WO2000078676A1 - Use of activated phyllosilicates in non-aqueous liquid detergents - Google Patents

Abstract

The invention relates to the use of phyllosilicates that have been activated by polar organic solvents such as for example methanol, ethanol, propylene carbonate, acetone, dipropylene glycol monomethyl ether, etc. The invention further relates to the use of mixtures of such activated phyllosilicates with activated polyamide derivatives to improve the rheological properties or to prevent the deposition of suspended particles in liquid detergents, liquid cleaning agents and other fluid to highly viscous media such as cosmetics, adhesives, paints, varnishes, enamel, waxes, varnish removers, oil drilling fluids, fats, inks, polyester resins, epoxy resins, sealing agents, etc. The invention relates to such activated phyllosilicates and to a method for their production. The invention also relates to liquid detergents and/or liquid cleaning agents that contain such activated phyllosilicates, and to a method of producing said detergents and/or agents.

Description

 Use of activated layered silicates in non-aqueous liquid detergents

The invention relates to the use of layered silicates, which by organic solvents such. B. methanol, ethanol, propylene carbonate, acetone etc. are activated in non-aqueous liquid detergents, non-aqueous liquid detergents and other fluid to highly viscous media such as cosmetics, adhesives, enamel, waxes, paint removers, oil drilling fluids, greases, inks, polyester resins, epoxy resins, sealants etc. The invention also relates to such activated layered silicates and a method for their production. In addition, the invention relates to non-aqueous liquid detergents and non-aqueous liquid detergents which contain these activated layered silicates, and to a process for the preparation of these compositions.

Layered silicates, also called leaf silicates or phyllosilicates, are of great interest for the stabilization of liquids, gels and pastes. Layered silicates can be used to adjust the theological properties of a viscous material. The most important theological behaviors of viscous materials are pseudoplastic, thixotropic, dilated and Newtonian flow. They result from the different dependence of the viscosity on the shear rate. In pseudoplastic flow, the viscosity decreases with increasing shear rate. This is also the case with thixotropic flow, here the viscosity increases again when the shear rate decreases, but this process is time-dependent and may only reach the values that corresponded to the same shear rates before shearing much later. Dilated flow denotes the increase in viscosity with increasing shear rate, while in Newtonian flow the viscosity remains constant regardless of the shear rate. Particularly pseudoplastic or thixotropic flow is often desired for viscous materials, since these are used for storage and transport, where low to low shear forces act, are more viscous and are less viscous and therefore easy to pour and process when used or processed where higher shear forces act.

The Rheology Handbook from Rheox International Inc., pages 14 to 22. describes the activation of the mostly organically modified layered silicate flakes as additives for solvent-based paints. The layered silicate platelets present in agglomerated platelet stacks are activated by wetting with solvent or binder and by mechanical energy, in that the agglomerates are first broken up, whereby an increase in viscosity already takes place. In a second step, chemical activator is added while shearing continues, which overcomes the mutual adhesion of the platelets. The small amounts of water present in the system to be activated enable the layered silicate to build up a theological structure via hydrogen bonds between the edges of the platelets in the third step. The swellability of many clay minerals with leaf structure is due to this water absorption between the silicon-oxygen layers. This is also the reason for the anisotropic compressibility of such layered silicates.

The amount of chemical activator that is required to activate the layered silicate platelets is in the rheology manual from Rheox International Inc., page 17, with 33% by weight for 95: 5 mixtures of methanol / water or propylene carbonate / water, 50% by weight for 95: 5 mixtures of ethanol / water, and 60% by weight for 95: 5 mixtures of acetone / water, based on the organically modified layered silicate. If the amount of chemical activator added is small, the platelets are insufficiently separated; if the amount is large, the binding forces between the platelets are disrupted by the activator. With the optimal addition of chemical activator, the best gelling of the layered silicate and maximum viscosity is achieved. Mixtures of 95% by weight of chemical activator and 5% by weight of water are used to build up the network structure formed via hydrogen bonds between the chemically activated platelets. Methanol, ethanol, propylene carbonate and acetone are mentioned as activators. Some easily dispersible layered silicates do not require a chemical activator in solvent-based systems, but water does. The layered silicates described by Rheox Inc. are intended to optimize the rheology of modern paints.

In the technical information "Adjusting the consistency and stabilizing liquid cleaning and care products with Optigel ^® and Tixogel ^® " from August 12, 1997 the Süd-Chemie discloses the incorporation of these theological smectite additives into products for various areas of application, but not for detergents. However, products for the kitchen, wet room and leather care are all watery. Only furniture care products, paint cleaners, car polishes and hand wash pastes for personal care are disclosed as non-aqueous products into which the theological additive can be incorporated. Optigel ^{® is incorporated} into aqueous, Tixogel ^® into non-aqueous solvent systems. The addition of chemical activators is described as necessary for the incorporation of certain Tixogel ^® types into solvents such as petrol or oils. In these solvents, as activators small polar molecules such as alcohols, acetone or propylene carbonate in amounts of 20 to 60 wt .-% can, based on Tixogel ^®, are used.

The technical information on the gelling agent Tixogel ^® UN from September 1996 from Süd-Chemie specifies weak polar to medium polar media for coating colors, printing inks, plastisols, organosols, mineral oils, putties and adhesives. Suitable solvents are aromatic and aliphatic hydrocarbons, turpentine, white spirit, hexane, heptane, mineral oil, paraffin and white spirit with a low aromatic content, which can also be mixed with polar media such as methanol, ethanol, propanol, butanol, methylene glycol, ethylene glycol acetate, etc. , the proportion of the polar component should not exceed 50% by weight. Tixogel UN® must be activated in low polar systems. In addition to shear, a polar activator is required. If there are already enough polar media in the batch, no activator is necessary. So z. B. for white spirit as activators and activator amounts 95: 5 mixture of methanol / water in amounts of 35% by weight, 95: 5 mixture of ethanol / water in amounts of 35% by weight, 95: 5 mixture of propylene carbonate / water in amounts of 100% by weight, based in each case on Tixogel ^® UN, recommended.

The organic modification of layered silicates, primarily with quaternary ammonium compounds, has been described in various patent applications.

European patent application EP-A-0 204 240 describes gel-forming organophilic phyllosilicates, the exchangeable cations of which have been wholly or partly replaced by certain quaternary ammonium salts. The pastes of these organo layered silicates have an increased storage stability and allow a higher initial concentration of organophilic silicate. These organophilic phyllosilicates are particularly suitable as additives with improved thixotropic properties and for reducing the Tendency to settle in systems based on organic solvents, e.g. B. for paints and anti-rust primers. Gel-shaped dispersions of 5 to 60% by weight of a gel-forming layered silicate in an organic solvent are also described.

German Offenlegungsschrift DE-A-34 34 983 describes gel-like dispersions of 5 to 60% by weight of a gel-forming layer silicate in an organic solvent, a gel-forming organophilic layer silicate being used as layer silicate, the exchangeable cations of which are at least partially replaced by organic cations and certain alkylimidazolinium ions are used as organic cations. In a preferred embodiment, the organic solvent is non-polar and contains 2 to 45% by weight of polar organic solvent. The organophilic phyllosilicate is prepared by reacting the preferably activated, i.e. H. layer silicate present here in Na form with alkylimidazolinium salt in aqueous solution at 50 to 100 ° C.

From German published patent application DE-A-31 49 131 it is known that organophilic phyllosilicates (organosmectites) can be produced from a layered silicate with exchangeable cations and aqueous solutions of an organic tetraalkylammonium salt (e.g. dimethydistearylammonium chloride or dimethybenzylstearylammonium chloride) of gels in organic solvents are suitable. To produce these layered silicates, the oxides of sodium, magnesium, silicon and aluminum are mixed in a certain molar ratio, the mixture is sheared and crystallized in an alkaline medium. After dilution and adjustment of the pH to 7 to 9, the quaternary ammonium compound is added. The organophilic phyllosilicates are generally pre-swollen in an organic solvent before they are used. Pastes are usually produced with about 10% by weight, so-called stock pastes, and stored at least 24 hours before use, so that the silicates can develop their full theological effectiveness. For this purpose, hydrocarbons such as toluene, xylene and gasoline serve as organic solvents, but also more polar solvents such as alcohols and ketones. Higher base pastes can be obtained from hydrocarbons with a higher molecular weight. When using non-polar solvents for the production of the master paste, it is often necessary to add small amounts (e.g. up to 40% by weight, based on the silicate used) of a polar solvent such as methanol.

The activation of layered silicates with polar organic solvents is disclosed in further patent applications. European patent application EP-A-0 798 267 from Rheox International Inc. describes organically modified silicates of the smectite type which contain one or more quaternary ammonium compounds which are derived from esters of organic acids. The organophilic clay material is said to impart theological properties to non-aqueous liquid systems. The smectite has a cation exchange capacity of 75 milliequivalents per 100 g of clay, the quaternary ammonium compound is present in sufficient quantity to cover at least 75% of the cation exchange capacity of the smectite. Furthermore, non-aqueous liquid systems are claimed which contain this organophilic layered silicate, preferably in amounts between 0.01 and 15% by weight. A distinction is made between organic solvent and polar activator. A 95: 5 mixture of methanol and water in the formulation of a paint is mentioned as the polar activator, the activator accounting for a proportion of 33.3% by weight, based on the layered silicate.

In addition to the maximum thickening of layered silicates, the structure activators are also used to improve the dispersion of the gelling agents in the organic solvent. In the US patents US 2,667,661, US 2,879,229 and US 3,294,683 are the polar organic solvents known as polar activators, dispersants or auxiliaries, such as acetone, methanol / water, ethanol / water, propylene carbonate, acetonylacetone, diacetone alcohol, dimethylformamide and γ-butyl lactone described as a dispersant for lubricants containing layered silicate, the layered silicate being treated with an essentially equal volume of polar material.

The methanol / water mixture is of particular importance in the gelation of layered silicates. US Pat. Nos. 4,450,095, 4,571,112, 4,695,402, 5,075,033 use between 29 and 34% by weight, based on the layer silicate, of a 95: 5 mixture of methanol and water for activating organophilic clay gelling agents.

In the US patents US 4,208,218, US 4,664,820 organically modified layered silicates are described which do not require a polar activator. Due to the low ignition temperatures of the polar organic solvents such as acetone or alcohols, these activators for paints, varnishes, waxes, enamel, epoxy resins, mastic coatings etc. were avoided. In addition, a separate process step for activating the layered silicates could be avoided. The so-called self-activating theological in the patents listed here Agents show significantly better theological properties than layered silicates. that are neither self-activated nor activated by polar means. The self-activated layered silicates are modified with a methylbenzyldialkyl or a dibenzyldialkylammonium compound. Without polar activators, the non-activated layered silicates, on the other hand, showed a worsened theological effect, lower viscosity and reduced control of the sinking of dispersed particulate ingredients, as well as an undesirably high storage stability, which has a negative effect on the originally desired theological properties with subsequent shear (e.g. casting) .

It was an object of the invention to provide activated layered silicates which, in liquid, fluid or highly viscous media, bring about improved theological properties, desired pseudoplastic or thixotropic flow or reduced tendency to sink the solid particles dispersed in the yellow phase.

Another object of the invention was to develop a method for activating such layered silicates.

A further object of the invention was to provide a liquid washing and / or cleaning agent containing phyllosilicates, which has improved theological properties, desired pseudoplastic or thixotropic flow and good physical storage stability of solids such as bleaching agents, bleach activators, enzymes, optical brighteners, inorganic and organic builders shows.

Another object of the invention was to develop a method for producing such a liquid washing and / or cleaning agent.

It has now been found that when organically modified layered silicates are activated with polar organic solvents or mixtures of these polar organic solvents with at most 30% by weight of water, based on the solvent-water mixture, when the structure activator is added in quantities of more than 35% by weight, advantageously of more than 50% by weight, preferably of more than 60% by weight, particularly preferably of more than 100% by weight, in particular of at least 120% by weight, based on that which may be organic modified layered silicate, a further increase in viscosity takes place when sheared and a maximum viscosity when sheared is achieved only in the case of amounts of structural activator which in some cases are well above 35% by weight or well above 50% by weight, preferably above 60% by weight, particularly preferably over 100% by weight, in particular at least 120% by weight, based on the optionally organically modified layered silicate. lie. This is an indication that only with these amounts of structure activator is the structure of the layered silicate fully formed, does the best gelation of the layered silicate take place and does not yet interfere with the binding forces between the platelets due to the amount of structure activator present.

The invention therefore relates in a first embodiment to the use of optionally organically modified layered silicates, which are activated by at least one structure activator, in liquid detergents, in liquid cleaning agents and other fluid to highly viscous media such as cosmetics, adhesives, paints. Varnishes, enamel, waxes, varnish removers, oil drilling fluids, greases, inks, polyester resins, epoxy resins, sealants etc., the proportion of structural activators being more than 35% by weight, based on the optionally organically modified layered silicates.

Layer silicates of natural and synthetic origin can be used as layer silicates. Layered silicates of this type are known, for example, from patent applications DE-B-23 34 899, EP-A-0 026 529 and DE-A-35 26405. Their usability is not limited to a special composition or structural formula. However, preference is given here to silicates with a three-layer structure, preferably dioctahedral smectites, in particular montmorillonites and bentonites, and / or trioctahedral smectites, in particular hectorites.

Suitable layered silicates, which belong to the group of water-swellable smectites, are e.g. B. those of the general formulas

(OH) ₄ Si ₈ _Al, (Mg _ϊ Al4-; c) O ₂ o montmorillonite, bentonite

(OH) ₄ Si ₈ _, Al (Al ₄ ^) O ₂ o beidellite

(OH) ₄ Si ₈ _ ₎ AlJ.Mg ₆ _ _r Li _z ) O ₂₀ hectorite

(OH) ₄ Si ₈ _ _v AL (Mg ₆ _ _{: r} Al _z ) θ2ö saponite, stevensite

with x = 0 to 4, y = 0 to 2, z = 0 to 6. In addition, small amounts of iron can be incorporated into the crystal lattice of the layered silicates according to the above formulas. Furthermore, due to their ion-exchanging properties, the layered silicates may contain hydrogen, alkali and / or alkaline earth ions, in particular Na ⁺ and Ca ²⁺ . The amount of water of hydration is usually in the range from 8 to 20% by weight and is from Source state or depending on the type of processing. Useful sheet silicates are known, for example, from US-A-3, 966,629, EP-A-0 026 529 and EP-A-0 028 432. Layer silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.

The layer silicates suitable for a system to be thickened should be selected depending on the polarity of the system to be thickened.

Preferred phyllosilicates are organically modified phyllosilicates, especially those which are anionically or cationically modified, in particular those modified by the incorporation of quaternary ammonium compounds.

The preferred specific weight of the layered silicates is 1.1 g / cm to 2.5 g / cm, in particular 1.5 g / cm ³ to 2.1 g / cm ³ , the preferred bulk density is 300 gl to 600 g / lb, in particular 350 g / £ to 500 g / £. In a further preferred embodiment, the layered silicates used have a sieve residue of 90 μm at most of 15% by weight and a moisture content of at most 3% by weight.

Structural activators generally improve the gel formation of the layered silicates. In many cases, such a chemical activator is helpful in order to separate the layer silicates normally present as platelets or platelet stacks and to achieve dispersion. Particularly suitable structural activators are low molecular weight polar substances, preferably polar organic solvents such as methanol, ethanol, propylene carbonate, acetone, acetonylacetone, diacetone alcohol, ethyl acetate, 2-propanol, dipropylene glycol monomethyl ether and dimethylformamide or mixtures thereof with at most 30% by weight of water, preferably at most 10% by weight, in particular 2 to 7% by weight, based on the mixture of the polar organic solvents with water. The structure activators are present in amounts of more than 35% by weight, based on the layered silicates which may be organically modified. Preferred amounts of structural activators are more than 50% by weight, preferably more than 60% by weight, based on the layered silicates which are optionally organically modified.

A preferred area of use for the activated sheet silicates is essentially non-aqueous liquid detergents and / or essentially non-aqueous liquid detergents. These agents contain at most 5% by weight of water and preferably solids such as bleaching agents, bleach activators, enzymes, optical brighteners, UV absorbers, inorganic and organic builders that are physically stabilized through the use of activated layered silicates. The non-aqueous liquid detergents and cleaning agents are explained in more detail below.

In a preferred embodiment, the proportion of structural activators, based on the optionally organically modified phyllosilicates, is over 50% by weight. advantageously above 60% by weight, particularly preferably above 100% by weight, in particular at least 120% by weight. In further special embodiments, 100: 0 to 70:30 mixtures of methanol / water in amounts of more than 35% by weight, in particular more than 50, are used as structure activators and as their amount, based in each case on the optionally organically modified sheet silicates % By weight of ethanol / water in quantities of more than 50% by weight, in particular more than 60% by weight, of acetone / water in quantities of more than 60% by weight, in particular more than 100% by weight. % and / or of propylene carbonate / water in amounts of more than 100% by weight, in particular at least 120% by weight, are preferred. In further special embodiments, 100: 0 to 70:30 mixtures of methanol / water, of ethanol / water, of acetone / water and / or of propylene carbonate / water in amounts of more than 100% by weight are used as structure activators. , in particular at least 120% by weight, in each case based on the optionally organically modified phyllosilicates, particularly preferred.

In a further embodiment, the invention relates to the use of any mixtures of phyllosilicates according to the invention with polyamide derivatives which are activated by at least one polyamide structure activator, as a theological additive in liquid washing or cleaning agents and other fluid to highly viscous media such as cosmetics, adhesives, paints, varnishes, Enamel, waxes, paint removers, oil drilling fluids, greases, inks, polyester resins, epoxy resins, sealants.

All natural and artificial polyamides can be used as polyamide derivatives, in particular polyamide ester compounds, as are disclosed in EP 528 363 and to which reference is explicitly made in this application. The preferred polyamide ester compounds result from the reaction product of polycarboxylic acids, a compound with active hydrogen, an alkoxylated compound with active hydrogen and a monocarboxylic acid. The polycarboxylic acids have between 5 and 36 carbon atoms per carboxylic acid group. Preferred polycarboxylic acids are those in which the number of carboxylic acid groups is two. Due to the production process, however, mixtures are often used which also include substances with only one carboxylic acid group and or three or more carboxylic acid groups. Such polycarboxylic acids are particularly preferred. which form dimeric and oligomeric units of natural fatty acids.

Compounds with active hydrogen follow the general formula: X _m -RY _n . wherein R represents a group with 2 to 12 carbon atoms, which may also contain non-reactive groups such as ether, alkoxy or halogen. X and Y are independent of one another and can be primary and secondary amino and hydroxyl groups. The variables m and n are at least 1 and the sum (m + n) is at least 2. The alkoxylated compound with active hydrogen is a polyether segment with at least 2 active hydrogen atoms. The active hydrogen alkoxylated compound must have an active amino or hydroxy group at each end of the polyether chain, and / or one end of the polyether chain is attached to a molecular fragment with at least one additional amino or hydroxy group and / or a linked polyether chain. This definition therefore includes not only polyalkylene glycols, polyalkylene diols or polyoxyethylenes with terminal amino groups, but also compounds of the following formula:

R ¹ : linear or branched alkyl chain with 6 to 30 carbon atoms

R: H, methyl or ethyl q, r: at least 1 and the sum (q + r) is from 2 to 50. s: 0 or 1 Alkoxylated substances with 3 or more active hydrogen atoms can also be present. An example of this is represented by the following formula:

R, R: independently of one another linear or branched alkyl chain with 6 to 30

Carbon atoms p: 1 to 20 x, y, z: independently of one another 0 or greater than 0, the sum of x + y + z from 1 to

50 is enough.

The monocarboxylic acid is used to stop the reaction from the polycarboxylic acids with the active hydrogen-carrying substances (alkoxylated and non-alkoxylated). The monocarboxylic acids have between 2 and 22 carbon atoms and can be both saturated and unsaturated. You can also carry other functional groups such as tert-amino, alkoxy, halo, keto, etc. However, those monocarboxylic acids which carry hydroxyl groups and / or are unsaturated are preferred.

The polyamide esters are produced using known techniques, as are also described in EP 528 363 A2. For example, the individual components can be reacted in a reaction vessel which is provided with a mechanical stirrer, a thermometer, a cooler and a nitrogen inlet. The reaction vessel can be heated, and the reaction mixture can be stirred under a nitrogen atmosphere. The end of the reaction is determined on the basis of the acid number (preferably less than 20). The polyamide ester is cooled and optionally ground. The polyamide derivatives Thixatrol TSR, Thixatrol SR 100, Thixatrol SR and in particular Thixatrol Plus, which are commercially available from Rheox, for example, can preferably be used. The polyamide derivatives suitable for preventing the settling of dispersed solids and for regulating the viscosity should be selected depending on the polarity of the fluid system.

Polyamide structure activators generally bring about an improved gelation of the polyamide derivatives. In many cases, such a chemical activator is helpful to build up a structured liquid matrix into which solid particles can be dispersed. Particularly suitable polyamide structure activators are aromatics and aliphatic alcohols which are liquid at 25 ° C., such as ethanol, propan-1-ol, propan-2-ol, butan-1-ol, butan-2-ol, isobutanol, isoamyl alcohol, cyclohexanol, glycol, Propane or butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether. Ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, diisopropylene glycol monomethyl or ethyl ether, methoxy or methoxy Butoxytriglycol, l-butoxyethoxy-2-propanol, butoxypropoxy propanol (BPP), 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures thereof. Preferred polyamide structure activators are liquid carboxylic acid and carbonic acid derivatives in which the ratio of oxygen to carbon per structure activator molecule is in the range from 3: 1 to 1: 3, preferably from 3: 2 to 2: 5 and in particular from 1: 1 to 1: 2 . Particularly preferred liquid carboxylic acid derivatives are the carboxylic acid esters and anhydrides, in particular mono- or polyacetylated compounds, such as triethylacetyl citrate, triethyl citrate,

Ethylene glycol diacetate and glycerol triacetate. Particularly preferred liquid carbonic acid derivatives are the linear and in particular cyclic carbonic acid esters, such as, for example, propylene carbonate and glycerol carbonate.

The polyamide structure activators can of course also in any mixtures with themselves or other organic solvents, such as ketones, aldehydes, ethers, polyethers, nitriles,. Aliphatics, halogenated hydrocarbons, amines, carboxylic acids and surfactants can be used. The polyamide structure activators are preferably used in amounts so that the weight ratio of polyamide structure activators to polyamide derivative is from 500: 1 to 1: 500, preferably from 50: 1 to 1:50, particularly preferably from 20: 1 to 1:20 and in particular from 10: 1 to 1:10.

Any mixtures of phyllosilicates according to the invention with polyamide derivatives which are activated by at least one polyamide structure activator are used, preference is given to a mixing ratio of 500: 1 to 1: 500, particularly preferably from 50: 1 to 1:50 and in particular from 20: 1 to 1:20 .

In a further embodiment, the invention relates to phyllosilicates which are activated by at least one structural activator, the phyllosilicates optionally being organically modified, the proportion of structural activators being more than 100% by weight, based on the optionally organically modified phyllosilicates. The layered silicates and structure activators and their respective preferred embodiments are described above.

In contrast to the first embodiment of the subject matter of the invention, the proportion of structural activators, based on the optionally organically modified layered silicates, is preferably at least 120% by weight. In further special embodiments, 100: 0 to 70:30 mixtures of methanol / water, of ethanol / water, of acetone / water and or of propylene carbonate / water, in particular in amounts of at least 120% by weight, are obtained as structure activators on the optionally organically modified phyllosilicates, preferred.

In a further embodiment, the invention relates to a process for the preparation of activated layered silicates, the proportion of structural activators being more than 35% by weight, based on the optionally organically modified layered silicates, and optionally in a solvent or different from the structural activators Solvent-mixed layered silicates are mixed with the structure activators.

The phyllosilicates described in the first embodiment of the subject matter of the invention are mixed with the structure activators likewise described there, optionally in the presence of one or more solvents which are different from the structure activators. This solvent comes first the task of causing or favoring the breaking up of the layer silicate platelet agglomerates which are generally initially present into individual platelets. In a preferred embodiment, these solvents or solvent mixtures, which differ from the structural activators, are surfactants. In a particularly preferred embodiment, nonionic surfactants and / or organic solvents and optionally anionic surfactants, cationic surfactants and or amphoteric surfactants are used. The solvents preferably have a water content which does not exceed 5% by weight.

Preferred anionic surfactants are surfactants of the sulfonate type, alk (en) yl sulfates. alkoxylated alk (en) yl sulfates, ester sulfonates and / or soaps are used.

Preferred surfactants of the sulfonate type are Cςr-C ₁₃ -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from C ₂ -C ₈ monoolefins with an end or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.

As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid half-esters of the Cιo-Cι ₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the Cs-C ₂₀ oxo alcohols and those half esters 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 prepared on a petrochemical basis. C ₁₂ -Ci ₆ alkyl sulfates and C ₁₂ -Ci ₅ alkyl sulfates, as well as C _M -C _J 5 alkyl sulfates and C ₄ -C ₆ alkyl sulfates are particularly preferred from the point of view of washing technology. In addition, 2,3-alkyl sulfates, which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched Cτ-C ₂ ι alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched Ccr-Cn alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 1 -C ₂ -fatty alcohols 1 to 4 EO are suitable. They are used in laundry detergents due to their high level Foam behavior is usually only used in relatively small amounts, for example in amounts of 0 to 5% by weight.

The esters of α-sulfofatty acids (ester sulfonates) are also suitable. e.g. the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Soaps are particularly suitable as further anionic surfactants. Particularly suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. B. coconut, palm kernel or tallow fatty acids, derived soap mixtures. Soap mixtures are preferred, of which 50 to 100 wt .-% of saturated _C12-C24 fatty acid soaps and set to O% to 50 wt .- oleic acid soap.

Another class of anionic surfactants is the class of ether carboxylic acids which is accessible by reacting fatty alcohol ethoxylates with sodium chloroacetate in the presence of basic catalysts. They have the general formula: RO- (CH ₂ - CHr-OV-CHr-COOH with R = C! -Cι ₈ and p = 0, \ to 20. Ethercarboxylic acids are water hardness-insensitive and have excellent surfactant properties. Production and application are described, for example, in soaps, oils, fats, waxes 101, 37 (1975); 115, 235 (1989) and surfactants Deterg. 25, 308 (1988).

Cationic surfactants contain the high molecular weight hydrophobic residue that causes surface activity when dissociated in aqueous solution in the cation. The most important representatives of the cationic surfactants are the quaternary ammonium compounds of the general formula: (R'R ² R ³ RV) X ^" . R stands for C ₈ -C ₈ alk (en) yl, R ² to R ⁴ independently of one another for C" H _{2π +} ι_ _p _ _x {Y (CO) R} _p (YH) _x , where n stands for integers without 0 and? And stands for integers or O. Y ¹ and Y ² independently of one another represent O, N or NH. R ⁵ denotes a C ₃ -C ₂₃ alk (en) yl chain. X is a counter ion, which is preferably selected from the group of halides, alkyl sulfates and alkyl carbonates. Cationic surfactants, in which the nitrogen group is also preferred, are particularly preferred two long acyl and two short alk (en) yl radicals is substituted.

Amphoteric or ampholytic surfactants have several functional groups which can ionize in aqueous solution and - depending on the conditions of the medium - give the compounds anionic or cationic character (cf. DIN 53900, July 1972). In the vicinity of the isoelectric point (around pH 4) the amphoteric surfactants form internal salts, which make them difficult or insoluble in water. Amphoteric surfactants are divided into ampholytes and betaines, the latter being in solution as zwitterions. Ampholytes are amphoteric electrolytes, ie compounds that have both acidic and basic hydrophilic groups and therefore behave acidic or basic depending on the condition. Betaines are compounds with the atomic grouping R ₃ N ⁺ -CH ₂ -COO ^~ that show typical properties of zwitterions.

The nonionic surfactants used are preferably alkoxylated and / or propoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) and or 1 to 10 moles of propylene oxide (PO) per mole of alcohol. Particularly preferred are Cg-Ci ₆ alcohol alkoxylates, advantageously ethoxylated and / or propoxylated Cιo-Ci ₅ alcohol alkoxylates, in particular Ci ₂ -C] ₄ alcohol alkoxylates, with a degree of ethoxylation between 2 and 10, preferably between 3 and 8, and / or a degree of propoxylation between 1 and 6, preferably between 1.5 and 5. The degrees of ethoxylation and propoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates and propoxylates have a narrow homolog distribution (narrow range ethoxylates / propoxylates, NRE / NRP). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.

In addition, as further nonionic surfactants, alkyl glycosides of the general formula RO (G) _x , z. B. as compounds, especially with anionic surfactants, are used in which R is a primary straight-chain or methyl-branched, in particular in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 C atoms and G is the symbol that 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 1.1 to 1.4.

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkylglycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters. preferably with 1 to

4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP-A-58/217 598 or which are preferably prepared by the process described in international patent application WO-A-90/13533. C 1-6 fatty acid methyl esters with an average of 3 to 15 EO, in particular with an average, are particularly preferred

5 to 12 EO.

Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

So-called gemini surfactants can be considered as further surfactants. These are generally understood to mean those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are generally separated from one another by a so-called “spacer”. This spacer is generally a carbon chain which should be long enough that the hydrophilic groups are sufficiently far apart that they can act independently of one another. Such surfactants are distinguished generally by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water, but in exceptional cases the term gemini surfactants means not only dimeric but also trimeric surfactants.

Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to German patent application DE-A-43 21 022 or dimer alcohol bis and trimeral alcohol tris sulfates and ether sulfates according to international patent application WO-A-96/23768. End group-capped dimeric and trimeric mixed ethers according to German patent application DE-A-195 13 391 are distinguished in particular by their bi- and multifunctionality. The end-capped surfactants mentioned have good wetting properties and are low-foaming, so that they are particularly suitable for use in machine washing or cleaning processes.

Gemini polyhydroxy fatty acid amides or poly polyhydroxy fatty acid amides, as described in international patent applications WO-A-95/1953, WO-A-95/19954 and WO95-A- / 19955, can also be used. The amounts of surfactants are from 0.1 to 90% by weight, preferably 10 to 80% by weight, in particular 20 to 70% by weight.

In a preferred embodiment, the proportion of structural activators is based on the optionally organically modified phyllosilicates. over 50% by weight. advantageously above 60% by weight, particularly preferably above 100% by weight, in particular at least 120% by weight. In further special embodiments, 100: 0 to 70:30 mixtures of methanol / water in amounts of more than 35% by weight, in particular more than 50, are used as structure activators and as their amount, based in each case on the optionally organically modified sheet silicates % By weight of ethanol / water in quantities of more than 50% by weight, in particular more than 60% by weight, of acetone / water in quantities of more than 60% by weight, in particular more than 100% by weight. % and / or of propylene carbonate / water in amounts of more than 100% by weight, in particular more than 120% by weight, are preferred. In further special embodiments, 100: 0 to 70:30 mixtures of methanol / water, of ethanol / water, of acetone / water and / or of propylene carbonate / water in amounts of more than 100% by weight, in particular, are used as structure activators at least 120% by weight, based in each case on the optionally organically modified sheet silicates, is particularly preferred.

The chemical activation of the layered silicates, especially organically modified layered silicates, is significantly favored by the low water contents generally present in the solvents and by the mixtures of polar organic solvents with a maximum of 30% by weight of water preferred as structure activators. This mode of action is described in the Rheox International Inc.'s Rheology Manual. In this case, the activator can introduce the water into the layered silicate system and ensure the hydrogen bond between the platelets of the layered silicate, which may be organically modified. The activator penetrates between the individual platelets of the organosilicate and pushes the platelets apart. The progressive separation of the platelets weakens the van der Waals forces that bind them together. This allows the shear forces to separate the plates completely. The water introduced by the chemical activator or by the solvent different from this migrates between the hydroxyl groups of adjacent layered silicate platelet edges and completes the hydrogen bonding and thus the gel structure. The layered silicate, structure activator and optionally solvent are mixed under shear, preferably in a highly dispersing device with strong shear action. The mixture is passed, for example, through at least one, rapidly rotating, perforated dispersion disk, as a result of which a fine dispersion of the layered silicates in the structure activator or structure activator-solvent mixture is formed. In a preferred embodiment, the components of the mixture are mixed in a stirred vessel, and the mixture is strongly sheared with one or more Zahnscheibenrührern, so-called dissolver, or with one or more rotor-stator stirrers (z. B. Ultra-Turrax ^®) and / or strongly sheared in a dispersing machine (e.g. a Cavitron) or a ball mill.

After activation by means of a structural activator with dispersion and shear, the so-called stock paste is obtained, the layered silicate activated and possibly present in a solvent, depending on the medium in which it is used as a rheological additive or structuring agent or to prevent further dispersed substances from sinking further process steps can be added.

In a further embodiment, the invention relates to a liquid detergent and / or liquid cleaning agent containing layered silicate, which was activated by the process described above.

This liquid detergent and / or liquid cleaning agent preferably contains activated layered silicates in quantities of 0.01 to 20% by weight, particularly preferably 0.1 to less than 10% by weight, in particular 0.5 to 5% by weight on the entire mean. In a particularly preferred embodiment, the mass ratio of structure activators to unactivated sheet silicates is more than 0.35: 1 to 1000: 1, preferably more than 0.5: 1 to 100: 1, preferably more than 0.6: 1 to 50 : 1, more preferably more than 1: 1 to 30: 1 and in particular 1.2: 1 to 20: 1.

In a preferred embodiment, the polyamide derivatives which have been activated by polyamide structure activators can contain amounts of up to 20% by weight, preferably up to 15% by weight and in particular up to 10% by weight, in each case based on the total agent. Preferred agents are essentially anhydrous, ie they contain at most 5% by weight, preferably at most 3% by weight, of free water. Further preferred agents contain organic solvents, wash-active substances and / or liquid bleach activators.

Preferred organic solvents here are

Dipropylene glycol monomethyl ether, polydiols, ethers, alcohols and / or esters, in amounts of 0 to 90% by weight, preferably 0.1 to 70% by weight, in particular 0.1 to 60% by weight.

Anionic surfactants, cationic surfactants can be used as wash-active substances. Amphoteric surfactants and or nonionic surfactants can be used, as described above.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below, bleach activators can be incorporated into the preparations. Preferred liquid bleach activators are triacetin, triethyl-O-acetyl citrate (TEOC), N-methyldiacetamide, isopropenyl acetate and / or N-acetylcaprolactam in amounts of 0.1 to 50% by weight, preferably 0.1 to 40% by weight, in particular 0.1 to 20 wt .-%.

Furthermore, the agents can bleach and optionally other detergent ingredients such. B. contain particulate bleach activators and enzymes.

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. Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, diperdodecanedioic acid or phthaloiminoperacids such as phthaliminopercaproic acid. Organic peracids, alkali perborates and / or alkali percarbonates are preferably used in amounts of 0.1 to 40% by weight, preferably 3 to 30% by weight, in particular 5 to 25% by weight.

Compounds which, under perhydrolysis conditions, give peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid can be used as bleach activators become. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multi-acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), are preferred. acylated triazine derivatives, in particular l, 5-diacetyl-2,4-dioxohexahydro-l, 3,5-triazine (DADHT), acylated glycolurils, in particular 1,3,4,6-tetraacetylglycoluril (TAGU). N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylieπe phenolsulfonates. in particular «-Nonanoyl- or Isononanoyloxybenzenesulfonat (n- or iso-NOBS). Carboxylic anhydrides, especially phthalic anhydride, isatoic anhydride and / or succinic anhydride, glycolide, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and the enol esters known from German patent applications DE 196 16 693 and DE 196 16 767 as well as acetylated sorbitol and mannitol or their mixtures described in European patent application EP 0 525 239 (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucone or triazolactol or triazole Triazole derivatives and / or particulate caprolactams and / or caprolactam derivatives, preferably N-acylated lactams, for example N-benzoylcaprolactam, 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 hydrophilically substituted acylacetals known from German patent application DE-A-196 16 769 and the acyl lactams described in German patent application DE-A-196 16 770 and international patent application WO-A-95/14075 are also preferably used. The combinations of conventional bleach activators known from German patent application DE-A-44 43 177 can also be used. Nitrile derivatives such as cyanopyridines, nitrile quats and / or cyanamide derivatives can also be used. Preferred bleach activators are sodium 4- (octanoyloxy) benzene sulfonate,

Undecenoyloxybenzenesulfonate (UDOBS), sodium dodecanoyloxybenzenesulfonate (DOBS), decanoyloxybenzoic acid (DOBA, OBC 10) and / or

Dodecanoyloxybenzenesulfonate (OBS 12). Bleach activators of this type are present in the customary quantitative range from 0.01 to 20% by weight, preferably in amounts from 0.1 to 15% by weight, in particular 1% by weight to 10% by weight, based on the total agent .

The bleach activator can be coated with coating substances in a known manner or, if appropriate using auxiliaries, in particular methyl celluloses and or carboxymethyl celluloses, may have been granulated or extruded / pelleted and, if desired, contain further additives, for example dye, the Dye has no coloring effect on the textiles to be washed. Such granules preferably contain more than 70% by weight, in particular 90 to 99% by weight, of bleach activator. A bleach activator is preferably used which forms peracetic acid under washing conditions.

In addition to the conventional bleach activators listed above or in their place, the sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes or transition metal complexes known from European patents EP-A-0446 982 and EP-A-0 453 003 can also be present as so-called bleaching catalysts. The transition metal compounds in question include, in particular, the manganese, iron, cobalt, ruthenium or molybdenum salen complexes known from German patent application DE-A-195 29 905 and their N known from German patent application DE-A-19620 267 - Analog compounds, the manganese, iron, cobalt known from German patent application DE-A-195 36 082. Ruthenium or molybdenum-carbonyl complexes, the manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes described in German patent application DE-A-196 05 688 with tripod ligands containing nitrogen, the cobalt, iron, copper and ruthenium amine complexes known from German patent application DE-A-196 20411, the manganese, copper and cobalt complexes described in German patent application DE 44 16438, which are described in European patent application EP -A-0 272 030 described cobalt complexes, the manganese complexes known from the European patent application EP-A-0 693 550, the manganese, iron, cobalt and from the European patent EP-A-0 392 592 Copper complexes and / or those described in European patent EP-A-0 443 651 or European patent applications EP-A-0458 397, EP-A-0458 398, EP-A-0 549 271, EP-A-0 549 272, EP-A-0 544 490 and EP-A-0 544 519 described manganese complexes. Combinations of bleach activators and transition metal bleach catalysts are known, for example, from German patent application DE-A-196 13 103 and international patent application WO-A-95/27775. Bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are used in customary amounts, preferably in an amount of up to 1% by weight, in particular 0.0025% by weight. % to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the total agent.

Enzymes include in particular those from the class of hydrolases, such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned in question. All of these hydrolases contribute to stain removal in laundry. like protein. greasy or starchy stains, and graying. By removing pilling and microfibrils, cellulases and other glycosyl hydrolases can help maintain color and increase the softness of the textile. Oxidoreductases can also be used for bleaching or for inhibiting color transfer.

Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, in particular, however, mixtures containing protease and / or lipase or mixtures with lipolytically active enzymes of particular interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. Cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since the different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 3% by weight.

Builders, cobuilders, soil repellents, alkaline salts and foam inhibitors, complexing agents, enzyme stabilizers, graying inhibitors, optical brighteners and UV absorbers can be included as further detergent ingredients.

As a builder, for example, finely crystalline, synthetic and bound water-containing zeolite can be used, preferably zeolite A and / or P. As zeolite P For example, zeolite MAP (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A. X and or P are also suitable. Of particular interest is also a cocrystallized sodium / potassium aluminum silicate made of zeolite A and zeolite X, which is commercially available as VEGOBOND AX * (commercial product from Condea) . The zeolite can preferably be used as a spray-dried powder. If the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₈ fatty alcohols with 2 to 5 Ethylene oxide groups. Cι ₂ -C] - fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water. In addition, phosphates can also be used as builder substances.

Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi _x θ _{2r +} ι ^• y rlj, where M is sodium or hydrogen, x is a number from 1.9 to 4 and v is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline phyllosilicates of the formula given are those in which M is sodium and x is 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ θ ₅ ^• v H ₂ O are preferred, whereby β-sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171 is.

The preferred builder substances also include amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delayed release and have secondary washing properties. The dissolution delay compared to conventional amorphous sodium silicates can be done in various ways, for example by surface treatment, compounding,

Compacting / ner seal or have been caused 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-rays, which are several times wide Have 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. Such so-called X-ray amorphous silicates. which also have a release delay compared to conventional water glasses are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

It is of course also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons. The sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable. Their content is generally not more than 25% by weight, preferably not more than 20% by weight, in each case based on the finished composition. In some cases, it has been shown that tripolyphosphates in particular, even in small amounts up to a maximum of 10% by weight, based on the finished agent, in combination with other builder substances lead to a synergistic improvement in the secondary washing ability. Preferred amounts of phosphates are less than 10% by weight, especially 0% by weight.

Organic builder substances which can be used as cobuilders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA) and their descendants, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

The acids themselves can also be used. In addition to their builder effect, the acids typically also have the property of an acidifying component and thus also serve to establish a lower and milder pH of detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular. Other acidifiers that can be used are known pH regulators such as sodium hydrogen carbonate and sodium hydrogen sulfate.

Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative 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 means of gel permeation chromatography (GPC), using a UV detector. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights of 2,000 to 10,000 g / mol, and particularly preferably 3,000 to 5,000 g / mol, can in turn be preferred from this group.

Suitable polymers can also comprise substances which consist partly or completely of units of vinyl alcohol or its derivatives.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol. The (co) polymeric polycarboxylates can be used either as an aqueous solution or preferably as a powder. The polymers can also use allylsulfonic acids to improve water solubility. as for example contained in EP-B-0 727 448 allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.

Also particularly preferred are biodegradable polymers composed of more than two different monomer units, for example those which, according to DE-A-43 00 772, are salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C -42 21 381 contain as monomers salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.

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

Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE-A-195 40 086 that in addition to cobuilder properties they also have a bleach-stabilizing effect.

Further suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0 280 223. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Both maltodextrins with a DE between 3 can be used and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2,000 to 30,000 g / mol. A preferred dextrin is described in British patent application 94 19 091.

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

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are further suitable cobuilders. Ethylene diamine N, N'-disuccinate (EDDS), the synthesis of which is described, for example, in US Pat. No. 3,158,615, is preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates, as described, for example, in US Pat. Nos. 4,524,009, 4,639,325, in European patent application EP-A-0 150 930 and in Japanese patent application JP-A-93/339 896 become. Suitable amounts for use in formulations containing zeolite and / or silicate are 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Such cobuilders are described, for example, in international patent application WO 95/20029.

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

Other suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these; in particular, alkali carbonate and amorphous alkali silicate, especially sodium silicate with a molar ratio Na ₂ O: SiO ₂ of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used.

Preferred agents contain alkaline salts, builder and or cobuilder substances, preferably sodium carbonate, zeolite, crystalline, layered sodium silicates and or trisodium citrate, in amounts of 0.5 to 70% by weight, preferably 0.5 to 50% by weight, in particular 0.5 to 30% by weight of anhydrous substance.

When used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of Cj ₈ -C ₂ fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes. The foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred. The salts of polyphosphonic acids are suitable as complexing agents or as stabilizers, in particular for per-compounds and enzymes which are sensitive to heavy metal ions. The sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate, diethylenetriaminepentamethylenephosphonate or ethylenediaminetetramethylenephosphonate are preferably used here in amounts of 0.1 to 5% by weight.

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed. For this purpose, water-soluble colloids of mostly organic nature are suitable, for example the water-soluble salts of (co) polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and other starch products than those mentioned above can also be used, e.g. B. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful. However, cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as

Methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, and also polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition.

The agents can optical brighteners such. B. derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. Are suitable for. B. Salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similar compounds, instead of the morpholino group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. In addition, brighteners of the substituted diphenylstyryl type may be present, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2- sulfostyryl) diphenyls. Mixtures of the aforementioned brighteners can also be used.

In addition, UV absorbers can also be used. These are compounds with a pronounced absorption capacity for ultraviolet radiation, which as light stabilizers (UV stabilizers) both contribute to the improvement of the light resistance of dyes and pigments and textile fibers and also protect the skin of the wearer of textile products from UV radiation penetrating through the textile. in the in general, the compounds effective by radiationless deactivation are derivatives of benzophenone, the substituents of which, such as hydroxyl and / or alkoxy groups, are usually in the 2- and / or 4-position. Substituted benzotriazoles are also suitable, furthermore phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position. Salicylates. organic nickel complexes as well as natural substances such as umbelliferone and the body's own urocanoic acid. In a preferred embodiment, the UV absorbers absorb UV-A and UV-B radiation and optionally UV-C radiation and radiate back with wavelengths of blue light, so that they additionally have the effect of an optical brightener. Preferred UV absorbers are also those in European patent applications EP-A-0 374 751, EP-A-0 659 877, EP-A-0 682 145, EP-A-0 728 749 and EP-A-0 825 188 disclosed UV absorbers such as triazine derivatives, e.g. B. hydroxyaryl-1,3,5-triazine, sulfonated 1,3,5-triazine, o-hydroxyphenylbenzotriazole and 2-aryl-2H-benzotriazole and bis (anilinotriazinylamino) stilbene disulfonic acid and their derivatives. Ultraviolet radiation-absorbing pigments such as titanium dioxide can also be used as UV absorbers.

Preferred liquid detergents are shear thinning, i.e. H. they show pseudoplastic or thixotropic flow as the theological property described at the beginning.

The agents can contain other common thickeners and anti-settling agents as well as viscosity regulators such as polyacrylates, polycarboxylic acids, polysaccharides and their derivatives, polyurethanes, polyvinylpyrrolidones, castor oil derivatives, polyamine derivatives such as quaternized and or ethoxylated hexamethylene diamines and any mixtures thereof. Preferred agents have a viscosity below 10,000 mPa ^· s when measured with a Brookfield viscometer at a temperature of 20 ° C and a shear rate of 50 min ^-1 .

The detergents can contain further typical detergent components such as perfumes and dyes, preference being given to those dyes which have no or negligible coloring effect on the textiles to be washed. Preferred quantitative ranges for the totality of the dyes used are below 1% by weight, preferably below 0.1% by weight, based on the composition. The agents can also white pigments such. B. contain TiO ₂ .

Preferred compositions have densities of 0.5 to 2.0 g / cm ³ , in particular 0.7 to 1.5 g / cm ³ . In a further embodiment, the invention relates to a process for the production of liquid detergents and or liquid cleaning agents containing activated layered silicate, in which

(a) layer silicates are activated in a first process step by at least one structure activator, the proportion of structure activators being at least 35% by weight, based on the optionally organically modified layer silicates, and optionally in a solvent or solvent mixture different from the structure activators dispersed layered silicates are mixed with the structural activators,

(b) the mixture obtained in process step (a) is mixed with further detergent components and optionally ground,

(c) optionally further substances, preferably substances that are sensitive to process step (b) or undesirable for process step (b), are added.

Step (a) has already been described in detail above as a method for activating the layered silicates. In step (a), the phyllosilicates are preferably dispersed in a portion of the solvent or solvent mixture different from the structural activators and, after activation, the dispersion is diluted by further addition of the solvent or solvent mixture different from the structural activators.

All of the substances listed above, such as surfactants, builders, cobuilders, bleaches, bleach activators, enzymes, solvents, soil repellents, alkaline salts, foam inhibitors, complexing agents, enzyme stabilizers, and graying inhibitors, can be used as further detergent ingredients and substances added in process steps (b) and (c) , optical brighteners, UV absorbers, thickeners, perfumes, dyes and other common detergent ingredients

Substances sensitive to process step (b) are, for example, enzymes that can be denatured, peracids, bleach activators and coated materials such as percarbonate that can be decomposed. In process step (b) undesirable substances are, for example, dyes, brighteners, fragrances, etc. B. give rise to increased effort in cleaning the system in the event of a product change. In a preferred embodiment, a grinding and / or comminution process is carried out in step (b), preferably in an annular gap ball mill or a roller mill. In a further preferred embodiment, step (a) and step (b), preferably steps (a) to (c), are carried out simultaneously as a one-pot process.

The particles obtained advantageously have a size of 5 to 200 μm, preferably 5 to 50 μm, in particular 10 to 30 μm, after the grinding and / or comminution process.

Agents containing layered silicates which have been activated by this process have improved rheological properties, desired pseudoplastic or thixotropic flow and reduced tendency to sink the solid particles dispersed in the gel phase.

Examples

example 1

The formulation for a non-aqueous liquid detergent is shown in Table 1.

Table 1: Recipe for a non-aqueous liquid detergent

Raw material weight content [%] nonionic surfactant ³ (Ci ₂ -Cj ₄ , 5 EO, 2 PO) 63.27

Perborate monohydrate 14.0

Tetraacetylethylenediamine 5.5

Trisodium citrate (anhydrous) 10.0

Soil repellent ^b 0.2 optical brightener ⁰ 0.1

Silicone anti-foaming agent 0.2

Perfume oil 1.5

Dye +

Layered silicate ⁰ 1.0

Propylene carbonate (structural activator) 1.2

Water for propylene carbonate 0.03

1-hydroxyethane-1, -diphosphonic acid disodium salt ^e 1.0

Protease 1.0

Amylase 1.0

^a Dehypon LS 52 R ex Henkel Chimica S. p. A. ^b Polyethylene terephthalate, Velvetol 251 C ^® ex Rhône-Poulenc ^c Tinopal CBS-X ^® ex Ciba-Geigy ^d Tixogel MP 250 ^® ex Süd-Chemie ^c Fostex 2 NZ ^® ex Henkel France SA Example 2

The recipe for another non-aqueous liquid detergent is shown in Table 2.

Table 2: Recipe for a non-aqueous liquid detergent

Raw material weight content [%] nonionic surfactant ³ (Ci ₂ -Cι ₄ , 5 EO, 2 PO) 65.1

Perborate monohydrate 12.0

Tetraacetylethylenediamine 4.0

Trisodium citrate (anhydrous) 9.3

Soil repellent ^b 0.2 optical brightener ⁰ 0.1

Silicone anti-foaming agent 0.2

Perfume oil 1.5

Dye +

Layered silicate ^d 1.5

Propylene carbonate (structural activator) 2.0

Water from raw materials 0.1

1-hydroxyethane-1, -diphosphonic acid -disodium salt ⁶ 1.0

Graying inhibitor 2.0

Protease 1.0

Amylase 1.0

^a Dehypon LS 52 R ^® ex Henkel Chimica S. p. A. ^b Polyethylene terephthalate, Velvetol 251 C ^® ex Rhône-Poulenc ^c Tinopal CBS-X ^® ex Ciba-Geigy ^d Tixogel MP 250 ^® ex Süd-Chemie ^e Fostex 2 NZ ^® ex Henkel France SA ^f Maleic acid-acrylic acid copolymer sodium salt (30:70), Sokalan CP 5 * powder, approx. 92%, molecular weight 70,000, ex BASF

Two steps are essential for the preparation of the recipes: the activation of the layered silicate and the mixing, optionally grinding process of the solids.

In the first process step, the layered silicate was mixed with part of the surfactant, so that an approximately 3% by weight suspension of layered silicate in surfactant was obtained. This suspension was brought to swell in a cavitron together with a structure activator by strong shear. Tixogel ^® MP 250 from Süd-Chemie AG, an organically modified smectite product, was used as the layer silicate. Propylene carbonate was used as the structural activator. The stock paste prepared in this way was then diluted with the remaining surfactant.

In a second process step, the base paste was mixed with other recipe components (perborate, citrate, perfume, phosphonate, foam inhibitor, optical brightener, soil repellent, dyes, etc.) and subjected to a grinding process in an annular gap mill to comminute the solid particles. Enzymes and bleach activator have not yet been processed in this step, as they would have been damaged by the grinding process. The particles obtained had sizes between 15 μm and 30 μm.

In a third step, enzymes and TAED were finally stirred in.

The agents obtained by this process were characterized by the stabilization by the activated layered silicate when stored for 4 weeks at 5 ° C, 20 ° C and 40 ° C excellent physical properties such as storage stability of the bleaching agents, bleach activators and enzymes and reduced tendency to decrease in the yellow-phase dispersed solid particles.

Claims

claims

1. Use of optionally organically modified layered silicates. which are activated by at least one structure activator, in liquid detergents, in liquid cleaning agents and other fluid to highly viscous media such as cosmetics, adhesives, paints, varnishes, enamels, waxes, varnish removers. Oil drilling fluids, greases, inks, polyester resins, epoxy resins, sealants etc. to improve the rheological properties of the medium or to prevent the sinking of solid particles dispersed in the medium. characterized in that the proportion of structural activators more than 35 wt .-%. based on the optionally organically modified phyllosilicates.

2. Use of layered silicates according to claim 1, characterized in that silicates with a three-layer structure, preferably dioctahedral smectites, in particular montmorillonites and bentonites, and / or trioctahedral smectites, in particular hectorites, are used as layered silicates.

3. Use of layered silicates according to claim 1 or 2, characterized in that the layered silicates are organically modified, especially by the incorporation of quaternary ammonium compounds.

4. Use of layered silicates according to one of claims 1 to 3, characterized in that the layered silicates used have a specific weight of

1.1 g / cm to 2.5 g / cm, preferably 1.5 g / cm to 2.1 g / cm.

5. Use of layered silicates according to one of claims 1 to 4, characterized in that the layered silicates used have a bulk density of 300 g / lb to 600 g / lb, preferably 350 g / lb to 500 g / lb.

6. Use of layered silicates according to one of claims 1 to 5, characterized in that the layered silicates used have a sieve residue to 90 microns of a maximum of 15 wt .-% and a moisture content of a maximum of 5 wt .-%.

7. Use of layered silicates according to one of claims 1 to 6, characterized in that the structure activators low molecular weight polar substances, preferably polar organic solvents such as methanol. Ethanol. Propylene carbonate, acetone, acetonylacetone, diacetone alcohol, ethyl acetate. 2-propanol, dipropylene glycol monomethyl ether and dimethylformamide or mixtures thereof with at most 30% by weight of water, preferably at most 10% by weight. in particular 2 to 7% by weight, based on the mixture of the polar organic solvents with water.

8. Use of layered silicates according to one of claims 1 to 7, characterized in that the proportion of structural activators more than 50 wt .-%, preferably more than 60 wt .-%, particularly preferably more than 100 wt .-%, in particular at least 120% by weight, based on the optionally organically modified phyllosilicates.

9. Use of layered silicates according to one of claims 1 to 7, characterized in that as structure activators and as their amount, based in each case on the optionally organically modified layered silicates, 100: 0 to 70:30 mixtures of methanol / water in amounts of more than 35% by weight, in particular more than 50% by weight, of ethanol / water in quantities of more than 50% by weight, in particular more than 60% by weight, of acetone / water in quantities of more than 60% by weight, in particular more than 100% by weight and / or propylene carbonate / water in amounts of more than 100% by weight, in particular at least 120% by weight.

10. Use of layered silicates according to claim 9, characterized in that as structure activators 100: 0 to 70:30 mixtures of methanol / water, of ethanol / water, of acetone / water and / or of propylene carbonate / water in amounts of more than 100% by weight, in particular at least 120% by weight, in each case based on the optionally organically modified phyllosilicates.

11. Use of layered silicates according to one of claims 1 to 10, characterized in that the activated layered silicates are used in essentially non-aqueous liquid detergents and / or essentially non-aqueous liquid detergents.

12. Use of layered silicates according to claim 11 for stabilizing solids such as bleaching agents, bleach activators, enzymes, optical brighteners, UN absorber, inorganic and organic builders in essentially non-aqueous, bleach-containing liquid detergents and or liquid cleaning agents.

13. Use of layered silicates according to one of claims 1 to 12, characterized in that the activated layered silicates in any mixtures with polyamide derivatives which are activated by at least one polyamide structure activator, preferably in a mixing ratio of 500: 1 to 1: 500, particularly preferably of 50: 1 to 1:50 and in particular from 20: 1 to 1:20.

14. Layered silicates which are activated by at least one structural activator, the layered silicates optionally being organically modified, characterized in that the proportion of structural activators is more than 100% by weight, based on the optionally organically modified layered silicates.

15. Layered silicates according to claim 14, characterized in that silicates with a three-layer structure, preferably dioctahedral smectites, in particular montmorillonites and bentonites, and or trioctahedral smectites, in particular hectorites, are used as layered silicates, the layered silicates preferably being organically modified, particularly by incorporating quaternary Ammonium compounds.

16. Layered silicates according to claim 14 or 15, characterized in that the layered silicates used have a specific weight of 1.1 g / cm ³ to 2.5 g / cm ³ , preferably 1.5 g / cm to 2.1 g / cm , a bulk density of 300 g / lb to 600 g / lb, preferably 350 g / lb to 500 g / lb, a sieve residue to 90 μm of a maximum of 15% by weight and a moisture content of a maximum of 5% by weight.

17. phyllosilicates according to one of claims 14 to 16, characterized in that the structure activators low molecular weight polar substances, preferably polar organic solvents such as methanol, ethanol, propylene carbonate, acetone, acetonyl acetone, diacetone alcohol, ethyl acetate, 2-propanol, dipropylene glycol monomethyl ether and dimethylformamide or whose mixtures are with at most 30% by weight of water, preferably at most 10% by weight, in particular 2 to 7% by weight, based on the mixture of the polar organic solvents with water.

18. Layered silicates according to one of claims 14 to 17, characterized in that the proportion of structural activators, based on the optionally organically modified layered silicates, is at least 120% by weight.

19. Layered silicates according to one of claims 14 to 18, characterized in that the layered silicates as structure activators 100: 0 to 70:30 mixtures of methanol / water, of ethanol / water, of acetone / water and / or of propylene carbonate / water , in particular in amounts of at least 120% by weight, based on the optionally organically modified phyllosilicates. contain.

20. A process for the preparation of activated layered silicates, characterized in that the proportion of structural activators is more than 35% by weight, based on the optionally organically modified layered silicates, with the layered silicates optionally dispersed in a solvent or solvent mixture different from the structural activators the structural activators are mixed under shear, preferably in a highly dispersing device with strong shear.

21. The method according to claim 20, characterized in that silicates with a three-layer structure, preferably dioctahedral smectites, in particular montmorillonites and bentonites, and / or trioctahedral smectites, in particular hectorites, are used as layer silicates, the layer silicates preferably being organically modified, particularly by incorporation quaternary ammonium compounds.

22. The method according to claim 20 or 21, characterized in that the layered silicates used have a specific weight of 1.1 g / cm ³ to 2.5 g / cm ³ , preferably 1.5 g / cm to 2.1 g / cm , a bulk density of 300 g / lb to 600 g / lb, preferably 350 g / lb to 500 g / lb, a sieve residue to 90 μm of a maximum of 15% by weight and a moisture content of a maximum of 5% by weight.

23. The method according to any one of claims 20 to 22, characterized in that the structure activators low molecular weight polar substances, preferably methanol, ethanol, propylene carbonate, acetone, acetonylacetone, diacetone alcohol, ethyl acetate, 2-propanol, dipropylene glycol monomethyl ether and dimethylformamide or mixtures thereof with at most 30 % By weight of water, preferably at most 10% by weight, in particular 2 to 7% by weight, based on the mixture of the polar organic solvents with water.

24. The method according to any one of claims 20 to 23, characterized in that the proportion of structural activators more than 50 wt .-%, preferably more than 60 wt .-%. particularly preferably more than 100% by weight, in particular at least 120% by weight. based on the optionally organically modified phyllosilicates.

25. The method according to any one of claims 20 to 24, characterized in that as structural activators and as their amount, based in each case on the optionally organically modified phyllosilicates, 100: 0 to 70:30 mixtures of methanol / water in amounts of more than 35% by weight, in particular more than 50% by weight, of ethanol / water in quantities of more than 50% by weight, in particular more than 60% by weight, of acetone / water in quantities of more than 60% by weight .-%, in particular more than 100% by weight and / or of propylene carbonate / water in amounts of more than 100% by weight, in particular at least 120% by weight.

26. The method according to claim 25, characterized in that as structural activators 100: 0 to 70:30 mixtures of methanol / water, of ethanol / water, of acetone / water and / or of propylene carbonate / water in amounts of more than 100 % By weight, in particular at least 120% by weight, in each case based on the optionally organically modified phyllosilicates.

27. The method according to any one of claims 20 to 26, characterized in that non-ionic surfactants, in particular ethoxylated and / or propoxylated alcohols, and / or organic solvents and, if appropriate, anionic surfactants, cationic surfactants and / or amphoteric surfactants as solvents or solvent mixtures different from the structure activators be used.

28. The method according to any one of claims 20 to 27, characterized in that as nonionic surfactants Cs-Ci _ö alcohol alkoxylates, preferably ethoxylated and / or propoxylated C ₁₀ -Ci ₅ alcohol alkoxylates, in particular Ci ₂ -Cj ₄ - alcohol alkoxylates, with a Degree of ethoxylation between 1 and 12, preferably between 2 and 10, in particular between 3 and 8, and / or a degree of propoxylation between 1 and 10, preferably between 1 and 6, in particular between 1.5 and 5.

29. The method according to any one of claims 20 to 28, characterized in that the water content of the solvent or solvent mixture different from the structure activators does not exceed 5% by weight.

30. The method according to any one of claims 20 to 29, characterized in that

(a) the components of the mixture are mixed in a stirred container and

(b) the mixture is strongly sheared with one or more toothed disk stirrers or with one or more rotor-stator stirrers and / or

(c) the mixture is strongly sheared in a dispersing machine or a ball mill.

31. Liquid detergent and / or liquid cleaning agent containing layered silicate, which was activated by a method according to any one of claims 20 to 30.

32. Agent according to claim 31, characterized in that the agent layered silicates in amounts of 0.01 to 20 wt .-%, preferably 0.1 wt .-% to less than 10 wt .-%, in particular 0.5 wt. -% to 5 wt .-%, based on the total agent contains.

33. Agent according to claim 31 or 32, characterized in that the mass ratio of structure activators to non-activated layered silicates more than 0.35: 1 to 1000: 1, preferably more than 0.5: 1 to 100: 1, preferably more than 0.6: 1 to 50: 1, particularly preferably more than 1: 1 to 30: 1 and in particular 1.2: 1 to 20: 1.

34. Agent according to one of claims 31 to 33, characterized in that the agents are essentially anhydrous and contain organic solvents, surfactants and / or liquid bleach activators.

35. Agent according to claim 34, characterized in that the agent organic solvents, preferably dipropylene glycol monomethyl ether, polydiols, ethers, alcohols and / or esters, in amounts of 0 to 90 wt .-%, preferably 0.1 to 70 wt .-% , in particular 0.1 to 60 wt .-% contain.

36. Agent according to claim 34 or 35. characterized in that the agent surfactants. preferably anionic surfactants. Cationic surfactants, amphoteric surfactants and / or nonionic surfactants, in particular ethoxylated and / or propoxylated alcohols, in amounts of 0.1 to 90 wt .-%, preferably 10 to 80 wt .-%, in particular 20 to 70 wt .-%.

37. Agent according to one of claims 34 to 36, characterized in that the agent liquid bleach activators, preferably triacetin, triethyl-O-acetyl citrate. Contain N-methyldiacetamide, isopropenylacetate and / or N-acetylcaprolactam in amounts of 0.1 to 50% by weight, preferably 0.1 to 40% by weight, in particular 0.1 to 20% by weight.

38. Agent according to one of claims 31 to 37, characterized in that the agent bleach and optionally further detergent components such. B. contain particulate bleach activators and enzymes.

39. Agent according to claim 38, characterized in that the agent bleach, preferably organic peracids, alkali perborates and / or alkali percarbonates, in amounts of 0.1 to 40 wt .-%, preferably 3 to 30 wt .-%, in particular 5 to Contain 25% by weight.

40. Agent according to claim 38 or 39, characterized in that the agent particulate bleach activators, preferably selected from tetraacetylethylenediamine, pentaacetylglucose, particulate caprolactams and / or caprolactam derivatives, sodium 4- (octanoyloxy) benzene sulfonate, undecenoyloxybenzene sulfonylsulfonate, 1,3,4,6-tetraacetylglycoluril and / or nitrile derivatives such as cyanopyridines, nitrile quats and / or cyanamide derivatives, in amounts of 0.01 to 20% by weight, preferably 0.1 to 15% by weight, in particular 1 to 10 % By weight.

41. Agent according to one of claims 38 to 40, characterized in that the agent alkaline salts, builder and / or cobuilder substances, preferably sodium carbonate, zeolite, crystalline, layered sodium silicates and / or trisodium citrate in amounts of 0.5 to 70 wt. -%, preferably 0.5 to 50 wt .-%, in particular 0.5 to 30 wt .-% of anhydrous substance.

42. Agent according to one of claims 31 to 41, characterized in that the agent polyamide derivatives, which have been activated by polyamide structure activators, in amounts up to 20 wt .-%, preferably up to 15 wt .-% and in particular up to 10 wt .-%, in each case based on the total composition.

43. Agent according to one of claims 31 to 42, characterized in that the agents are pseudoplastic.

44. A method for producing liquid detergents and / or liquid cleaning agents according to one of claims 31 to 42, characterized. that

(a) layer silicates are activated in a first process step according to a process according to one of claims 20 to 30,

(b) the mixture obtained in process step (a) is mixed with further detergent constituents and optionally ground,

(c) optionally further substances, preferably substances that are sensitive to process step (b) or undesirable for process step (b), are added.

45. The method according to claim 44, characterized in that step (a) and step (b), preferably steps (a) to (c), are carried out simultaneously as a one-pot process.

46. The method according to claim 44 or 45, characterized in that the layered silicates in step (a) are dispersed in a part of the solvent or solvent mixture different from the structure activators and the dispersion after activation by further addition of the solvent or solvent mixture different from the structure activators diluted.

47. The method according to any one of claims 44 to 46, characterized in that in step (b) a grinding and / or comminution process, preferably in an annular gap ball mill or a roller mill, and the particles obtained after the grinding and / or comminution process preferably a size from 5 to 200 μm, particularly preferably 5 to 50 μm, in particular 10 to 30 μm.