DE10035849A1 - Particulate composite material for the controlled release of an active ingredient - Google Patents

Abstract

A particulate composite material is claimed for the controlled release of an active substance or an active substance preparation, in which the active substance or the active substance preparation is coated with an LCST polymer, characterized in that the LCST polymer is mixed with an additive with which the film formation is improved or which LCST temperature can be set. The composite material can, for example, be incorporated into detergents and cleaning agents.

Description

The present invention relates to a particulate composite material for release an active ingredient or an active ingredient preparation, wherein the active ingredient or Active ingredient preparation is made up with an LCST polymer, the use of this Composite material in various applications as well as a detergent and cleaning agent, that contains the composite material.

The controlled release of active substances plays a role wherever the active substance not immediately after feeding but only in a later stage of a multi-stage process should have its effect. In many cases, the active ingredients that are only in one metered later stage, are fed manually.

In the pharmaceutical sector, this is used for active ingredients to be administered orally different solution behavior of polymers in acidic and alkaline environments, d. H. how in the stomach and intestines, by using such polymers for coating tablets etc. be used. Medications that are supposed to get into the intestine are common coated with a gastric juice-resistant polymer that only dissolves in the intestine.

In other processes, temperature curves are run through, for example in the Steri lization and pasteurization of food.

Washing and cleaning processes also have several heating and cooling phases, in particular in the last stage of the process, in the so-called rinse cycle the active ingredients are added. These active ingredients are in the usual washing and Cleaning procedures are usually added as separate agents, but are not actually Chen detergent or cleaning agents included.

An encapsulated material is disclosed in international patent application WO 98/49910 Beard where at least part of the material is heat treated in an aqueous encapsulated in the environment and released after cooling after this heat treatment is set. This material has a layer of a hydrophobic film-forming material  and a layer of a material with a lower critical separation temperature (LCST) coated below the temperature of the heat treatment. As a possible approach Utilization of the encapsulated materials disclosed is the food industry, where this Material is used in foods that are sterilized.

The application of layers is technically very complex and requires production of particulate materials an additional operation.

In the older German patent application 199 58 471.0 a washing and Cleaning agents claimed the usual ingredients and an active ingredient preparation that is made up with an LCST polymer. In German patent application 199 58 472.0 becomes a composite material for the controlled release of an active ingredient described, the an active ingredient or a preparation containing this active ingredient in a mixture contains an LCST substance, the material being passed through one or more Heat treatments in a liquid medium remain at least partially unchanged and after cooling after the heat treatment, the active ingredient is released.

It was found that when the drug is packaged with the LCST polymer Problems can occur in particular if the active ingredient or the Active ingredient preparation to be coated with the LCST polymer. The Film properties of the LCST polymers are not always satisfactory. Especially if the LCST polymers are applied from an aqueous solution as a coating film, are in some cases the mechanical properties of the films being formed unsatisfactory, these films are often brittle.

The present invention was based on the object, a particulate To provide composite material coated with an LCST polymer, wherein the film-forming properties of the polymers are improved. Preferably should the film properties of the polymers to the respective field of application and the external Conditions of these areas of application can be adjusted.

Surprisingly, it was found that the properties of the Composite material can improve, if you in the LCST polymer in Used in combination with an additive that improves film formation or by which the LCST temperature can be set.  

The present invention relates to a particulate composite material for controlled release of an active ingredient or an active ingredient preparation, wherein the active ingredient or the active substance preparation is coated with an LCST polymer which characterized in that the LCST polymer is mixed with an additive with which the film formation is improved or the LCST temperature is set can be.

Active substance or active substance preparation in the sense of the present invention means that it can be a single or a mixture of active ingredients, which is either immediate is assembled with the LCST polymer or already as a finished preparation, optionally in a mixture with other substances, and then used with the LCST polymer is made up.

The particulate composite material according to the invention is particularly suitable for such Suitable applications in which the active ingredient or the active ingredient preparation in Process is used where one or more heat treatments in a liquid Medium and material as it passes through Heat treatments remain at least partially unchanged and the active ingredient or the active ingredient preparation after cooling after the Heat treatment is released.

LCST substances are substances that are active at low temperatures have better solubility than at higher temperatures. They are also called Substan zen with lower critical separation temperature. Depending on Conditions of use should be the lower critical segregation temperature between Room temperature and the temperature of the heat treatment, for example between 20 ° C, preferably 25 ° C and 100 ° C, in particular between 25 ° C and 50 ° C. The LCST Substances are preferably selected from alkylated and / or hydroxyalkylated Polysaccharides, cellulose ethers, polyisopropylacrylamide, copolymers of Polyisopropylacrylamids and blends of these substances.

Examples of alkylated and / or hydroxyalkylated polysaccharides are hydroxypropyl methyl cellulose (HPMC), ethyl (hydroxyethyl) cellulose (EHEC), hydroxypropyl cellulose (HPC), methyl cellulose (MC), ethyl cellulose (EC), propyl cellulose (PC), Carboxymethyl cellulose (CMC), carboxymethyl methyl cellulose (CMMC), Hydroxybutylcellulose (HBC), Hydroxybutylmethylcellulose (HBMC), Hydrdoxyethylcellulose (HEC), Hydroxyethylcarboxymethylcellulose (HECMC), Hydroxyethylethylcellulose (HEEC),  Hydroxypropyl cellulose (HPC), hydroxypropyl carboxymethyl cellulose (HPCMC), hydroxy ethylmethylcellulose (HEMC), methylhydroxyethylcellulose (MHEC), methylhydroxyethylpro pylcellulose (MHEPC) and mixtures thereof, carboxymethyl cellulose, methyl cellulose, Methylhydroxyethylcellulose and methylhydroxyproplcellulose as well as the alkali salts of the CMC and the slightly ethoxylated MC or mixtures of the foregoing are preferred.

Further examples of LCST substances are cellulose ethers and mixtures of Cellulose ethers with carboxymethyl cellulose (CMC). Other polymers that have a lower show critical separation temperature in water and which are also suitable Polymers of mono- or di-N-alkylated acrylamides, copolymers of mono- or di-N- substituted acrylamides with acrylates and / or acrylic acids or mixtures of intertwined networks of the above (co) polymers. Are suitable also polyethylene oxide or copolymers thereof, such as ethylene oxide / propylene oxide copo polymers and graft copolymers of alkylated acrylamides with polyethylene oxide, polymeth acrylic acid, polyvinyl alcohol and copolymers thereof, polyvinyl methyl ether, certain pro teine like Poly (VATGVV), a repeating unit in the natural protein elastin and certain alginates. Mixtures of these polymers with salts, low molecular weight Organic compounds or surfactants can also be used as the LCST substance become. Such can the LCST (lower critical separation temperature) be modified accordingly.

The active ingredient used and delayed release can be used in a manner known per se processed the LCST substance and / or the further material, d. H. be assembled. The substances are used as a coating on the active ingredient or the preparation applied, the substances z. B. as a melt or in the form of a solution or Dispersion can be sprayed on, or the mixture can be in the melt, solution or Dispersion can be immersed or mixed with it in a suitable mixer. That too Coating in a fluid bed apparatus is possible. All are suitable for the spraying process Processes established in pharmacy and food technology for the production of coated tablets, capsules and particles. The polymer suspension or solution is sprayed either discontinuously in small portions, the particles z. B. on transported on a conveyor belt through a liquid curtain and then in the Airflow can be dried or continuously while drying by the injected air flow in fluidized bed, fluidized bed or flight bed wrapping devices sprayed. The coating process is also conceivable if the coating syrups are LCST polymers are added in a sufficiently high concentration. The application of the second layer is done analogously. Coating in commercially available drum coats is also possible.  

Are suitable for. B. commercially available coaters, e.g. B. from Lödige, Driam, Manesty, GS, smooth.

The layer thicknesses of the LCST substances depend on the respective application.

In particular, the time available during a process to complete the LCST The layer dissolve and the mechanical stress on the film fluctuate from application to application. For formulations for use as dishwashing detergents in one Dishwashers typically have a layer thickness between 10 µm and 100 µm. When used for textile washing in a household washing machine, the Layers be even thicker.

As additives, according to the invention the application properties of the LCST polymers can improve or by which adjust the LCST temperature lets, in particular polymers, are common plasticizers that are in at room temperature are in liquid form, surfactants and inorganic, water-insoluble particles with a Particle size from 1 to 500 microns to name.

The additives are used in such amounts, each based on the amount of LCST Polymer used, that the LCST properties of the polymer are not lost, i.e. H. that they have better solubility at low temperatures than at higher ones Temperatures.

Examples of suitable polymers are e.g. B. polyvinyl alcohols, polyacrylic acid derivatives and Polyvinylpyrolidone. If these substances themselves have an LCST, this should be clearly differ from the LCST of the actual LCST material. The polymers are used in particular when the LCST polymers are used to coat the Active substances or active substance preparations are used, the Film formation properties are insufficient for formulation. This makes it possible to To improve film properties, in particular their mechanical properties. In particular, LCST polymers can be used in this way, which are in pure form do not form a stable film at all, e.g. B. PVME.

The film-forming properties of the LCST polymers can also be improved using classic plasticizers or surfactants. Classic plasticizers are usually substances that can be mixed with the polymer solution or the polymer itself without macroscopic phase separation. The substances are usually liquid at room temperature. The glass temperature of the LCST polymer can be reduced by adding these plasticizers. Examples of such substances are glycerol, polyethylene glycols, preferably polyethylene glycols liquid at room temperature, triacetin, trialkyl citrate, triethyl citrate, glycols, e.g. B. ethylene glycol, propylene glycol, butylene glycol and glycol ether, polypropylene glycol, PEG-PPGs etc. Surfactants are also suitable to improve the film-forming properties of the LCST polymers. Nonionic surfactants and anionic surfactants are particularly preferably used, the C ₈ -C ₂₂ alcohol alkoxylates and the C ₈ -C ₂₂ alkyl sulfates being particularly mentioned. The surfactants are described in more detail below.

Inorganic water-insoluble materials have been suitable as further additives proven, such as titanium dioxide or natural or modified layered silicates. Such particles preferably have a particle size of 1 to 500 microns.

Layered silicates are in particular crystalline, layered sodium silicates. They have the general formula NaMSi _x O _2x + 1.H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates are Na ₂ Si ₂ O ₅ . yH ₂ O preferred. Talc is also suitable.

The additives used according to the invention can in a manner known per se with the LCST polymers or polymer solutions are mixed before these the active ingredient or the combination of active ingredients are made up. As Confection form have the coating of the active ingredient respectively Active ingredient preparations proven to be particularly suitable.

In a preferred embodiment of the present invention, the active ingredients can the application of the layer containing the LCST polymer and the additive initially with a layer of a water-soluble polymer, e.g. B. polyvinyl alcohol coated to which the LCST substance is then applied.

The water-soluble polymer serves as a protective layer for the active ingredients and so does the diffusive Avoid water ingress and thus premature dissolution and release or slow down. It is obvious to the person skilled in the art that the application of further Layers under the coating with LCST substance are also possible if the Active ingredients are made up without a carrier.  

After the packaging according to the invention with the LOST polymer including additive can the active ingredients used according to the invention with another material be coated. This further material is preferably at a temperature above the LCST temperature of the polymer used is soluble or has one Melting point above this temperature or a retarded solubility in water. This layer serves in particular to pre-mix the active substance and LCST substance Water or other media that can dissolve them before the heat treatment protect. This additional layer should not be liquid at room temperature and is planning preferably a melting point or softening point at a temperature equal to or is above the lower critical segregation temperature of the LCST polymer. The melting point of this layer is particularly preferably between the lower critical Segregation temperature and the temperature of the heat treatment. The further layer can be in a conventional manner in the form of a melt or as a solution / emulsion sprayed on or applied by dipping.

Depending on the application, the further substance preferably has a melting range which is between about 35 ° C and about 75 ° C. In the present case, this means that the Melting range occurs within the specified temperature interval and does not indicate the width of the melting range.

Preferred substances that can be applied as a further layer are hydrophilic, soluble polymers, such as polyvinyl alcohols, polyethylene glycols, polyvinyl pyrrolidone, water-soluble polysaccharides, water-soluble polyurethanes, xanthan, guar gum, alginates, Gelatin, chitosan, crageenan, polyacrylic acids and polyacrylates and copolymers thereof. Shellac, for example Shellac-KPS-Dreiring-SP (Kalkhoff GmbH), is also available Substance can be used.

So-called waxes are further suitable properties. Under "Grow" is a A range of natural or man-made substances understood, which are usually above 40 ° C melt without decomposition and proportionately a little above the melting point are low viscosity and non-stringy. They exhibit a strongly temperature-dependent Consistency and solubility. The waxes are divided into three groups according to their origin, natural waxes, chemically modified waxes and synthetic waxes.

Natural waxes include, for example, vegetable waxes such as candelilla wax, Carnauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax,  Rice germ oil wax, sugar cane wax, ouricury wax, or montan wax, animal waxes such as Beeswax, shellac wax, walrus, lanolin (wool wax), or pretzel fat, mineral waxes such as Ceresin or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin wax or micro wax.

The chemically modified waxes include hard waxes such as Montanester waxes, Sassol waxes or hydrogenated jojoba waxes.

Synthetic waxes generally include polyalkylene waxes or Understand polyalkylene glycol waxes. Connections can also be used as covering materials from other classes of substances that meet the stated softening point requirements fulfill. Suitable synthetic compounds have, for example, higher esters of Phthalic acid, especially dicyclohexyl phthalate, commercially available under the name Unimoll® 66 (Bayer AG) is available. Synthetic waxes made of are also suitable lower carboxylic acids and fatty alcohols, for example dimyristyl tartrate, which under the Name Cosmacol® ETLP (Condea) is available. Conversely, synthetic or Semi-synthetic esters from lower alcohols with fatty acids from native sources can be used. In this class of substances includes, for example, Tegin® 90 (Goldschmidt), a glycerol monostearate palmitate. Also shellac, for example shellac-KPS-Dreiring-SP (Kalkhoff GmbH) used.

The waxes, for example, are also included in the scope of the present invention so-called wax alcohols. Wax alcohols are higher molecular weight, water-insoluble fatty alcohols usually with about 22 to 40 carbon atoms. The Wax alcohols come in the form of wax esters of higher molecular fatty acids, for example (Wax acids) as the main component of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol. The The solid particles coated according to the invention can optionally also be coated Wool wax alcohols, including triterpenoid and steroid alcohols, for example Lanolin, understands that, for example, under the trade name Argowax® (Pamentier & Co) is available. Can also be used at least in part as part of the casing Within the scope of the present invention, however, fatty acid glycerol esters or fatty acid alkanolamides optionally also water-insoluble or only slightly water-soluble polyalkylene glycol links.  

Other suitable hydrophobic substances with a melting point above the LCST of the underlying coating material are saturated aliphatic hydrocarbons (Paraffins).

A major advantage of the particulate composite material according to the present Invention is that active ingredients are released in a process step after a heating step be set. There are a large number of processes in which the individual components ei Go through a heating step, e.g. B. in food, feed and non-food Food industry, for example in pasteurization or sterilization processes. In these The heating step is used to destroy microorganisms or the pro to close the product (e.g. glasses or bottles etc.). Reopening these products is not possible without re-contamination. Such procedures who which is also used in the pharmaceutical industry, in which the products are removed aseptically need to be filled. The addition of other ingredients during or after the asepti refilling is only possible if these other components are also sterile. The release of other ingredients after the heating step without the Verpac Having to open kung etc. offers a variety of advantages.

Also for washing and cleaning processes both in the commercial sector and in Household will go through different temperature levels. Especially at maschi Normal operations are carried out in the rinse aid stages, which involve a washing or cleaning stage increased temperature follow, usually other components added. This later Process stages are usually rinse aid cycles, in which the users, depending on the process, add certain active ingredients. These active ingredients are usually dosed separately either manually or using specially designed devices. Even with these The composite material according to the invention offers a number of advantages when it comes to processes.

The particulate composite material of the invention can be used in a variety of applications applications are used. Accordingly, another subject relates to the present Invention the use of the composite material described above in pharmaceutical and cosmetic products, food, detergents and cleaning agents as well as glue materials.

The active ingredients to be used are based on the corresponding application Right.  

Examples of active ingredients that are only in a process stage after a heating step are released z. B. in the food industry vitamins, proteins, peptides, hy drolysate, nutritional supplements, etc. Examples of active ingredients used in all Erwär steps, also outside of the food industry, are dyes, antioxidants, thickeners, enzymes, preservatives, etc.

As active ingredients and ingredients in detergents and cleaning agents that contain the LCST substance are packaged, tensides, builders, cobuilders, acids are preferred Citric acid, amidosulfonic acid or acidic salts such as citrate and hydrogen sulfate, enzymes, Fragrances, dyes, bleaching agents based on halogen or oxygen, together with bleach activators or catalysts, complexing agents, such as. B. phosphonates, including complexing Surfactants or polymers effective as builders or cobuilders, such as, for. B. polycarboxylates or sulfonated polyacrylates. Machine dishwashing detergents also contain especially rinse aid surfactants and corrosion inhibitors. Textile detergent included Usually, in addition to the components mentioned, fluorescent agents as active ingredients, optical brighteners, soil repellants, run-in preventers, textile finish anti-crease agents, antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, enzymes, Ironing aids, phobing and impregnating agents as well as UV absorbers and fragrances. This Active substances are assembled according to the invention with an LCST substance and can be in the agent according to the invention can be incorporated. In the washing process they are in one Rinse cycle released after the main rinse or wash cycle.

Machine dishwashing detergents preferably contain rinse aid surfactants as active ingredient (s), Surfactants, builders, cobuilders, fragrances, dyes, scale inhibitors, corrosion inhibitors, or bleach, preferably an active chlorine carrier.

In a preferred embodiment of the present invention, the composite material a particulate rinse aid for automatic dishwashing detergents, the active ingredients of which are surfactants, contains in particular rinse aid surfactants, builders and / or cobuilders.

Textile detergents preferably contain enzymes, fragrances, dyes, Fluorescent agents, optical brighteners, anti-shrink agents, fluorescent agents, optical agents brighter, anti-shrink agent, anti-aging components, anti-crease agent, antimicrobial effect substances, germicides, fungicides, antioxidants, antistatic agents, ironing aids, phobing and im impregnating agent as well as UV absorbers and fragrances. These active ingredients are according to the invention made up with an LCST substance and can be incorporated into the agent according to the invention  become. In the washing process, they are washed in one rinse after the main or wash cycle released.

In a preferred embodiment of the present invention, the composite material a particulate laundry aftertreatment agent that acts as fabric softener, contains in particular cationic surfactants, and / or fragrances.

Another object of the present invention relates to washing and cleaning medium, which contains surfactants, builders and optionally other conventional ingredients and the at least one particulate composite material for the controlled release of a Active ingredient or a preparation containing the active ingredient in a mixture with contains additive LCST substance, the composite material after passing through of one or more temperature levels after heat treatment in a liquid Medium remains at least partially unchanged and after cooling after the Heat treatment is released.

The washing and cleaning agent can be used particularly advantageously in mechanical processes use where active ingredients in a rinse cycle after the washing or rinsing step should be released. Examples are machine textile washing and machine washing Cleaning dishes both in the home and in the commercial sector. The Active ingredients can be targeted in one rinse after the main rinse or wash cycle to be released.

In addition to the active ingredients, the detergents and cleaning agents contain other ingredients at least one surfactant, preferably selected from the anionic, nonionic, cat ionic and amphoteric surfactants. The surfactants are preferably in an amount of 0.1 to 50% by weight, preferably 0.1 to 40% by weight and in particular 0.1 to 30% by weight, based on the composition.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO to 7 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 7 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol holoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention. Here block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers. Of course, mixed alkoxylated nonionic surfactants can also be used, in which EO and PO units are not distributed in blocks but statistically. Such products can be obtained by the simultaneous action of ethylene and propylene oxide on fatty alcohols.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in the pure primary straight-chain or methyl branched, in particular in the 2-position methyl branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Another class of nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms men in the alkyl chain, especially fatty acid methyl esters.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dime thylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable. The amount of these nonionic surfactants is preferably not more than that of ethoxylated fatty alcohols, especially not more than half of them.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula I,

in the RCO for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group of polyhydroxy fatty acid amides also includes compounds of the formula II

in which R ² for a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ³ for a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R ⁴ for a linear, branched or cyclic alkyl radical or represents an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 alkyl or phenyl radicals being preferred and [Z] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated derivatives of this residue.

[Z] is preferably obtained by reductive amination of a sugar, for example Glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy or N-aryloxy-substituted compounds can, for example, by reaction with fatty acid remethyl esters in the presence of an alkoxide as a catalyst in the desired polyhy droxy fatty acid amides are transferred.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfates such as are obtained, for example, from C _12-18 monoolefins with a terminal or internal double bond by sulfonation Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulf oxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfofatty acids (ester sulfonates), e.g. B. the α-sulfonated methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.

As alk (en) yl sulfates, the alkali and especially the sodium salts of sulfuric acid are half-esters of C ₁₂ -C ₁₈ fatty alcohols, for example made from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ - Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred from a washing technology interest. 2,3-Alkyl sulfates are also suitable anionic surfactants.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Under fatty acid gly Cerinestern are to be understood as the mono-, di- and triesters and their mixtures, as in the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or obtained in the transesterification of triglycerides with 0.3 to 2 mol of glycerol. before pulled sulfated fatty acid glycerol esters are the sulfonation products of saturated fat acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, Ca. pric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 moles of ethylene oxide (EO) or C _{12 18} fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in surfactant compositions or cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _{8 18} fatty alcohol radicals or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Other suitable anionic surfactants include soaps, in particular can be used at higher pH values. Saturated and unsaturated fat are suitable acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hy third erucic acid and behenic acid and in particular from natural fatty acids, e.g. B. Ko cos, palm kernel, olive oil or tallow fatty acids, derived soap mixtures.

The anionic surfactants including the soaps can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or tri ethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, especially in the form of the sodium salts.

Another group of ingredients are the builders. In the invention Detergents and cleaning agents can all usually be found in washing and cleaning medium used builders may be included, in particular thus zeolites, silicates, car bonate, organic cobuilders and - if no ecological concerns about their use exist - also the phosphates.

As builders, for example, those already mentioned above also come in accordance with the invention usable additives called sheet silicates in question.

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed release and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compaction / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-ray radiation which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (approx. 80 wt X), which was developed by CONDEA Augusta S. p. A. is sold under the brand name VEGOBOND AX® and through the formula

n Na ₂ O. (1-n) K ₂ O. Al ₂ O ₃ . (2-2.5) SiO ₂ . (3.5-5.5) H ₂ O

can be described. Suitable zeolites have an average particle size of few less than 10 µm (volume distribution; measurement method: Coulter Counter) and contain preferably 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

It goes without saying that the generally known phosphates are also used as buildersub punching possible, provided that such use is not avoided for ecological reasons should be. Among the multitude of commercially available phosphates are the alkali metal phosphates with particular preference for pentasodium or pentapotassium tri phosphate (sodium or potassium tripolyphosphate) in the detergent and cleaning agent ind struck the greatest importance.

Alkali metal phosphates is the summary term for the alkali metal (esp special sodium and potassium -) - salts of the various phosphoric acids in which one Can distinguish representatives. The phosphates combine several advantages: They act as an alkali carrier, prevent lime deposits on machine parts or lime incrustations in tissues and also contribute to cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm-3, melting point 60 °) and as a monohydrate (density 2.04 gcm-3). Both salts are white, water-soluble powders that lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ Q ₇ ), at higher temperatures in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below).

NaH ₂ PO _{4 is} acidic; it occurs when phosphoric acid is adjusted to pH 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH2PO4, is a white salt with a density of 2.33 gcm-3, has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is easily soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm ^-3 water loss at 95 °), 7 mol. (Density 1.68 gcm ^-3 melting point 48 ° with loss of 5H ₂ O) and 12 mol. Water (density 1, 52 gcm ^-3 melting point 35 ° with loss of 5H ₂ O), becomes anhydrous at 100 ° and changes to diphosphate Na ₄ P ₂ O ₇ when heated more strongly. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K2HPO4, is an amorphous, white salt that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which, as do decahydrate, have a density of 1.62 gcm ^-3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C and in water-free form (corresponding to 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 . Trina triumphosphate is easily soluble in water with an alkaline reaction and is prepared by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or triphase potassium phosphate), K ₃ PO ₄ , is a white, flowable, granular powder with a density of 2.56 gcm ^-3 has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises e.g. B. when heating Tho masschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ is formed by heating disodium phosphate to <200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.

Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ produces higher moles. Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. For the latter in particular, a large number of terms are used: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or 6H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n - Na with n = 3. In 100 g of water about 17 g of the salt free from water of crystallization dissolve at room temperature, about 20 g at 60 ° and around 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (<23% P ₂ O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

According to the invention, these are exactly like sodium tripolyphosphate, potassium tripolyphosphate or Mixtures of these two can be used; also mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and natri umkalium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripoly Phosphate and sodium potassium tripolyphosphate can be used according to the invention.

As organic cobuilders, the agents according to the invention can in particular Polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid,  Polyacetals, dextrins, other organic cobuilders (see below) and phosphonates be used. These classes of substances are described below.

Usable organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, with such carboxylic acids under polycarboxylic acids can be understood that carry more than one acid function. For example, these are Citro Nenoic acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, Fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if one of the like use for ecological reasons is not objectionable, as well as mixtures of this. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipine acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

The acids themselves can also be used. The acids have besides their buil the effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH value of washing or rice nigungsmitteln. In particular, citric acid, succinic acid, glutaric acid, adi pinic acid, gluconic acid and any mixtures of these.

Polymeric polycarboxylates are also suitable as builders, for example the Alka limetal salts of polyacrylic acid or polymethacrylic acid, for example those with egg ner molecular weight of 500 to 70,000 g / mol.

For the purposes 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 gel permeation chromatography (GPC), using a UV detector. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These figures deviate significantly from the molecular weight data for which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrene sulfonic acids are generally significantly higher than the molar masses specified in this publication.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of Have 2000 to 20,000 g / mol. Because of their superior solubility, this can Group in turn the short-chain polyacrylates, the molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may be preferred.  

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As special copolymers of acrylic acid with maleic acid which have 50 to 90% by weight have proven suitable Contain acrylic acid and 50 to 10 wt .-% maleic acid. Your relative molecular mass sse, based on free acids, is generally from 2000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be either as a powder or as an aqueous solution be used. The content of (co) polymeric polycarboxylates in the agent is before preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

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

Biodegradable polymers of more than two ver. Are also particularly preferred different monomer units, for example those that act as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as Mo nomere salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives th.

Further preferred copolymers are those which are preferably acrolein and Have acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Likewise, other preferred builder substances are polymeric aminodicarboxylic acids, de ren salts or their precursors. Polyaspa are particularly preferred Ragic acids or their salts and derivatives.

Other suitable builder substances are polyacetals, which are produced by the implementation of Dial dehydrogenated with polyol carboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups have pen, can be obtained. Preferred polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyolcar receive bonic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches that can. The hydrolysis can be carried out according to customary methods, for example acid or enzyme catalysis based procedures. They are preferably hydrolysis products  with average molecular weights in the range of 400 to 500000 g / mol. There is a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 preferred, DE being a common measure of the reducing effect of a poly saccharids compared to dextrose, which has a DE of 100. Are usable 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 ones 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. A product oxidized at the C _{6 of} the saccharide ring is also suitable.

Also oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine di succinate, are other suitable cobuilders. This is ethylenediamine-N, N'-disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Continue to be In this connection, glycerol disuccinates and glycerol trisuccinates are also preferred. Suitable amounts are in formulations containing zeolite and / or silicate at 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acid ren or their salts, which may optionally also be in lactone form and wel che at least 4 carbon atoms and at least one hydroxyl group and maximum contain two acid groups.

Another class of substances with cobuilder properties are the phosphonates it is especially hydroxyalkane or aminoalkanephosphonates. Among the Hydroxyalkanephosphonaten is the 1-hydroxyethane-1,1-diphosphonate (HEDP) from special of importance as a cobuilder. It is preferably used as the sodium salt, the Disodium salt neutral and the tetrasodium salt reacts alkaline (pH 9). As an aminoalkane phosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), Diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues in Question. They are preferably in the form of the neutral sodium salts, e.g. B. as Hexasodium salt of EDTMP or as hepta and octa sodium salt of DTPMP. HEDP is preferably used as the builder from the class of the phosphonates. The Aminoalkanephosphonates also have a strong ability to bind heavy metals. Accordingly, it may be preferred, especially if the compositions also contain bleach  be to use aminoalkanephosphonates, in particular DTPMP, or mixtures of to use the phosphonates mentioned.

In addition, all compounds that are capable of complexing with alkaline earth ions train as cobuilders.

Another class of active substances contained in the agents according to the invention can be bleaches that can be selected from the group of Sauer Fabric or halogen bleach, especially chlorine bleach.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphate, citrate perhydrates and H ₂ O ₂ -supplying acidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced. If such bleach tablets are to be used for textile washing, a combination of sodium percarbonate with sodium sesquicarbonate is preferred, irrespective of which other ingredients are contained in the shaped bodies. If cleaning or bleaching agent tablets for machine dishwashing are produced, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaches are the diacyl peroxides, such as. B. 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) the peroxybenzoic acid and its 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-phthalimidoxythoxy-oxohexanoic acid (PAP)], o-carboxybenzamidoperoxyca pronic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacassoxy acid, dalsoxybriperic acid, dalsoxybriperic acid, dalsoxybryanoic acid, diperoxybrenic acid -Decyldiperoxybutan-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Chlorine or bromine-releasing compounds can also be present as bleaching agents. Suitable chlorine or bromine releasing materials include, for example  heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, Tribromo isocyanuric acid, dibromo isocyanuric 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. The ahead compounds mentioned above are preferably used in dishwashing detergents, their use in textile detergents should not be excluded.

In order to achieve an improved bleaching effect, bleach activators can be invented agents according to the invention are incorporated. Compounds which under perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbene result in zoic acid. Substances containing O- and / or N-acyl are suitable groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups wear. Multi-acylated alkylenediamines, in particular tetraacetylethylene, are preferred diamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro- 1,3,5-triazine (DADHT), acylated glycolurils, especially 1,3,4,6-tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfo nates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), acylated hydroxycarboxylic acids, such as triethyl-O-acetyl citrate (TEOC), carboxylic anhydrides, in particular phthalic anhydride, isatoic anhydride and / or succinic anhydride, Carboxamides, such as N-methyldiacetamide, glycolide, acylated polyhydric alcohols, ins special triacetin, ethylene glycol diacetate, isopropenylacetate, 2,5-diacetoxy-2,5-dihydrofu ran and those from German patent applications DE 196 16 693 and DE 196 16 767 known enol esters and acetylated sorbitol and mannitol or their in the European patent application EP 0 525 239 mixtures described (SORMAN), acy lated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraa cetylxylose and octaacetyl lactose as well as acetylated, optionally N-alkylated glucamine or gluconolactone, triazole or triazole derivatives and / or particulate caprolactams and / or caprolactam derivatives, preferably N-acylated lactams, for example N-benzoylca prolactam and N-acetylcaprolactam, which are known from international patent applications WO-A- 94/27970, WO-A-94/28102, WO-A-94/28103, WO-A-95/00626, WO-A-95/14759 and WO-A- 95/17498 are known. The be from the German patent application DE-A-196 16 769 knew hydrophilically substituted acylacetals and those described in German patent application DE- A-196 16 770 and international patent application WO-A-95/14075 Acyl lactams are also preferred. Even those from the German patent Message DE-A-44 43 177 known combinations of conventional bleach activators can be used. Nitrile derivatives such as cyanopyridines, nitrile quats and / or  Cyanamide derivatives are used. Preferred bleach activators are sodium 4- (octa noyloxy) benzenesulfonate, undecenoyloxybenzenesulfonate (UDOBS), sodium dodecanoyloxy benzenesulfonate (DOBS), decanoyloxybenzoic acid (DOBA, OBC 10) and / or dodecanoyl oxybenzenesulfonate (OBS 12). Such bleach activators are in the usual range of amounts from 0.01 to 20% by weight, preferably in amounts of 0.1 to 15% by weight, in particular 1 wt .-% to 10 wt .-%, based on the total composition.

In addition to the conventional bleach activators or in their place can also mentioned bleaching catalysts may be included. These fabrics are pale reinforcing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru, or Mo salt complexes or carbonyl complexes. Also 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 are suitable as bleaching catalysts, such compounds before trains are used, which are described in DE 197 09 284 A1.

Enzymes in particular come in the washing and cleaning agents according to the invention those from the classes of hydrolases such as proteases, esterases, lipases or lipolytic enzymes, amylases, glycosyl hydrolases and mixtures of these Enzymes in question. All of these hydrolases help remove soils like stains containing protein, fat or starch. Oxidoreduk can also be used for bleaching tasen be used. Bacterial strains or fungi are particularly suitable such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens and enzy obtained from its genetically modified variants active ingredients. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used. There are Enzymmi creations, for example from protease and amylase or protease and lipase or lipoly enzymes or protease, amylase and lipase or lipolytic act Enzymes or protease, lipase or lipolytically active enzymes, in particular, however Protease and / or lipase-containing mixtures or mixtures with lipolytically active Enzymes of special interest. Examples of such lipolytic enzymes are the well-known cutinases. Peroxidases or oxidases have also been found in some cases len proved suitable. Suitable amylases include, in particular, alpha-amyla sen, iso-amylases, pullulanases and pectinases.

The enzymes can be adsorbed on carriers or embedded in coating substances in order to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about  4.5% by weight. The enzymes can be used in both washing and cleaning processes during the heat treatment as well as in the rinse cycle after the heat treatment, in a mixture with the LCST substance.

Dyes and fragrances can be added to the agents according to the invention in order to improve the äs improve the theoretical impression of the resulting products and the consumer a visually and sensory "typical and distinctive" product To make available. Individual fragrance compounds can be used as perfume oils or fragrances gene, e.g. B. the synthetic products of the type of esters, ethers, aldehydes, ketones, alcohols and hydrocarbons are used. Fragrance compounds are of the ester type z. B. benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, di methylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methyl phenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzyl salicylate. To the Ethers include, for example, benzyl ethyl ether, the aldehydes e.g. B. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hy droxycitronellal, Lilial and Bourgeonal, to the ketones z. B. the Jonone, α-isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, Phenylethyl alcohol and terpineol, the hydrocarbons mainly include Terpenes like limes and pinene. However, mixtures of different are preferred Fragrances are used, which together produce an appealing fragrance. Such par Fu oils can also contain natural fragrance mixtures, such as those derived from plants Sources are accessible, e.g. B. 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, linden blossom 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 fragrances can be incorporated directly into the cleaning agents according to the invention the, but it can also be advantageous to apply the fragrances to carriers that the Haf increase the perfume on the laundry and by a slower fragrance release for long-lasting fragrance of the textiles. As such carrier materials have been found for example, cyclodextrins have proven themselves, with the cyclodextrin-perfume complexes additionally can be coated with other auxiliaries. Also working into it Composite material according to the invention is possible, so that the fragrances only in the rinse cycle are released, which leads to a scent impression when opening the machine.

In a preferred embodiment of the present invention, this includes in the Composite material incorporated according to the invention surfactants as active ingredients. The  The presence of surfactants in the rinse cycle of an automatic dishwashing process works has a positive effect on the gloss and the reduction of limescale deposits. As active ingredients in Rinse aids are usually only low-foaming nonionic surfactants used, the use of other surfactants, e.g. B. anionic surfactants, not excluded shall be.

As further active ingredients that can or can be incorporated into the composite material are already released in the main rinse or wash cycle, which can be as a machine Ge Detergents used contain corrosion inhibitors. The corrosion inhibitors are included in particular to protect the dishes or the machine, being especially silver protection agents in the area of automatic dishwashing Have meaning. The known substances of the prior art can be used. In general, silver protection agents can be selected from the group of triazoles, the Benzotriazoles, the Bisbenzotriazole, the Aminotriazole, the Alkylaminotriazole and the Über gear metal salts or complexes are used. To be used particularly preferably are benzotriazole and / or alkylaminotriazole. One finds about it in cleaner formulations In addition, agents often containing active chlorine, which significantly reduce the corroding of the silver surface can reduce. Chlorine-free cleaners especially contain oxygen and nitrogen organic redox-active compounds, such as di- and trihydric phenols, e.g. B. Hydro quinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or De derivatives of these classes of compounds. Also salt and complex inorganic compounds gene, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. before the transition metal salts are selected here, which are selected from the group of Man gan 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 and manganese sulfate. Zinc compounds can also be used Prevention of corrosion on the wash ware.

Detergents and cleaning agents that are used for textile washing can act as substances that are only released in the rinse cycle contain cationic surfactants.

Examples of cationic surfactants are, in particular, quaternary ammonium compounds, cationi cal polymers and emulsifiers.

Suitable examples are quaternary ammonium compounds of the formulas (III) and (IV),

where in (III) R ^a and R ^{b are} an acyclic alkyl radical having 12 to 24 carbon atoms, R ^{c is} a saturated C ₁ -C ₄ alkyl or hydroxyalkyl radical, R ^{d is} either equal to R ^a , R ^b or R ^c or stands for an aromatic residue. X ^- represents either a halide, methosulfate, methophosphate or phosphate ion and mixtures of these. Examples of cationic compounds of the formula (III) are didecyldimethylammonium chloride, ditallow dimethylammonium chloride or dihexadecylammonium chloride.

Compounds of formula (IV) are so-called ester quats. Esterquats are characterized by excellent biodegradability. Here R ^e stands for an aliphatic acyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds; R ^t stands for H, OH or O (CO) R ^h , R ^g independently of R ^{f stands} for H, OH or O (CO) R ⁱ ; where R ^h and R ⁱ each independently represent an aliphatic acyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds. m, n and p can each independently have the value 1, 2 or 3. X ^- can be either a halide, methosulfate, methophosphate or phosphate ion, as well as mixtures of these. Preferred compounds are those which contain the group O (CO) R ^h for R ^f and alkyl radicals having 16 to 18 carbon atoms for R ^c and R ^h . Compounds in which R ^{g is} also OH are particularly preferred. Examples of compounds of the formula (IV) are methyl-N- (2-hydroxyethyl) -N, N di (tallow acyl-oxyethyl) ammonium methosulfate, bis- (palmitoyl) -ethyl-hydroxyethyl-methyl-monium methosulfate or methyl -N, N-bis (acyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulfate. If quaternized compounds of the formula (1V) are used which have unsaturated alkyl chains, preference is given to the acyl groups whose corresponding fatty acids have an iodine number between 5 and 80, preferably between 10 and 60 and in particular between 15 and 45 and which have a cis / trans isomer ratio (in% by weight) of greater than 30:70, preferably greater than 50:50 and in particular greater than 70:30. Commercial examples are the methylhydroxyalkyldialkoyloxyalkylammonium methosulfates sold by Stepan under the trademark Stepantex® or the products from Cognis known under De hyquart® or the products from Goldschmidt-Witco known under Rewoquat®. Further preferred compounds are the diesterquats of the formula (V), which are available under the names Rewoquat® W 222 LM or CR 3099 and, in addition to the softness, also ensure stability and color protection.

R ^k and R ^l each independently represent an aliphatic acyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds.

In addition to the quaternary compounds described above, other known compounds can also be used, such as quaternary imidazolinium compounds of the formula (VI),

where R ^{m is} H or a saturated alkyl radical with 1 to 4 carbon atoms, R ⁿ and R ^o independently of one another each represent an aliphatic, saturated or unsaturated alkyl radical with 12 to 18 carbon atoms, R ⁿ alternatively also for O (CO) R ^p may, where R ^{p is} an aliphatic, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms, and Z is an NH group or oxygen and X ^{- is} an anion. q can take integer values between 1 and 4.

Further suitable quaternary compounds are described by formula (VII)

where R ^q , R ^r and R ^s independently represent a C _1-4 alkyl, alkenyl or hydroxyalkyl group, R ^t and R ^u each independently represent a C _8-28 alkyl group and r is a number between 0 and 5 is.

In addition to the compounds of the formulas III to VII, short-chain, water-soluble, quaternary ammonium compounds are used, such as trihydroxyethylmethylammonium methosulfate or the alkyl trimethyl ammonium chlorides, dialkyl dimethyl ammonium chlorides  and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethyl ammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, Lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride.

Also protonated alkylamine compounds that have a softening effect, as well as the non-quaternized, protonated precursors of the cationic emulsifiers are suitable.

The quaternized compounds represent further cationic compounds which can be used according to the invention Protein hydrolyzates.

Suitable cationic polymers include the polyquaternium polymers as described in CTFA Cosmetic Ingredient Dictionary (The Cosmetic, Toiletry and Fragrance, Inc., 1997), in particular the polyquaternium-6, polyquaternium-7, also known as merquats Polyquaternium-10 polymers (Ucare Polymer IR 400; Amerchol), Polyquaternium-4-Copoly mers, such as graft copolymers with a cellulose skeleton and quaternary ammonium groups, which are bound via allyldimethylammonium chloride, cationic cellulose derivatives, such as cationic guar such as guar hydroxypropyl triammonium chloride and the like quaternized Guar derivatives (e.g. Cosmedia Guar, manufacturer: Cognis GmbH), cationic quaternary zuc Kerderivate (cationic alkyl polyglucosides), e.g. B. the commercial product Glucquat®100, according to CTFA nomenclature a "Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride", Co polymers of PVP and dimethylaminomethacrylate, copolymers of vinylimidazole and vinyl pyrrolidone, aminosilicone polymers and copolymers,

Polyquaternized polymers (e.g. Luviquat Care from BASF) and also cationic chitin-based biopolymers and their derivatives, for example the one below polymer available under the trade name Chitosan® (manufacturer: Cognis).

Also suitable according to the invention are cationic silicone oils such as those in the Commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethyl silylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino modifier silicone, also known as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) Abil®-Quat 3270 and 3272 (manufacturer: Gold Schmidt-Rewo; diquartary polydimethylsiloxanes, Quaternium-80), and Siliconquat Rewo quat® SQ 1 (Tegopren® 6922, manufacturer: Goldschmidt-Rewo).

Compounds of the formula (VIII) can also be used,

the alkylamidoamines can be in their non-quaternized or, as shown, their quaternized form. R ^v can be an aliphatic acyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds. s can take values between 0 and 5. R ^w and R ^x each independently represent H, C _1-4 alkyl or hydroxyalkyl. Preferred compounds are fatty acid amidoamines such as stearylamidopropyldimethylamine, which is available under the name Tego Amid®S 18, or 3-tallowamidopropyltrimethylammonium methosulfate, which is available under the name Stepantex® X 9124, which, in addition to having a good conditioning effect, are also characterized by an ink transfer inhibiting action and especially by are characterized by their good biodegradability.

The detergents and cleaning agents according to the invention can be either in solid to gel-like as well as powder, granules, extrudates, single or multi-phase shaped bodies (Tablets), capsules in any form or as pouches, d. H. Pouch made of water-soluble Foil. The individual forms are made by conventional manufacturing processes that the Are known to those skilled in the art.

The agents according to the invention and the composite materials can be produced separately and later combined with each other. It is also possible to put the composite material in the To integrate means.

In a preferred embodiment of the present invention, the agents shaped bodies according to the invention, also referred to in the prior art as tablets, represent, which have several phases, hereinafter called phases A and B, which in the different wash and rinse cycles can be used, the Phase (s) A the active ingredients assembled with the LCST substance and optionally Carrier materials included. The phase (s) A itself can also be performed with the additive LCST Substance be coated.

The active substances in phase (s) A are preferably only in one process step after heat treatment, preferably released in the rinse cycle and the active ingredients the phases B before or during the heat treatment, e.g. B. in the main wash or rinse cycle.  

Phases A and B of the shaped bodies can each be independent of one another pressing or non-pressing process can be produced. To the pressing method counts z. B. tableting in a tablet press. examples for non-pressing processes are sintering processes, microwave processes, melting processes, Injection molding, continuous casting or extrusion processes.

The agents can be prepared in a manner known per se. In one possible Embodiment phases A and B are produced separately and then connected with each other.

In this embodiment, phase A contains surfactants, in particular, as active ingredients Rinse aid surfactants, builders / cobuilders, bleaches, bleach activators, corrosion inhibitors, Base inhibitors, silver protection agents, fragrances and possibly other in small quantities Ingredients.

It has proven to be particularly advantageous if the active substances of phase (s) A or Phase (s) A itself can be coated with the LCST substance. Depending on the Water solubility of the active ingredients can initially, as already described above, a so-called Undercoating with a water-soluble polymer and then the LCST Substance to be applied.

Phase B can in turn consist of several individual phases, which may be on the The outer surface of the molded body is optically distinguishable, e.g. B. by different Surface quality, color, etc. Even the individual phases of phase B can can be obtained by different methods.

Phase B preferably provides a base tablet made from conventional ingredients mechanical detergents and cleaning agents, in particular dishwashing detergents, which already has pre-made recesses (cavity) for the incorporation of phases A. In the Phase B, one or more phases A can be introduced. Connecting the Phases A and B can be done by simply inserting, gluing, pouring or Presses.

In a further embodiment, phases B are present as a loose premix in which the Phases A are inserted and then pressed or hardened in some other way becomes.  

In a further embodiment, the agents according to the invention are in the form of moldings, the moldings and the composite material being produced separately and then can be connected to each other, the moldings can already for Composite material have prefabricated recesses. The connection can for example by simply inserting it into the recess or gluing the two fixed components respectively.

In a particularly preferred embodiment of the above The embodiment according to the invention is an automatic dishwashing detergent is present as a shaped body, and the composite material is a particulate rinse aid, which as Contains active ingredients surfactants, especially rinse aid surfactants, builders and / or cobuilders.

In a further preferred embodiment of the above-mentioned embodiment is the detergent according to the invention, textile detergent, which is in the form of a molding, and Composite material is a particulate laundry treatment agent that acts as an active ingredient Contains fabric softeners, especially cationic surfactants, and / or fragrances.

In a further embodiment, the composite material is in a suitable Tableting device with the premix for the dishwashing detergent or textile detergent processed into moldings.

In the agent according to the invention, some of the active ingredients are incorporated in such a way that they Main rinse or wash cycle (and also in optional pre-rinse cycles) not or only in released to a minor extent. This ensures that active ingredients only in Rinse aid takes effect. In addition to this chemical packaging is dependent on Type of dishwasher or textile washing machine a physical Packaging required so that the active ingredient-containing particles when changing water in the The machine cannot be pumped out and is therefore no longer available for the rinse aid stand.

Domestic dishwashers contain, for example, in front of the drain pump, which the water or the cleaning solution after the individual cleaning cycles the machine pumps, a sieve insert that clogs the pump due to dirt residues should prevent. The assembly of the composite material is regarding its size and shape preferably designed so that it is the sieve insert of the dishwasher after the cleaning cycle, d. H. after exposure to movement in the machine and the  Cleaning solution, not happened. This ensures that there is rinse aid gang the active ingredient is present and is only released in this rinse cycle and the ge brings the desired rinse aid effect. Preferred ma in the context of the present invention Fast dishwashing detergents are characterized in that they contain the active ingredient material or the active ingredient itself is made up in such a way that it has particle sizes between 2 and 30 mm, preferably between 2.5 and 25 mm and in particular between 3 and 20 mm.

In one embodiment of the present invention, the inventive LCST substances custom-made agents or preparations powdered or granular machine dishwashing agents added.

This can contain the active ingredient in the washing and cleaning agents according to the invention ting composite material with the above sizes from the matrix of the others Particulate ingredients protrude, but the other particles can also Have sizes that are in the range mentioned, so that a washing and Detergent is formulated that consists of large detergent particles and the active ingredient containing particles. Especially when the particles containing the active ingredient are colored, for example have a red, blue, green or yellow color it for optical reasons for the appearance of the product, d. H. of the entire Reini agent is advantageous if these particles are visibly larger than the matrix from the Particles of the other ingredients in the product. Here are particulate according to the invention Preferred detergents and cleaning agents (without taking the rinse aid particles into account) Particle sizes between 200 and 3000 microns, preferably between 300 and 2500 microns and have in particular between 400 and 2000 microns.

The optical appeal of such compositions can, in addition to coloring the composite materials also by contrasting coloring of the powder matrix or by the shape of the Composite material can be increased. Since in the manufacture of the composite material on tech nically uncomplicated procedures can be used, it is easily possible to offer them in various forms. In addition to the particle shape, which is approximately Has spherical shape, for example cylindrical or cube-shaped particles and applicable. Other geometric shapes can also be realized. Special pro Product configurations can contain, for example, asterisk-shaped composite material. Also disks or shapes that form the basis of plants and animal bodies, for example Tree, flower, blossom, sheep, fish, etc. can be easily produced. interesting Optical incentives can also be created in this way by, if the  Composite material released in the rinse cycle of a machine dishwashing process is produced in the form of a stylized glass in order to achieve the rinse aid effect in the product op to underline the table. There are no limits to your imagination.

If the cleaning agents according to the invention are formulated as a powder mixture, especially with very different sizes of composite material, the z. B. rinse aid lerparticles and detergent matrix - on the one hand when the package is shaken partial segregation occur, on the other hand the dosing can be carried out in two successive steps cleaning cycles may be different since the consumer is not always mandatory same amount of detergent and composite material, e.g. B. rinse aid, dosed. Should be desired can technically always use the same amount per cleaning cycle, this can be done via the packaging of the agents according to the invention in bags familiar to the person skilled in the art water-soluble film can be realized. Also particulate detergents and cleaning agents, in which a dosing unit is sealed in a bag made of water-soluble film is the subject of the present invention.

As a result, the consumer has only one bag, for example a cleaning medium powder and several optically prominent effects incorporated into the composite material contains substances in the dosing compartment of his washing machine or dishwasher. This embodiment of the present invention is therefore an optically attractive alterna tive to conventional detergent tablets.

The desired retention of the composite material in the The machine can also be used for water changes in addition to the enlargement mentioned above Particles of the composite material also by reducing the holes in the sieve insert realize. In this way you can machine dishwashing detergent or textile detergent formulate, which have a uniform mean particle size, which is smaller than for example 4 to 12 mm. For this, the product according to the invention, in which the composite material has smaller particle sizes, a sieve insert is added, the replaces or covers the insert in the machine. Another subject of The present invention is therefore a kit-of-parts that contains a powdered one according to the invention machine dishwashing detergent or textile detergent and a sieve insert for Household dishwashers or washing machines includes.

As already mentioned, the combination of agent and sieve insert according to the invention allows the formulation of agents in which the composite material also has smaller particle sizes having. Kits-of-parts according to the invention, in which the particle sizes of the  agent according to the invention (taking into account the particles of the composite material) in Range from 400 to 2500 microns, preferably from 500 to 1600 microns and especially from 600 to 1200 microns are preferred.

In order to prevent clogging of the enclosed sieve insert due to dirt residues etc. the mesh size or hole size should not be chosen too small. Here are 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 additives are larger than this mesh size or Hole size of the sieve insert.

The kit of parts according to the invention is not based on the specific shape of the sieve insert limited, in which this replaces or covers the insert in the machine. According to the invention, it is also possible and preferred for the kit of parts to have a sieve insert enclose, which has the shape of a basket, which in a known manner in the Dishwasher - for example on the cutlery basket - can be hung or can be placed in the drum of the washing machine. This way it replaces a sieve insert designed in this way the dosing chamber, d. H. the consumer doses the agent according to the invention directly in this sieve insert, the cleaning and Rinse aid acts in the manner described above.

In a further embodiment of the present invention, the agent according to the invention a textile detergent that acts as an active ingredient and ingredients with the LCST substance are made up, contains cationic surfactants. As above for the Dishwashing detergents described can also use the detergent as a single or multi-phase Shaped bodies are present analogously to the configurations described.

If the agents according to the invention are used as or in textile detergents, then Dosing via the induction chamber or using a dosing aid directly into the drum respectively. The particle size should be such that it is larger than that Hole size in the washing drum or in the sieves.  

Examples 1. Change the LCST temperature of polyisopropylacylamide by adding surfactants

Polyisopropylacrylamide (hereinafter referred to as PIPAAm) has an LCST temperature of 32 ° C

By adding sodium dodecyl sulfate (SDS) to an aqueous solution of PIPAAM their cloud point could be increased (see Table 1). In each case 5% were aqueous solutions used.

Table 1

2.1. Together Menet tongues

For the following examples 2.1 and 2.2, granules of the following composition were produced in a Lödige mixer:
5% water glass 2.4 over-dried
5% Luviskol® VA64 (BASF)
10% Erkol® 48/20 (Wacker)
40% Erkol® 05/140 (Wacker)
40% Polytergent® SLF 1 8845 (Olin Chemicals)

This granulate was then used for the hydraulic tablet press Weber company pressed tablets of 1.5 g each.

2.2 04722 00070 552 001000280000000200012000285910461100040 0002010035849 00004 04603. Use of polymer blends

The following example shows how the mechanical properties of a PIPAAm film that is applied from an aqueous solution can be improved:
An aqueous solution of the following composition was prepared:
PIPAAm: 4.5%
PVA1 (Erkol® 05/140): 0.5%
Water: 95%

The in Example 2.1. The tablets obtained were coated with this solution in a coating pan from ERWEKA or by immersion (2x). After drying, the tablets were coated with a further layer consisting of:
33% shellac
67% isopropanol

Alternatively, a paraffin coating with a melting point of 45 ° C was applied. After this layer had dried or solidified, the tablets according to the invention became together with a commercially available dishwasher detergent tablet (Somat®, commercial product the applicant) in a Miele GS 683 SC dishwasher and at 55 ° C and tested in the 65 ° C program.

In both temperature programs, it was observed that the tablets according to the invention remained largely unchanged during the main (HSG) and intermediate rinse cycle (ZSG) and dissolve in the rinse aid (KSG).

Comparative example

Without the PVA1 being added to the PIPAAm, the 55 ° C program does Desired effect achieved in the dishwasher, the films break in the 65 ° C program however due to their insufficient mechanical stability in the HSG and set the Active ingredient released prematurely.  

2.3. Increase in LCST through surfactants

The following example shows how it warms up slightly when used Have inlet water functional IT switches manufactured:

A total of 5% aqueous coating solutions of the following substance mixtures were produced:
90% PIPAAm
10% SDS
and
80% PIPAAm
20% SDS

With these coating solutions, as in Example 2.2. method. Likewise, that was Shellac or paraffin coating as in Example 2.2. applied.

These cores were again used in a Miele GS 683 SC rinsing test with a commercial dishwasher detergent tablet (Somat®) at 55 ° C and 65 ° C Program carried out. When using cold inlet water (12 ° C) the were Tablets according to the invention function perfectly, d. H. the active ingredient was in the KSG released.

In a further experiment, the dishwasher was operated with feed water on Was preheated to 25 ° C. Here, too, the tablets according to the invention remained during the HSG and ZSG largely unchanged and resolved as desired in the KSG, though the temperature at the beginning of the KSG had not dropped below 35 ° C.

Comparative example

Instead of the surfactant-containing, aqueous coating, a coating solution of the following composition was prepared:
PIPAAm: 8% (w / w)
Acetone: 36.8% (v / v)
Isopropanol: 55.2% (v / v)

The coating steps were analogous to the examples above.

In the rinsing experiments, these cores were cold (12 ° C) feed water functional, but they came off when using the preheated to 25 ° C Inlet water not until the end of the KSG and remained in the sieve of the rest Dishwasher.  

2.4. Another example of polymer blends

The following example shows how a resin-like, non-filming LCST material (polyvinyl methyl ether, Lutonal® M40 (BASF))) can be processed into functional IT switches by mixing with a film former (Eudragit® E 100) and particles:
Granules of the following composition were produced in the mixer:
11.7% Erkol® WX 48/20
46.7% Erkol® M 051140
5.8% Luviskol® VA 64 powder
30.0% Polytergent® SLF-1 8B-45 (100%)
5.8% water glass 2.4 over-dried

This granulate was pressed in a tablet press into pellets of 2 g each.

A 20% acetone solution of the following components was also prepared:
16.6% Lutonal® M (BASF)
16.6% Eudragit® E100 (Röhm)
66.6% Bentone® LT

The tablets described above were coated with this solution. After this As in Examples 2.1 and 2.2, a shellac coating or a paraffin Coating applied.

The tablets obtained were analogous to Examples 2.2. and 2.3. dishwashing carried out. It was shown that both the 55 ° C and 65 ° C programs in the The HSG and ZSG remained largely unchanged and dissolved in the KSG.

Claims (19)

1. Particulate composite material for the controlled release of an active substance or an active substance preparation, in which the active substance or the active substance preparation is coated with an LCST polymer, characterized in that the LCST polymer is mixed with an additive with which the film formation is improved or the LCST Temperature can be adjusted. 2. Composite material according to claim 1, characterized in that the LCST Polymer is selected from alkylated and / or hydroxyalkylated polysaccharides, Cellulose ethers, polyisopropylacrylamide, copolymers of polyisopropylacrylamide as well as blends of these substances. 3. Composite material according to one of claims 1 or 2, characterized in that that the LCST temperature is between 20 ° C and 100 ° C. 4. Composite material according to one of claims 1 to 3, characterized in that the additive is selected from one or more polymers, in particular Polyvinyl alcohol, polyacrylic acid and their derivatives. 5. Composite material according to one of claims 1 to 3, characterized in that the additive is selected from low molecular weight plasticizers, in particular Glycerin, polyethylene glycols liquid at room temperature, triacetin, trialkyl citrate, Alkylene glycols, such as ethylene glycol, propylene glycol and any mixtures of the above. 6. Composite material according to one of claims 1 to 3, characterized in that the additive is selected from nonionic and anionic surfactants, in particular C ₈ -C ₂₂ alkali alkoxylates and C ₈ -C ₂₂ alkyl sulfates. 7. Composite material according to one of claims 1 to 3, characterized in that the additive is selected from inorganic water-insoluble particles, preferably those with a particle size of 1 to 500 microns.   8. Composite material according to claim 7, characterized in that the inorganic particles are selected from TiO ₂ and natural or synthetic layered silicates, talc. 9. Composite material according to one of claims 1 to 8, characterized in that it is coated with another substance that is at a temperature above that lower separation temperature of the LCST substance is soluble or a melt point above this temperature or has a delayed solubility in water. 10. Use of the composite material according to one of claims 1 to 9 in pharmazeu tables and cosmetic products, preservatives, food, wax regulators, dyes, fragrances, pesticides and herbicides, adhesives as well as washing and cleaning agents. 11. Detergent or cleaning agent containing usual ingredients, characterized net that it is a particulate composite material for the controlled release of a Contains active ingredient or a preparation in which the active ingredient with an LCST Polymer in a mixture is coated with an additive with which the film formation improved or the LCST temperature can be set, the Composite material when going through one or more heat treatments in a liquid medium remains at least partially unchanged and after Cooling is released after the heat treatment. 12. washing or cleaning agent according to claim 11, characterized in that it in solid form, especially as powder, granulate, extrudate or as a shaped body is present. 13. washing or cleaning agent according to one of claims 11 or 12, characterized characterized in that the composite material is powdery or granular Dishwasher detergent is added. 14. washing or cleaning agent according to one of claims 11 or 12, characterized ge indicates that it is an automatic dishwashing detergent and that with the Additive-derived active ingredients are selected from Surfactants, especially rinse aid surfactants, fragrances, dyes, scale inhibitors, Corrosion inhibitors, bleaches, builders, cobuilders and any mixtures the previous one.   15. washing or cleaning agent according to claim 14, characterized in that the dishwashing detergent is in the form of a shaped body. 16. Washing or cleaning agent according to one of claims 11 or 12, characterized marked that it is a textile detergent and that with the additive LCST Substances made up of substances are selected from avivage components, Enzymes, fragrances, dyes, fluorescent agents, optical brighteners, Anti-shrink agents, anti-crease agents, antimicrobial agents, germicides, Fungicides, antioxidants, antistatic, ironing aids, phobing and Impregnating agents, UV absorbers and any mixtures of the above. 17. Washing or cleaning agent according to claim 16, characterized in that the textile detergent is in the form of a shaped body. 18. Detergent or cleaning agent according to one of claims 11 to 17, characterized characterized that those made up with the additive LCST substance Active substances are in particulate form and a particle size between 2 and 30 mm, preferably between 2, 5 and 25 mm and in particular between 3 and 20 mm exhibit. 19. Washing or cleaning agent according to one of claims 15 or 17, characterized characterized in that the composite material is embedded in the molded body.