copolymerization at least one monomer from each of the following three

Copolymers obtained in groups: d6i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, d6ii) unsaturated carboxylic acids, dόiii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group d6ii) with saturated or unsaturated, unsaturated or branched C _{8 8-} ι - alcohol d7) terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester d8) tetra- and pentapolymers of D8i) crotonic acid or allyloxyacetic d8ii) vinyl acetate or vinyl propionate dδiii) branched allyl or methallyl esters d8iv) Vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters d9) crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinymethyl ether, acrylamide and their water-soluble salts d10) Teφolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic in α-stelamate branched monocarboxylic acid

e) water-soluble cationic polymers from the group of

el) quaternized cellulose derivatives e2) polysiloxanes with quaternary groups e3) cationic guar derivatives e4) polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid e5) copolymers of vinylpyrrolidone with quaternized derivatives of dialkylmino acrylate vinylpyrrolidone methoimidazolinium chloride copolymers e7) quaternized polyvinyl alcohol e8) polymers specified under the LNCI names Polyquatemium 2, Polyquatemium 17, Polyquatemium 18 and Polyquatemium 27.

Water-soluble polymers in the sense of the invention are those polymers which are more than 2.5% by weight soluble in water at room temperature.

The capsules according to the invention can be produced from individual polymers mentioned above, but it is also possible to use mixtures or multilayered layers composed of the polymers. The polymers are described in more detail below.

Water-soluble polymers preferred according to the invention are nonionic. Suitable non-ionogenic polymers are, for example:

Polyvinylpyrrolidones, such as those sold under the name Luviskol (BASF). Polyvinylpyrrolidones are preferred nonionic polymers in the context of the invention.

Polyvinylpyrrolidones [poly (l-vinyl-2-pyrrolidinone)], abbreviation PVP, are polymers of the general formula (X)

which are prepared by free-radical polymerization of 1-vinylpyrrolidone by solution or suspension polymerization using free-radical formers (peroxides, azo compounds) as initiators. The ionic polymerization of the monomer only provides products with low molecular weights. Commercially available polyvinylpyrrolidones have molar masses in the range from approx. 2500-750000 g / mol, which are characterized by the specification of the K values and - depending on the K value - glass transition temperatures of Own 130-175 °. They are presented as white, hygroscopic powders or as aqueous ones. Solutions offered. Polyvinylpyrrolidones are readily soluble in water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc.).

Vinylpyrrolidone / Vinylester copolymers, as are marketed, for example under the trademark Luviskol ^® (BASF). Luviskol ^® VA 64 and Luviskol ^® VA 73, each vinylpyrrolidone-vinyl acetate copolymers, are particularly preferred nonionic polymers.

The vinyl ester polymers are polymers accessible from vinyl esters with the grouping of the formula (XI)

as a characteristic basic building block of macromolecules. Of these, the vinyl acetate polymers (R = CH ₃ ) with polyvinyl acetates as by far the most important representatives have the greatest technical importance.

The vinyl esters are polymerized by free radicals using various processes (solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization). Copolymers of vinyl acetate with vinyl pyrrolidone contain monomer units of the formulas (I) and (II)

Cellulose ethers such as hydroxypropyl cellulose, hydroxyethyl cellulose and hydroxypropylcellulose Methylhy-, as sold for example under the trademark Culminal® "and Benecel ^® (AQUALON). Cellulose ethers can be represented by the general formula (XII) describe

in R represents H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical. In preferred products at least one R in formula (III) is -CH ₂ CH ₂ CH ₂ -OH or -CH ₂ CH ₂ -OH. Cellulose ethers are manufactured industrially by etherification of alkali cellulose (eg with ethylene oxide). Cellulose ethers are characterized by the average degree of substitution DS or the molar degree of substitution MS, which indicate how many hydroxyl groups of an anhydroglucose unit of cellulose have reacted with the etherification reagent or how many moles of etherification reagent have been attached to an anhydroglucose unit on average , Hydroxyethyl celluloses are soluble in water from a DS of approx. 0.6 or an MS of approx. 1. Commercial hydroxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1.35 (DS) and 1.5-3 (MS). Hydroxyethyl and propyl celluloses are marketed as yellowish white, odorless and tasteless powders in widely differing degrees of polymerization. Hydroxyethyl and propyl celluloses are soluble in cold and hot water and in some (water-containing) organic solvents, but insoluble in most (water-free) organic solvents; their aqueous solutions are relatively insensitive to changes in pH or electrolyte addition.

Polyvinyl alcohols, abbreviated as PVAL, are polymers of the general structure

[-CH ₂ -CH (OH) -] "

which in small proportions also structural units of the type

[-CH ₂ -CH (OH) -CH (OH) -CH ₂ ] contain. Since the corresponding monomer, the vinyl alcohol, is not stable in its free form, polyvinyl alcohols are prepared in solution via polymer-analogous reactions by hydrolysis, but technically in particular by alkaline-catalyzed conversion of polyvinyl acetates with alcohols (preferably methanol). These technical processes also make PVAL accessible which contain a predeterminable residual proportion of acetate groups.

Commercial PVAL (e.g. Mowiol ^® types from Hoechst) are commercially available as white-yellow powders or granules with degrees of polymerization in the range of approx. 500-2500 (corresponding to molar masses of approx. 20,000-100,000 g / mol) and have different degrees of hydrolysis of 98 -99 or 87-89 mol%. They are therefore partially saponified polyvinyl acetates with a residual acetyl group content of approx. 1-2 or 11-13 mol%.

The water solubility of PVAL can be reduced by post-treatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus adjust to the desired values.

Other polymers suitable according to the invention are water-soluble amphopolymers. Ampho-polymers include amphoteric polymers, ie polymers that contain free amino groups as well as free -COOH or SO ₃ H groups in the molecule and are capable of forming internal salts, zwitterionic polymers that contain quaternary ammonium groups and - COO ^" - or -SO ₃ ^" groups, and summarized such polymers that contain -COOH or SO ₃ H groups and quaternary ammonium groups. An example of the present invention amphopolymer suitable is that available under the name Amphomer ^® acrylic resin which is a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) -acrylamide and two or more monomers from the group of acrylic acid, Methacrylic acid and its simple esters. Likewise preferred amphopolymers are composed of unsaturated carboxylic acids (e.g. acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (e.g. acrylamidopropyl-trimethyl-ammonium chloride) and optionally further ionic or non-ionic monomers, as described, for example, in German Offenlegungsschrift 39 29 973 and the one cited therein State of the art men are. Tepolymers of acrylic acid, methyl acrylate and methacrylamidopropyltrimonium chloride, as are commercially available under the name Merquat ^® 2001 N, are particularly preferred amphopolymers according to the invention. Other suitable amphoteric polymers are for example those available under the names Amphomer ^® and Amphomer ^® LV-71 (DELFT NATIONAL) octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers.

Suitable zwitterionic polymers are, for example, the polymers disclosed in German patent applications DE 39 29 973, DE 21 50 557, DE 28 17 369 and DE 37 08 451. Acrylamidopropyltrimethylammonium chloride / acrylic acid or methacrylic acid copolymers and their alkali and ammonium salts are preferred zwitterionic polymers. Further suitable zwitterionic polymers are Methacroy- lethylbetain / methacrylate copolymers, which are available under the name Amersette® ^® (AMERCHOL).

Anionic polymers suitable according to the invention include a .:

Vinyl acetate / crotonic acid copolymers, such as are commercially available for example under the names Resyn ^® (National Starch), Luviset ^® (BASF) and Gafset ^® (GAF).

In addition to monomer units of the aforementioned formula (II), these polymers also have monomer units of the general formula (IV):

[-CH (CH ₃ ) -CH (COOH) -] _n (IV)

Vinyl pyrrolidone vinyl acrylate copolymers, obtainable for example under the trade name Luviflex ^® (BASF). A preferred polymer is that available under the name Luviflex VBM-35 ^® (BASF) acrylate terpolymers vinylpyrrolidone.

Acrylic acid / ethyl acrylate / N-tert-butyl acrylamide particles, which are sold, for example, under the name Ultrahold ^® strong (BASF). Graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols

Such grafted polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture with other copolymerizable compounds on polyalkylene glycols, are obtained by polymerization in the heat in a homogeneous phase by converting the polyalkylene glycols into the monomers of the vinyl esters, esters of acrylic acid or methacrylic acid , stirred in the presence of radical generator.

Suitable vinyl esters include, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and as esters of acrylic acid or methacrylic acid, those which are used with low molecular weight aliphatic alcohols, in particular ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1-hexanol, are available.

Polyalkylene glycols in particular include polyethylene glycols and polypropylene glycols. Polymers of ethylene glycol which have the general formula XIII

H- (O-CH ₂ -CH ₂ ) _n -OH (XIII)

are sufficient, where n can take values between 1 (ethylene glycol) and several thousand. There are various nomenclatures for polyethylene glycols that can lead to confusion. The specification of the average relative molecular weight following the specification "PEG" is customary in technical terms, so that "PEG 200" characterizes a polyethylene glycol with a relative molecular weight of approximately 190 to approximately 210. A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and immediately after the hyphen is followed by a number which corresponds to the number n in the formula V mentioned above. According to this nomenclature (so-called INCI- Nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, 5 ^th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997) include PEG-4, PEG-6, PEG-8, PEG-9, PEG-10, PEG- 12, PEG-14 and PEG-16 can be used. Commercially available polyethylene glycols are, for example, under the trade name Carbowax ^® PEG 200 (Union Carbide), Emkapol ^® 200 (ICI Americas), Lipoxol ^® 200 MED (Huls America), polyglycol ^® E-200 (Dow Chemical), Alkapol ^® PEG 300 (Rhone -Poulenc), Lutrol ^® E300 (BASF) and the corresponding trade names with higher numbers.

Polypropylene glycols (PPG) are polymers of propylene glycol that have the general formula XIV

H- (O-CH-CH ₂ ) _n -OH (XIV)

CH ₃

are sufficient, where n can have values between 1 (propylene glycol) and several thousand. Of particular technical importance here are di-, tri- and tetrapropylene glycol, i.e. the representatives with n = 2, 3 and 4 in formula VI.

In particular, the vinyl acetate copolymers grafted onto polyethylene glycols and the polymers of vinyl acetate and crotonic acid grafted onto polyethylene glycols can be used.

grafted and crosslinked copolymers from the copolymerization of i) at least one monomer of the non-ionic type, ii) at least one monomer of the ionic type, iii) of polyethylene glycol and iv) a crosslinker

The polyethylene glycol used has a molecular weight between 200 and several million, preferably between 300 and 30,000. The non-ionic monomers can be of very different types and the following are preferred: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, allyl laurate, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, stearyl vinyl ether and 1-witch.

The non-ionic monomers can likewise be of very different types, of which crotonic acid, allyloxyacetic acid, vinyl acetic acid, maleic acid, acrylic acid and methacrylic acid are particularly preferably contained in the graft polymers.

Efhylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para-divinylbenzene, tetraallyloxyethane and polyallylsucrose with 2 to 5 allyl groups per molecule of saccharin are preferred as crosslinkers.

The grafted and crosslinked copolymers described above are preferably formed from: i) 5 to 85% by weight of at least one monomer of the nonionic type, ii) 3 to 80% by weight of at least one monomer of the ionic type, iii) 2 to 50% by weight, preferably 5 to 30% by weight, of polyethylene glycol and iv) 0.1 to 8% by weight of a crosslinker, the percentage of the crosslinker being formed by the ratio of the total weights of i), ii) and iii) is.

Copolymers obtained by copolymerizing at least one monomer of each of the following three groups: i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, ii) unsaturated carboxylic acids, iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group ii) with saturated or unsaturated, linear or branched C _{8 8-} ι - alcohol Short-chain carboxylic acids or alcohols are to be understood as meaning those having 1 to 8 carbon atoms, the carbon chains of these compounds optionally being interrupted by double-bonded hetero groups such as -O-, -NH-, -S_.

Teφolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester

These polymers contain monomer units of the general formulas (II) and (IV) (see above) and monomer units of one or more allyl or methallyesters of the formula XV:

R ¹ R ^J

R -CC (O) -O-CH ₂ - C = CH ₂ (XV)

CH ₃

wherein R ^{3 is} -H or -CH ₃ , R ^{2 is} -CH ₃ or -CH (CH ₃ ) ₂ and R ^{1 is} -CH ₃ or a saturated straight-chain or branched Cι _-6 - alkyl radical and the sum of the carbon atoms in the radicals R ¹ and R ^{2 is} preferably 7, 6, 5, 4, 3 or 2.

The above-mentioned polymers preferably result from the copolymerization of 7 to 12% by weight of crotonic acid, 65 to 86% by weight, preferably 71 to 83% by weight of vinyl acetate and 8 to 20% by weight, preferably 10 to 17% by weight .-% Allyl- or Methally- letsre of formula XV.

Tetra- and pentapolymers of i) crotonic acid or allyloxyacetic acid ii) vinyl acetate or vinyl propionate iii) branched allyl or methallyl esters iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters Crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinymethyl ether, acrylamide and their water-soluble salts

Teφolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the α-position.

In the case of anionic polymers, particularly suitable capsule materials are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, polyaspartic acid, polyacetals and dextrins, which are described below.

Usable organic capsule materials are, for example, the polycarboxylic acids which can be used in the form of their sodium salts but also in free form. Polymeric polycarboxylates are, for example, the alkali metal salts of polyacrylic acid or polymefhacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.

In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the investigated polymers. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn 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. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

To improve water solubility, the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.

Also particularly preferred as capsule materials are biodegradable polymers made from more than two different monomer units, for example those which are salts of acrylic acid and maleic acid as monomers and vinyl alcohol or vinyl alcohol derivatives or salts of acrylic acid and 2-alkylallylsulfonic acid as monomers and Contain sugar derivatives.

Further preferred copolymeric capsule materials are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

Polymeric aminodicarboxylic acids, their salts or their precursors may also be mentioned as further preferred capsule materials. Polyaspartic acids or their salts and derivatives are particularly preferred.

Further suitable capsule materials are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid. Other polymers which can preferably be used as capsule materials are cationic polymers. The permanent cationic polymers are preferred among the cationic polymers. According to the invention, “permanently cationic” refers to those polymers which, regardless of the pH of the composition (ie both the capsule and any other composition present) have a cationic group. These are generally polymers which have a quaternary nitrogen atom, for example in the form of an ammonium group.

Preferred cationic polymers are, for example

quaternized cellulose derivatives, as are commercially available under the names Celquat "and Polymer JR ^® . The compounds Celquat ^® H 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternized cellulose derivatives. Polysiloxanes with quaternary groups, such as for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethyl silylamodimethicon), Dow Coming ^® 929 emulsion (containing a hydroxylamino-modified silicone which is also known as amodimethicone), SM-2059 (manufacturer : General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80),

Cationic guar derivatives, such as, in particular, the products sold under the trade names Cosmedia ^® Guar and Jaguar ^® ,

Polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. Under the names Merquat ^® 100 (Poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) commercially available products are examples of such cationic polymers.

Copolymers of vinyl pyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate, such as, for example, vinyl pyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat ^® 734 and Gafquat ^® 755. Vinylpyrrolidone-methoimidazolinium chloride copolymers, as are offered under the name Luviquat ^® . quaternized polyvinyl alcohol and those under the names

Polyquatium 2,

Polyquatium 17,

Polyquaternium 18 and

Polyquatium 27 known polymers with quaternary nitrogen atoms in the main polymer chain. The polymers mentioned are named according to the so-called INCI nomenclature, with detailed information in the CTFA International Cosmetic Ingredient Dictionary and Handbook, 5 ^th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997, to which express reference is made here becomes.

Cationic polymers preferred according to the invention are quaternized cellulose derivatives and polymeric dimethyldiallylammonium salts and their copolymers. Cationic cellulose derivatives, in particular the commercial product Polymer JR 400, are very particularly preferred cationic polymers.

The capsules according to the invention can be used, for example, in pharmaceutical and cosmetic preparations, in surfactant compositions, washing, rinsing, auxiliary washing, cleaning and textile aftertreatment compositions. For example, it is possible to provide a washing and cleaning agent which only comprises the capsules according to the invention which are dosed by the consumer in the washing machine or dishwasher. Of course, it is also possible to add the capsules to an otherwise ready-made cosmetic agent or a detergent and cleaning agent in order to give it an additional benefit through the controlled release of certain active ingredients.

The agents to which the capsules according to the invention are added can be liquid, gel-like, pasty, powder-like or granular or in the form of compact shaped bodies, the formulation freedom being virtually unlimited. The temperature-controlled release mechanism from the capsules according to the invention can achieve a controlled release of the capsule contents, which opens up new performance dimensions for the products.

For example, it is possible to add the capsules according to the invention to a particulate cleaning agent for machine dishwashing. The capsules according to the invention are designed in such a way that the release of the ingredients is initiated only after the medium surrounding them (rinsing liquor) has cooled. When it cools down, the medium surrounding the capsule enters the capsule and initiates a reaction that at least partially destroys the capsule wall. The duration of this process and thus the time that elapses between the cooling of the external medium and the release of the active substances from the capsule can depend on the thickness of the capsule wall, on the physical and / or chemical stability of the capsule wall, on the type of the capsule wall destructive reaction or the aggressiveness of the ingredients against the capsule wall after access to the external medium. It is thus possible to produce capsules according to the invention which do not release their ingredients in the main wash cycle (and also in optional pre-wash cycles) in a household dishwasher. After the main rinse, the intermediate rinses are rinsed with cold water so that the external medium enters the capsule. Using a suitable packaging of the capsule, it is now calibrated that the active substances are only released in the rinse cycle and have their effect here. For example, rinse aid surfactants, acidifying agents or scale inhibitors can be ingredients of the capsule, which has a rinse aid effect. In addition to this chemical assembly, depending on the type of dishwasher, physical assembly is required so that the capsules according to the invention are not pumped out when the water is changed in the machine and are therefore no longer available for the rinse aid. Standard household dishwashers contain a sieve insert in front of the drain pump, which pumps the water or cleaning solution out of the machine after the individual cleaning cycles, which is intended to prevent the pump from becoming blocked by dirt residues. If heavily soiled crockery is washed by the consumer, this sieve insert must be cleaned regularly, which is easily possible due to the easy accessibility and removability. The capsules of the invention are now preferably designed in terms of their size and shape so that they Do not pass the sieve of the dishwasher even after the cleaning cycle, ie after exposure to movement in the machine and the cleaning solution. In this way it is ensured that capsules according to the invention are in the dishwasher in the final rinse cycle, which release the active substance (s) under the action of the colder water after the main rinse cycle by at least partially destroying the capsule wall and bring the desired final rinse effect. Particulate machine dishwashing agents preferred in the context of the present invention are characterized in that the capsules according to the invention contained therein have particle sizes between 1 and 20 mm, preferably between 1.5 and 15 mm and in particular between 2 and 12 mm.

In such particulate dishwashing detergents, the capsules according to the invention with the above-mentioned sizes can protrude from the matrix of the other particulate ingredients, but the other particles can also have sizes that lie in the range mentioned, so that overall a cleaning agent is formulated that consists of large cleaning agent particles and Capsules. In particular, if the capsules according to the invention are colored, for example have a red, blue, green or yellow color, it is important for the appearance of the product, i.e. of the entire cleaning agent is advantageous if the capsules are visibly larger than the matrix of the particles of the other ingredients of the cleaning agent. Particulate machine dishwashing detergents are preferred here which (without taking into account the capsules) have particle sizes between 200 and 3000 μm, preferably between 300 and 2500 μm and in particular between 400 and 2000 μm.

If such cleaning agents are formulated as a powder mixture, partial segregation can occur on the one hand when the package is shaken - especially with very different capsule and cleaning agent matrix sizes; on the other hand, the dosage can be different in two successive cleaning cycles, since the consumer is not always the same lots of detergent and capsules dosed. If it is desired to technically always use the same amount per cleaning cycle, this can be achieved by packaging the agents according to the invention in bags made of water-soluble film, which is familiar to the person skilled in the art. Also particulate ma Rapid dishwashing detergents in which a dosing unit is welded into a bag made of water-soluble film are the subject of the present invention. Completely analogously, of course, other cosmetic or pharmaceutical preparations or detergents and cleaning agents, for example textile detergents, can also be provided.

As a result, the consumer only has to insert a bag, which contains, for example, a detergent powder and several optically protruding capsules, into the dosing compartment of his dishwasher. This embodiment of the present invention is therefore an optically attractive alternative to conventional detergent tablets.

The cleaning agents according to the invention can be produced in a manner known per se. A method of producing powdered automatic dishwashing detergents with a rinse aid effect, in which a powdered automatic dishwashing agent known per se is mixed with capsules according to the invention which contain surfactants and / or acidifying agents and / or scale inhibitors, is therefore a further subject of the present invention.

The desired retention of the capsules in the machine described above in this example, even when changing water, can be achieved in addition to the above-mentioned enlargement of the capsules by reducing the size of the holes in the sieve insert. In this way, machine dishwashing detergents can be formulated which have a uniform mean particle size which is smaller than, for example, 4 to 12 mm. For this purpose, a sieve insert is added to the product according to the invention, in which the capsules also have smaller particle sizes, which replace or cover the insert located in the machine. Another object of the present invention is therefore a kit-of-parts, which comprises a powdered machine dishwashing detergent according to the invention and a sieve insert for household dishwashing machines.

As already mentioned, the combination of agent and sieve insert according to the invention allows the formulation of agents in which the capsules also have smaller particle sizes. Kits-of-parts according to the invention, in which the particle sizes of the machine Dishwashing detergents (taking into account the capsules) in the range from 400 to 2500 μm, preferably from 500 to 1600 μm and in particular from 600 to 1200 μm are preferred.

The mesh size or hole size should not be too small to prevent the enclosed sieve insert from becoming blocked by dirt residues. Here kits-of-parts according to the invention are preferred, in which the mesh size or hole size of the sieve insert is 1 to 4 mm and the rinse aid articles are larger than this mesh size or hole size of the sieve insert.

The kit-of-parts according to the invention is not limited to the specific shape of the sieve insert in which it replaces or covers the insert located in the machine. It is also possible and preferred according to the invention to include a sieve insert in the kit-of-parts, which has the shape of a basket which can be hung in a known manner into the dishwasher - for example on the cutlery basket. In this way, a sieve insert designed in this way replaces the dosing chamber, i.e. the consumer doses the automatic dishwasher detergent according to the invention directly into this sieve insert, which acts in the cleaning and rinsing cycle in the manner described above.

The above example was closely based on the conditions in household dishwashers. It is readily apparent that powder detergents can be made up completely analogously, which, for example, release fabric softener active ingredients only after the main wash cycle from capsules according to the invention which contain such active ingredients. Also in the field of pharmacy, cosmetics, dishwashing detergents and general cleaning agents, agents can be formulated completely analogously, which release the desired active substance from the capsules according to the invention.

It is of course also possible to add the capsules according to the invention to compact means or to insert them into them. For example, molded detergent and cleaning products can be produced which contain one or more of the capsules according to the invention. The capsules (n) can either be attached to or in the molded body respectively. The first-mentioned embodiment can be realized, for example, by sticking one or more capsule (s) onto a molded body produced in a manner known per se. The last-mentioned embodiment comprises, for example, inserting one or more capsules according to the invention into the cavities of previously produced molded bodies which have troughs or through holes. The insertion of a capsule according to the invention into an annular shaped body is particularly attractive.

Examples

Production of capsules for use in automatic dishwashing detergents

example 1

The lower parts of hard gelatin capsules of size 000 (volume 1.37 ml) or those of size 0 (volume 0.68 ml) from WEPA were filled with the substances shown in Table 1. Then the capsule was put together and the upper and lower parts were firmly glued. The capsules were coated with a basic polyacrylate (Eudragit E from Röhm), a polymer layer with a thickness of between 0.2 and 0.3 mm being produced. The 0.5 mm diameter opening was made in the lower part of the capsule by means of a needle.

The capsule thus prepared was then placed in a beaker with water at 20 ° C. The water was heated to 65 ° C (level I); the capsule remained at this temperature for 10 minutes after reaching the temperature. The capsule was then placed in 35 ° C. water (stage II) for 5 minutes, which was then heated again to 65 ° C. (stage III). This test sequence simulates the temperature-time sequence of a universal program at 65 ° C in a dishwasher.

The contents of the individual capsules, the capsule weight during the course and at the end of the experiment are shown in Table 1 below. Table 1

Citric anhydride and soda were used in a weight ratio of 1: 1

1 Polytergent ^® SLF-18 B 45: ethylene oxide-propylene oxide block copolymer (alcohol alkoxylate from Olin Chemicals, softening point 25-45 ° C)

2 polyethylene glycol with a molecular weight of 1550

Example 2

In this example, hard gelatin capsules of size 000 (volume 1.37 ml) from WEPA were further treated as follows: The lower part of the capsules was first prepared with 80-100 mg of polyethylene glycol (PEG 3000), an inner coating being applied in the area of the capsule end , The capsule base was then filled with the following composition:

The capsule capacity is 1.3 g. After the capsule has been put together, the remaining volume of the air enclosed in the capsule is 10% of the total volume.

Various coatings were then applied to the capsules, the composition of which is given in% by weight in the following table.

The following capsules were made:

Type 1: 0.25 mm application from recipe 2

Type 2: 0.04 mm application from recipe 1, then 0.15 mm application from recipe 3

The capsules were then provided with a hole (diameter 0.5 mm) at the end of the capsule).

The capsules produced in this way were each used in a 55 ° C. and a 65 ° C. program of commercially available dishwashers (Bosch S 712, Miele G 590) together with a tablet-shaped cleaning agent. The rinse aid tank of the machines was emptied before the tests, so that any rinse aid effects that occur are caused by the capsules according to the invention.

An observation over the running time of the different programs showed that the capsules of type 1 and type 2 did not change visually during the cleaning cycle and the intermediate rinsing. During the rinse cycle, the capsules decomposed and the ingredients were released. The rinse aid effects on glasses, plates and pots were at least as pronounced in all trials as in comparative trials with the usual rinse aid dosage using the automatic machine.

Claims

claims

1. Capsule for the controlled release of active substance, containing

(A) a substance which is suitable for destroying the capsule wall by reaction with the capsule material and / or with a further substance,

(B) a gas that does not react with the ingredients contained in the capsule under storage conditions,

(C) active substance, the capsule wall having an opening for the outlet of the components contained therein.

2. Capsule according to claim 1, characterized in that an acid-soluble, alkali-soluble or water-soluble polymer or a polymer softening at higher temperatures is used as the material for the capsule wall.

3. The method according to claim 1 or claim 2, characterized in that the opening in the capsule wall has a size up to 1 mm.

4. Capsule according to one of claims 1 to 3, characterized in that component A is selected from crystalline acids and / or bases, from components or mixtures which form a gas in reaction with water and / or substances swellable in water.

5. Capsule according to one of claims 1 to 4, characterized in that the gas is selected from air, N ₂ , O ₂ , CO ₂ .

6. Use of the capsule according to one of claims 1 to 5 in machine cleaning compositions for cleaning textiles and hard surfaces, in particular Geschiπ.

7. Use according to claim 6, characterized in that the active substance is selected from rinse aid surfactants, textile treatment agents (fabric softener), en- zymes, bleaches, bleach catalysts, bleach activators, and / or optical brighteners.

8. Use according to claim 7, characterized in that the rinse aid is selected from nonionic surfactants, preferably selected from the group of fatty alcohol polyethylene glycol ethers, fatty alcohol polyethylene / polypropylene glycol ethers, mixed ethers and / or hydroxyalkyl polyethylene glycol ethers.

9. Use of the capsule according to one of claims 1 to 5 for the administration of cosmetic or pharmaceutical active ingredients.