CA2311994A1 - Use of activated layer silicates in nonaqueous liquid laundry detergents and other fluid to high viscosity media - Google Patents

Abstract

The invention relates to the use of layer silicates activated by polar organic solvents, for example methanol, ethanol, propylene carbonate, acetone, dipropylene glycol monomethyl ether, etc., and to the use of mixtures of activated layer silicates with activated polyamide derivatives for improving the rheological properties or preventing the sedimentation of suspended particles in liquid laundry detergents, in liquid dishwashing detergents and other fluid to high-viscosity media, such as cosmetics, adhesives, paints, lacquers, enamels, waxes, paint strippers, oil drilling fluids, fats, inks, polyester resins, epoxy resins, sealants, etc. Activated layer silicates such as these and a process for their production are described. In particular, liquid laundry detergents and/or liquid dishwashing detergents containing the activated layer silicates and a process for producing the detergents are described.

Description

USE OF ACTIVATED LAYER SILICATES IN NONAQUEOUS LIQUID
LAUNDRY DETERGENTS AND OTHER FLUID TO HIGH-VISCOSITY
MEDIA
Field of the Invention This invention relates to the use of layer silicates activated by organic solvents, for example methanol, ethanol, propylene carbonate, acetone, etc., in nonaqueous liquid laundry detergents, nonaqueous liquid dishwashing detergents and other fluid to high-viscosity media, such as cosmetics, adhesives, enamels, waxes, paint strippers, oil drilling fluids, fats, inks, polyester resins, epoxy resins, sealants, etc. The invention also relates to such activated layer silicates and to a process for their production. In addition, the invention relates to nonaqueous liquid laundry detergents and nonaqueous liquid dishwashing detergents which contain these activated layer silicates and to a process for the production of these detergents.
Background of the Invention Layer silicates, also known as sheet silicates or phyllosilicates, are of considerable interest for stabilizing liquids, gels and pastes. The rheological properties of a viscous material can be adjusted by layer silicates. The most important modes of rheological behavior of viscous materials are pseudoplastic, thixotropic, dilatant and Newtonian flow. They derive from the different extents to which viscosity is determined by the shear rate. In the case of pseudoplastic flow, viscosity decreases with increasing shear rate. This is also the case with thixotropic flow where, although viscosity increases again after a reduction in the shear rate, this process is time-dependent and, in some cases, only returns much later to the values which corresponded to the same shear rates before shearing.

Dilatant flow designates the increase in viscosity with increasing shear rate whereas, with Newtonian flow, viscosity remains constant irrespective of the shear rate. Pseudoplastic or thixotropic flow in particular is often desirable for viscous materials because such materials have relatively high viscosities during storage and transportation, where low to very low shear forces are active, but become less viscous, i.e. are easy to pour and process, during use or processing where relatively powerful shear forces are active.
The rheology handbook of Rheox International Inc., pages 14 to 22, describes the activation of the generally organically modified layer silicate platelets as additives for solvent-containing paints. The layer silicate platelets present in agglomerated stacks are activated by wetting with solvent or binder and by mechanical energy. i.e in a first step, the agglomerates are broken up which in itself produces an increase in viscosity. In a second step, chemical activator is added with continued shearing, overcoming the mutual adhesion of the platelets. Small quantities of water present in the system to be activated enable the layer silicate to build up a rheological structure in a third step via hydrogen bridges between the edges of the platelets. The swellability of many clay minerals with a sheet structure is attributable to this absorption of water between the silicon/oxygen layers which also accounts for the anisotropic compressibility of such layer silicates.
According to the rheology handbook of Rheox International Inc., page 17, the quantity of chemical activator required for activating the layer silicate platelets is said to be 33% by weight for 95:5 mixtures of methanol and water or propylene carbonate and water, 50% by weight for 95:5 mixtures of ethanol and water and 60% by weight for 95:5 mixtures of acetone and water, based on the organically modified layer silicate. If the chemical activator is added in smaller quantities, the platelets are not sufficiently separated. If the chemical activator is added in larger quantities, the binding forces between the platelets are destroyed by the activator. When the chemical activator is added in the optimal quantity, the best gelation of the layer silicate and maximal viscosity are achieved.
Mixtures of 95% by weight of chemical activator and 5% by weight of water are used to build up the net-like structure formed via hydrogen bridges between the chemically activated platelets. Methanol, ethanol, propylene carbonate and acetone are mentioned as activators. Some readily dispersible layer silicates do not need any chemical activator in solvent-containing systems, but do require water. The layer silicates described by Rheox Inc. are intended for opimizing the rheology of modern paints.
Slid-Chemie's technical pamphlets "Konsistenzeinstellung and Stabilisierung von fliisssigen Putz- and Pflegemittlen mit Optigel~
and Tixogel~" of 12th August 1997 disclose the incorporation of these rheological smectite additives in products for various applications, but not for detergents. However, products for kitchens, bathrooms and leather care are all water-based. Only furniture care preparations, paint cleaners, car polishes and handwashing pastes for body care are disclosed as nonaqueous products in which the rheological additive can be incorporated. Optigel~ in incorporated in water-based solvent systems while Tixogel~ is incorporated in nonaqueous solvent systems. The addition of chemical activators is described as necessary for the incorporation of certain Tixogel~ types in solvents, such as spirits or oils.
Small polar molecules, such as alcohols, acetone or propylene carbonate, may be used as activators in these solvents in quantities of 20 to 60% by weight, based on Tixogel~.
Sud-Chemie's technical information pamphlet on the gelling agent Tixogel~ UN of September, 1996 mentions weakly polar to medium-polar media for paints, printing inks, plastisols, organosols, mineral oils, cements and adhesives as applications. Suitable solvents are said to be aromatic and aliphatic hydrocarbons, turpentine, white spirit, hexane, heptane, mineral oil, paraffin and low-aromatic thinner, which may even be present in admixture with polar media, such as methanol, ethanol, propanol, butanol, methylene glycol, ethylene glycol acetate, etc., although the per-centage content of the polar component should not exceed 50% by weight.
In low-polar systems, Tixogel UN~ has to be activated. Besides shearing, a polar activator has to be used for this purpose. If sufficient polar media are already present in the mixture, no activator is necessary. Activators recommended for white spirit for example include a 95:5 mixture of methanol and water in quantities of 35% by weight, a 95:5 mixture of ethanol and water in quantities of 35% by weight, a 95:5 mixture of propylene carbonate and water in quantities of 100% by weight, based on Tixogel~ UN.
The organic modification of layer silicates, primarily with quaternary ammonium compounds, is described in various patent applications.
European patent application EP-A-0 204 240 describes gel-forming organophilic layer silicates of which the exchangeable cations are completely or partly replaced by certain quaternary ammonium salts. The pastes of these organic layer silicates have high stability in storage and accommodate a relatively high initial concentration of organophilic silicate.
These organophilic layer silicates are particularly suitable as additives with improved thixotropicizing properties and for reducing the tendency towards sedimentation in systems based on organic solvents, for example for paints and rustproofing primers. In addition, gel-form dispersions of 5 to 60% by weight of a gel-forming layer silicate in an organic solvent are described.
DE-A-34 34 983 describes gel-form dispersions of 5 to 60% by weight of a gel-forming layer silicate in an organic solvent, the layer silicate used being a gel-forming organophilic layer silicate, of which the exchangeable cations are at least partly replaced by organic cations and certain alkyl imidazolinium ions being used as the organic cations. In one preferred embodiment, the organic solvent is nonpolar and contains 2 to 45% by weight of polar organic solvent. The organophilic layer silicate is produced by a reaction of the preferably activated layer silicate, i.e. the layer silicate present here in the Na form, with alkyl imidazolinium salt in aqueous solution at 50 to 100°C.
It is known from DE-A-31 49 131 that organophilic layer silicates (organosmectites) suitable for the production of gels in organic solvents can be produced from a layer silicate containing exchangeable cations and aqueous solutions of an organic tetraalkyl ammonium salt (for example dimethyl distearyl ammonium chloride or dimethyl benzyl stearyl ammonium chloride). To produce these layer silicates, the oxides of sodium, magnesium, silicon and aluminium are mixed in a certain molar ratio, the mixture is sheared and then crystallized in alkaline medium. The quaternary ammonium compound is added after dilution and adjustment of the pH to a value of 7 to 9. The organophilic layer silicates are generally preswollen in an organic solvent before use. 10% by weight pastes, so-called stock pastes, are normally prepared and stored for at least 24 hours before use so that the silicates are able to develop their full rheological activity. The organic solvents used for this purpose are hydrocarbons, such as toluene, xylene and spirit, and also more polar solvents, such as alcohols and ketones. Relatively firm stock pastes can be obtained from hydrocarbons of relatively high molecular weight. Where nonpolar solvents are used for preparing the stock paste, small quantities (for example up to 40% by weight, based on the silicate used) of a polar solvent, such as methanol, often have to be used.
The activation of layer silicates with polar organic solvents is disclosed in other patent applications.
European patent application EP-A-0 798 267 of Rheox International Inc. describes organically modified silicates of the smectite type which contain one or more quaternary ammonium compounds derived from esters of organic acids. The organophilic clay material is said to impart rheological properties to nonaqueous liquid systems. The smectite has a cation exchange capacity of 75 milliequivalents per 100 g of clay; the quaternary ammonium compound is present in a sufficient quantity to cover at least 75% of the cation exchange capacity of the smectite. The European patent application in question also claims nonaqueous liquid systems which contain this organophilic layer silicate, preferably in quantities of 0.01 to 15% by weight. A distinction is made between organic solvent and polar activator. A 95:5 mixture of methanol and water is mentioned as polar activator for a paint formulation, the activator making up 33.3% by weight, based on the layer silicate.
The structure activators are used not only for the maximal thickening of layer silicates, but also for improving the dispersion of the gelling agents in the organic solvent. In US Patents 2,667,661, 2,879,229 and 3,294,683, the polar organic solvents known as polar activators, dispersants or dispersion aids, such as acetone, methanol/water, ethanol/
water, propylene carbonate, acetonyl acetone, diacetone alcohol, dimethyl formamide and y-butyl lactone, are described as dispersants for lubricants containing layer silicate, the layer silicate being treated with a substantially equal volume of polar material.
Particular significance is attributed in the gelation of layer silicates to the mixture of methanol and water. According to US patents 4,450,095, 4,571,112, 4,695,402 and 5,075,033, between 29 and 34% by weight, based on the layer silicate, of a 95:5 mixture of methanol and water is used for activating organophilic clay gelling agents.
US patents 4,208,218 and 4,664,820 describe organically modified layer silicates which do not require the addition of a polar activator. In view of the low ignition temperatures of the polar organic solvents, such as acetone or alcohols, it was preferred not to use these activators for paints, lacquers, waxes, enamels, epoxy resins, mastix coatings, etc. In addition, a separate process step for activating the layer silicates could be avoided in this way. The so-called self-activating rheological agents mentioned in the US patents in question show distinctly better rheological properties than layer silicates which are neither self-activated nor activated by polar solvents. The self-activated layer silicates are modified with a methyl benzyl dialkyl compound or a dibenzyl dialkyl ammonium compound. By contrast, without polar activators, the non-activated layer silicates showed inferior rheological activity, lower viscosities and reduced control of the sedimentation of dispersed particulate ingredients and, in addition, undesirably high stability in storage which adversely affects the rheological properties originally desired in the event of subsequent shearing (for example pouring).
Now, the problem addressed by the present invention was to provide activated layer silicates which, in liquid, fluid or high-viscosity media, would produce improved rheological properties, desirable pseudoplastic or thixotropic flow and a reduced tendency towards sedimentation of the solid particles dispersed in the gel phase.
Another problem addressed by the invention was to provide a process for activating layer silicates such as these.
Another problem addressed by the invention was to provide a liquid laundry and/or dishwashing detergent containing layer silicates which would show improved rheological properties, desirable pseudoplastic or thixotropic flow and high physical storage stability of solids, such as bleaching agents, bleach activators, enzymes, optical brighteners, inorganic and organic builders.
Yet another problem addressed by the invention was to provide a process for producing the liquid laundry and/or dishwashing detergent.
Description of the Invention It has now been found that, where optionally organically modified layer 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, addition of the structure activator in quantities of more than 35% by weight, advantageously more than 50% by weight, preferably more than 60% by weight, more preferably more than 100% by weight and most preferably at least 120% by weight, based on the optionally organically modified layer silicate, produces a further increase in viscosity on shearing and enables a maximal viscosity to be developed on shearing with quantities of structure activator which in some cases are well above 35% by weight or well above 50% by weight, preferably above 60%
by weight, more preferably above 100% by weight and most preferably at least 120% by weight, based on the optionally organically modified layer silicate. This an indication of the fact that it is only with such quantities of structure activator that the structure of the layer silicate is fully developed, the best gelation of the layer silicate is achieved and the binding forces between the platelets are still not destroyed by the quantity of structure activator present.
In a first embodiment, therefore, the present invention relates to the use of optionally organically modified layer silicates activated by at least one structure activator in liquid laundry detergents, in liquid dishwashing detergents and other fluid to high-viscosity media, such as cosmetics, adhesives, paints, lacquers, enamels, waxes, paint strippers, oil drilling fluids, fats, inks, polyester resins, epoxy resins, sealants etc., the percentage content of structure activators being more than 35% by weight, based on the optionally organically modified layer silicates.
Layer silicates of natural and synthetic origin may be used as the layer silicates. Layer silicates such as these are known, for example, from patent applications DE-B-23 34 899, EP-A-0 026 529 and DE-A-35 26 405.
Their suitability is not confined to a particular composition or structural formula. However, silicates with a three layer structure, preferably dioctahedral smectites, more particularly montmorillonites and bentonites, _g_ and/or trioctahedral smectites, more particularly hectorites, are preferably used.
Suitable layer silicates which belong to the group of water-swellable smectites are, for example, those corresponding to the following general formulae:
(OH)4Si8_yAly(MgXAl4_x)02o montmorillonite, bentonite (OH)4Si$_yAly(AI4+y)02o beidellite (OH)4Si$_yAly(Mgs_ZLiZ)02o hectorite (OH)4Si$_yAly(Mg6_ZAIZ)02o saponite, stevensite where x = 0 to 4, y = 0 to 2 and z = 0 to 6. Small quantities of iron may additionally be incorporated in the crystal lattice of the layer silicates corresponding to the above-formulae. In addition, the layer silicates may contain hydrogen, alkali metal and/or alkaline earth metal ions, more particularly Na+ and Ca2+, by virtue of their ion-exchanging properties. The quantity of water of hydration is generally in the range from 8 to 20% by weight and is dependent upon the degree of swelling and upon the treatment method. Useful layer silicates are known, for example, from US-A-3,966,629, EP-A- 0 026 529 and EP-A-0 028 432. Layer silicates which have been substantially freed from calcium ions and strongly coloring iron ions by an alkali treatment are preferably used.
Suitable layer silicates for a system to thickened should be selected according to the polarity of the system to be thickened.
Preferred layer silicates are organically modified layer silicates, particularly anionically or cationically modified layer silicates and especially those which have been modified by the incorporation of quaternary ammonium compounds.
The preferred specific gravity of the layer silicates is 1.1 g/cm3 to 2.5 g/cm3 and, more particularly, 1.5 g/cm3 to 2.1 g/cm~ while the preferred bulk density is 300 g/I to 600 g/I and, more particularly, 350 g/I to 500 g/I. In another preferred embodiment, the layer silicates used have a sieve residue to 90 pm of at most 15% by weight and a moisture content of at most 3% by weight.
Structure activators generally improve the gelation of the layer silicates. In many cases, a chemical activator such as this is helpful in separating the layer silicates normally present as platelets or stacks of platelets and in achieving dispersion. Suitable structure activators are, above all, low molecular weight polar substances, preferably polar organic solvents, such as methanol, ethanol, propylene carbonate, acetone, acetonile acetone, diacetone alcohol, ethyl acetate, 2-propanol, dipropylene glycol monomethyl ether and dimethyl formamide or mixtures thereof with at most 30% by weight of water, preferably at most 10% by weight and more preferably 2 to 7% by weight, based on the mixture of the polar organic solvent with water. The structure activators are present in quantities of more than 35% by weight, based on the optionally organically modified layer silicates. Preferred quantities of structure activators are more than 50% by weight and preferably more than 60% by weight, based on the optionally organically modified layer silicates.
A preferred application for the activated layer silicates is in substantially nonaqueous liquid laundry detergents and/or substantially nonaqueous liquid dishwashing detergents. These detergents 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, which are physically stabilized by the use of activated layer silicates. These nonaqueous liquid laundry and dishwash-ing detergents are described in more detail hereinafter.
In one preferred embodiment, the percentage content of structure activators, based on the optionally organically modified layer silicates, is more than 50% by weight, advantageously more than 60% by weight, preferably more than 100% by weight and more preferably at least 120%
by weight. In other special embodiments, preferred structure activators and percentage contents, based on the optionally organically modified layer silicates, are 100:0 to 70:30 mixtures of methanol and water in quantities of more than 35% by weight and, more particularly, more than 50% by weight, ethanol and water in quantities of more than 50% by weight and, more particularly, more than 60% by weight, acetone and water in quantities of more than 60% by weight and, more particularly, more than 100% by weight and/or propylene carbonate/water in quantities of more than 100%
by weight and, more particularly, at least 120% by weight. In other special embodiments, particularly preferred structure activators are 100:0 to 70:30 mixtures of methanol and water, ethanol and water, acetone and water and/or propylene carbonate and water in quantities of more than 100% by weight and, more particularly, at least 120% by weight, based on the optionally organically modified layer silicates.
In another embodiment, the present invention relates to the use of mixtures of layer silicates according to the invention with polyamide derivatives activated by at least one polyamide structure activator as a rheological additive in liquid laundry or dishwashing detergents and other fluid to high-viscosity media, such as cosmetics, adhesives, paints, lacquers, enamels, waxes, paint strippers, oil drilling fluids, fats, inks, poly-ester resins, epoxy resins and sealants. The polyamide derivatives used may be any natural and synthetic polyamides, more particularly the poly-amide ester compounds disclosed in EP 528 363 to which reference is expressly made in this specification.
The preferred polyamide ester compounds emanate from the reaction product of polycarboxylic acids, a compound containing active hydrogen, an alkoxylated compound containing active hydrogen and a monocarboxylic acid. The polycarboxylic acids contain between 5 and 36 carbon atoms per carboxylic acid group. Polycarboxylic acids where the number of carboxylic acid groups is two are preferred. Due to the produc-tion process, however, mixtures which also contain substances with only one carboxylic acid group and/or three or more carboxylic acid groups are often used. Polycarboxylic acids which form dimeric and oligomeric units of natural fatty acids are particularly preferred.
Compounds containing active hydrogen correspond to the following general formula: Xm-R-Y", in which R is a group with 2 to 12 carbon atoms which may also contain non-reactive groups, such as ether, alkoxy or halogen. X and Y independently of one another represent 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 containing active hydrogen is a polyether segment containing at least two active hydrogen atoms. The alkoxylated compound containing active hydrogen must have an active amino group or hydroxy group at each end of the polyether chain and/or one end of the polymer chain is attached to a molecule fragment by at least one additional amino or hydroxy group and/or a polyether chain attached thereto.
Accordingly, this definition covers not only polyalkylene glycols, poly-alkylene diols or polyoxyethylenes with terminal amino groups, but also compounds corresponding to the following formula:
(CH2CHR0)q-H

R-.Cs--N
(CH2CHR0 )r-H
in which R' is a linear or branched alkyl chain containing 6 to 30 carbon atoms, R represents H, methyl or ethyl, q and r have a value of at least 1 and the sum (q+r) is a number of 2 to 50, s=Oor1.
Alkoxylated substances containing 3 or more active hydrogen atoms may also be present. One example of such a substance is represented by the following formula:
~(CHZC~HO}X-H
R-N-(CH2~-N
(CH2CR~H0}y-H
(CH2C~H0)Z-H
in which R3 and R2 independently of one another represent a linear or branched alkyl chain containing 6 to 30 carbon atoms, p=1 to20and x,y and z independently of one another have a value of 0 or greater than 0, the sum of x+y+z being a number to 1 to 50.
The monocarboxylic acid is used to terminate the reaction of the polycarboxylic acids with the substances containing active hydrogen (alkoxylated and nonalkoxylated). The monocarboxylic acids have between 2 and 22 carbon atoms and may be both saturated and unsaturated. In addition, they may contain other functional groups such as, for example, tert.amino, alkoxy, halo, keto, etc. However, monocarboxylic acids which contain hydroxyl groups and/or are unsaturated are preferred.
The polyamide esters are produced by known methods, as also described in EP 528 363 A2. For example, the individual components may be reacted in a reaction vessel equipped with a mechanical stirrer, a thermometer, a cooler and a nitrogen inlet. The reaction vessel may be heated and the reaction mixture may be stirred in a nitrogen atmosphere.
The end of the reaction is determined from the acid value (preferably below 20). The polyamide ester is cooled and optionally ground. The polyamide derivatives Thixatrol TSR, Thixatrol SR 100, Thixatrol SR and in particular Thixatrol Plus commercially obtainable, for example, from Rheox are preferably used.
The polyamide derivatives suitable for preventing dispersed solids from sedimenting and for controlling viscosity should be selected according to the polarity of the fluid system.
Polyamide structure activators generally improve the gel formation of the polyamide derivatives. In many cases, a chemical activator of this type is useful for building up a structured liquid matrix in which solid particles can be dispersed. Suitable polyamide structure activators are, above all, aromatic solvents liquid at 25°C and aliphatic alcohols, such as ethanol, propan-1-ol, propan-2-ol, butan-1-ol, butan-2-ol, isobutanol, isoamyl alcohol, cyclohexanol, glycol, propane and butane diol, 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 monoethyl ether, diisopropylene glycol monomethyl or monoethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, butoxypropoxypropanol (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 where the ratio of oxygen to carbon per structure activator molecule is in the range from 3:1 to 1:3, preferably in the range from 3:2 to 2:5 and more preferably in the range from 1:1 to 1:2. Particularly preferred liquid carboxylic acid derivatives are the carboxylic acid esters and anhydrides, more particularly monoacetylated or polyacetylated compounds such as, for example, triethyl acetyl 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 may of course also be used in the form of mixtures with one another or with other organic solvents such as, for example, ketones, aldehydes, ethers, polyethers, nitrites, aliphatics, halogenated hydrocarbons, amines, carboxylic acids and surfactants.
The polyamide structure activators are preferably used in such quantities that the ratio by weight of polyamide structure activators to polyamide derivative is from 500:1 to 1:500, preferably from 50:1 to 1:50, more preferably from 20:1 to 1:20 and most preferably from 10:1 to 1:10.
Mixtures of layer silicates according to the invention with polyamide derivatives activated by at least one polyamide structure activator in a ratio of preferably 500:1 to 1:500, more preferably from 50:1 to 1:50 and most preferably from 20:1 to 1:20 are used.
In another embodiment, the present invention relates to layer silicates activated by at least one structure activator, the layer silicates optionally being organically modified and the percentage content of structure activators being more than 100% by weight, based on the optionally organically modified layer silicates. The layer silicates and structure activators and preferred embodiments thereof are described in the foregoing.
In contrast to the first embodiment of the invention, the percentage content of structure activators, based on the optionally organically modified layer silicates, is preferably at least 120% by weight. In other special embodiments, 100:0 to 70:30 mixtures of methanol and water, ethanol and water, acetone and water and/or propylene carbonate and water, more particularly in quantities of at least 120% by weight, based on the optionally organically modified layer silicates, are preferably used as structure activators.
In another embodiment, the present invention relates to a process for the production of activated layer silicates, the percentage content of structure activators being more than 35% by weight, based on the optionally organically modified layer silicates, characterized in that the layer silicates optionally dispersed in a solvent or solvent mixture different from the structure activators are mixed with the structure activators.
The layer silicates described in reference to the first embodiment of the invention are mixed with the structure activators also described there, optionally in the presence of one or more solvents different from the structure activators. The function of this solvent is above all to break up or assist in breaking up the layer silicate platelet agglomerates generally present to begin with into individual platelets. In one preferred embodiment, these solvents or solvent mixtures different from the structure activators are surfactants. In one 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 of no more than 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.
Preferred surfactants of the sulfonate type are C9_~3 alkyl benzenesulfonates, olefin sulfonates, i.e. mixtures of alkene and hydroxy alkane sulfonates, and the disulfonates obtained, for example, from C~2_1$
monoolefins with an internal or terminal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
Preferred alk(en)yl sulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric acid semiesters of C,o_~s fatty alcohols, for example cocofatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or C$_2o oxoalcohols and the corresponding semiesters of secondary alcohols with the same chain length. Other preferred alk(en)yl sulfates are those with the chain length mentioned which contain a synthetic, linear alkyl chain based on a petrochemical.
C~2_~6 alkyl sulfates and C~2_~5 alkyl sulfates and also C~4_~5 alkyl sulfates are particularly preferred from the washing performance point of view.
Other suitable anionic surfactants are 2,3-alkyl sulfates which may be produced, for example, in accordance with US 3,234,258 or US 5,075,041 and which are commercially obtainable as products of the Shell Oil Company under the name of DAN~.
The sulfuric acid monoesters of linear or branched C~_2~ alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C9_~~ alcohols containing on average 3.5 moles of ethylene oxide (EO) or C~2_~$ fatty alcohols containing 1 to 4 EO, are also suitable. In view of their high foaming capacity, they are only used in relatively small quantities, for example in quantities of 1 to 5% by weight, in detergents.
The esters of a-sulfofatty acids (ester sulfonates), for example the a-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow acids, are also suitable.
Other suitable anionic surfactants are, in particular, soaps. Suitable soaps are, in particular, saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, end soap mixtures derived in particular from natural fatty acids, for example coconut, palm kernel or tallow acids. Soap mixtures of which 50 to 100% consist of saturated C,2_24 fatty acid soaps and 0 to 50% by weight of oleic acid soap are particularly preferred.
Another class of anionic surfactants is the class of ether carboxylic acids obtainable by reacting fatty alcohol ethoxylates with sodium chloroacetate in the presence of basic catalysts. They have the general formula: ROE(CH2ECH2E0)pECH2ECOOH, where R = C~_~8 and p = 0.1 to 20. Ether carboxylic acids are unaffected by water hardness and possess excellent surfactant properties. Their production and use are described, for example, in Seifen, Ole, Fette, Wachse 101, 37 (1975); 115, 235 (1989) and Tenside Deterg. 25, 308 (1988).
Cationic surfactants contain the high molecular weight hydrophobic residue which is responsible for surface activity on dissociation in aqueous solution in the cation. The most important representatives of the cationic surfactants are quaternary ammonium compounds with the general formula: (R'R2R3R4N+) X~, where R' represents C~_$ alkyl(en)yl, R2 to R4 independently of one another represent CnH2~+~_p_XfY'(CO)R5)p(Y2H)x, where n is an integer except 0 and p and x stand for integers or 0. Y' and Y2 independently of one another represent O, N or NH, R5 is a C3_23 alk(en)yl chain. X is a counterion preferably selected from the group of halides, alkyl sulfates and alkyl carbonates. Cationic surfactants where the nitrogen group is substituted by two long acyl chains and two short alk(en)yl chains are particularly preferred.
Amphoteric or ampholytic surfactants contain several functional groups which are capable of ionizing in aqueous solution and, depending on the conditions of the medium, imparting anionic or cationic character to the compounds (cf. DIN 53900, July 1972). In the vicinity of the isoelectric point (around pH 4), the amphoteric surfactants form inner salts so that they become insoluble or substantially insoluble in water. Amphoteric surfactants are divided into ampholytes and betaines, betaines being present in solution as zwitterions. Ampholytes are amphoteric electrolytes, i.e. compounds which contain both acidic and basic hydrophilic groups and which therefore show acidic or basic behavior according to the conditions.
Betaines are compounds containing the atomic group R3N+ECH2EC00~
which show properties typical of zwitterions.
Preferred nonionic surfactants are alkoxylated and/or propoxylated, more particularly primary alcohols preferably containing 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. C$_~6 alcohol alkoxylates, advantageously ethoxylated and/or propoxylated C~o_~5 alcohol alkoxylates, more particularly C~2_~4 alcohol alkoxylates, with a degree of ethoxylation of 2 to 10 and prefereably 3 to 8 and/or a degree of propoxylation of 1 to 6 and preferably 1.5 to 5 are particularly preferred.
The degrees of ethoxylation and propoxylation mentioned are statistical mean values which, for a special product, may be either a whole number or a broken number. Preferred alcohol ethoxylates and propoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE/NRP). In addition to these nonionic surfactants, fatty alcohols containing more than 12 EO may also be used. Examples of such fatty alcohols are (tallow) fatty alcohols containing 14 EO, 16E0, 20E0, 25 EO, 30 EO or 40 EO.
In addition, alkyl glycosides with the general formula RO(G)X where R is a primary, linear or methyl-branched, more particularly 2-methyl-branched, aliphatic radical containing 8 to 22 and preferably 12 to 18 carbon atoms and G is a glycose unit containing 5 or 6 carbon atoms, preferably glucose, may be used as further nonionic surfactants, for example as compounds, particularly with anionic surfactants. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is a number of 1 to 10 and preferably a number of 1.1 to 1.4.
Another class of preferred nonionic surfactants which are used either as sole nonionic surfactant or in combination with other nonionic surfactants, particularly together with alkoxylated fatty alcohols and/or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters preferably containing 1 to 4 carbon atoms in the alkyl chain, more particularly the fatty acid methyl esters which are described, for example, in Japanese patent application JP 581217598 or which are preferably produced by the process described in International patent application WO-A-90113533. C~2_~g fatty acid methyl esters con-taining on average 3 to 15 EO and, more particularly, 5 to 12 EO are particularly preferred.
Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethyl amine oxide, and the fatty acid alkanolamide type are also suitable. The quantity in which these nonionic surfactants are used is preferably no more, in particular no more than half, the quantity of ethoxylated fatty alcohols used.
Other suitable surfactants are so-called gemini surfactants. Gemini surfactants are generally understood to be compounds which contain two hydrophilic groups and two hydrophobic groups per molecule. These groups are generally separated from one another by a so-called Aspacer-.
The spacer is generally a carbon chain which should be long enough for the hydrophilic groups to have a sufficient spacing to be able to act independently of one another. Gemini surfactants are generally dis-tinguished by an unusually low critical micelle concentration and by an ability to reduce the surface tension of water to a considerable extent. In exceptional cases, however, gemini surfactants are not only understood to be dimeric surfactants, but also trimeric surfactants.
Suitable gemini surfactants are, for example, the sulfated hydroxy mixed ethers according to German patent application DE-A-43 21 022 and the dimer alcohol bis- and trimer alcohol tris-sulfates and -ether sulfates according to German patent application DE-A-195 03 061. The end-capped dimeric and trimeric mixed ethers according to German patent application DE-A-195 13 291 are distinguished in particular by their bi-functionality and multifunctionality. Thus, the end-capped surfactants mentioned exhibit good wetting properties and are low-foaming so that they are particularly suitable for use in machine washing or cleaning processes.
However, the gemini polyhydroxyfatty acid amides or poly-polyhy-droxyfatty acid amides described in International patent applications WO-A-95/19953, WO-A-95/19954 and WO-A-95119955 may also be used.
The surfactants are used in quantities of 0.1 to 90% by weight, preferably in quantities of 10 to 80% by weight and more preferably in quantities of 20 to 70% by weight.
In one preferred embodiment, the percentage content of structure activators, based on the optionally organically modified layer silicates, is more than 50% by weight, advantageously more than 60% by weight, preferably more than 100% by weight and more preferably at least 120%
by weight. In other special embodiments, preferred structure activators and percentage contents thereof, based on the optionally organically modified layer silicates, are 100:0 to 70:30 mixtures of methanol and water in quantities of more than 35% by weight and, more particularly, more than 50% by weight, ethanol and water in quantities of more than 50% by weight and, more particularly, more than 60% by weight, acetone and water in quantities of more than 60% by weight and, more particularly, more than 100% by weight and/or propylene carbonate and water in quantities of more than 100% by weight and, more particularly, more than 120% by weight. In other special embodiments, particularly preferred structure activators are 100:0 to 70:30 mixtures of methanol and water, ethanol and water, acetone and water and/or propylene carbonate and water in quantities of more than 100% by weight and, more particularly, at least 120% by weight, based on the optionally organically modified layer silicates.
The small quantities of water generally present in the solvents and the mixtures of polar organic solvents with at most 30% by weight water preferred as structure activators clearly promote the chemical activation of the layer silicates, above all organically modified layer silicates. This mode of action is described in the rheology handbook of Rheox International Inc.
In this case, the activator can introduce the water into the layer silicate system and can guarantee the hydrogen bridge bond between the platelets of the optionally organically modified layer silicate. To this end, the activator penetrates between the individual platelets of the organolayer silicate and forces the platelets apart from one another. The advancing separation of the platelets weakens the van-der-Waals forces which bond them to one another. The active shear forces are thus able completely to separate the platelets. The water introduced by the chemical activator or by the solvent different therefrom migrates between the hydroxyl groups of adjacent layer silicate platelet edges and completes hydrogen bridge formation and hence the gel structure.
The layer silicate, structure activator and optionally solvent are mixed under the effect of shear forces, preferably in a high-shear highly dispersing mixer. In this mixer, the mixture is passed, for example, through at least one multiple-hole dispersing disk rotating at high speed so that a fine dispersion of the layer silicates in the structure activator or structure activator/solvent mixture is formed. In one preferred embodiment, the components of the mixture are mixed in a stirring vessel and the resulting mixture is intensively sheared by one or more toothed-disk stirrers, so-called dissolver disks, or by one or more rotor/stator stirrers (for example Ultra-Turrax~) and/or in a dispersing machine (for example a Cavitron) or a ball mill.
On completion of activation by the structure activator with dispersion and shearing, the so-called stock paste, the activated layer silicate optionally present in a solvent, is obtained and may be subjected to further process steps according to the medium in which it is to be used as a rheological additive or structurant or to prevent the sedimentation of other dispersed substances.
In another embodiment, the present invention relates to a liquid laundry detergent and/or a liquid dishwashing detergent containing layer silicate which has been activated by the process described above.
This liquid laundry detergent and/or liquid dishwashing detergent contains activated layer silicates in quantities of preferably 0.01 to 20% by weight, more preferably 0.1 to less than 10% by weight and most preferably 0.5 to 5% by weight, based on the detergent as a whole. In one particularly preferred embodiment, the ratio by weight of structure activators to non-activated layer silicates is more than 0.35:1 to 1000:1, preferably more than 0.5:1 to 100:1, more preferably more than 0.6:1 to 50:1, most preferably more than 1:1 to 30:1 and, more particularly, 1.2:1 to 20:1.
In one preferred embodiment, the polyamide derivatives activated by polyamide structure activators may be present in quantities of up to 20% by weight, preferably in quantities of up to15% by weight and more preferably in quantities of up to 10% by weight, based on the detergent as a whole.
Preferred detergents are substantially water-free, i.e. contain at most 5% by weight and preferably at most 3% by weight of free water. Other preferred detergents contain organic solvents, detersive substances and/or liquid bleach activators.
Preferred organic solvents are dipropylene glycol monomethyl ether, polydiols, ethers, alcohols and/or esters which are used in quantities of 0 to 90% by weight, preferably 0.1 to 70% by weight and more preferably 0.1 to 60% by weight.
The detersive substances used may be selected from the anionic surfactants, cationic surfactants, amphoteric surfactants and/or nonionic surfactants described in the foregoing.
In order to obtain an improved bleaching effect where washing is carried out at temperatures of 60°C or lower, bleach activators may be incorporated in the preparations. Preferred liquid bleach activators are tracetin, triethyl-O-acetyl citrate (TEOC), N-methyl diacetamide, isopropenyl acetate and/or N-acetyl caprolactam which are used in quantities of 0.1 to 50% by weight, preferably 0.1 to 40% by weight and more preferably 0.1 to 20% by weight.
In addition, the detergents may contain bleaching agents and optionally other detergent ingredients such as, for example, particulate bleach activators and enzymes.
Among the compounds yielding H202 in water which serve as bleaching agents, sodium perborate tetrahydrate and sodium perborate monohydrate are particularly important. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhy-drates and H202-yielding peracidic salts ar peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, diperdodecanedioic acid or phthaloiminoperacids, such as phthaliminopercaproic acid. Organic per acids, alkali metal perborates and/or alkali metal percarbonates in quantities of 0.1 to 40% by weight, preferably 3 to 30% by weight and more preferably 5 to 25% by weight are preferably used.
Suitable bleach activators are compounds which form aliphatic peroxocarboxylic acids containing preferably 1 to 10 carbon atoms and more preferably 2 to 4 carbon atoms and/or optionally substituted perbenzoic acid under perhydrolysis conditions. Substances bearing O-and/or N-acyl groups with the number of carbon atoms mentioned and/or optionally substituted benzoyl groups are suitable. Preferred bleach activators are polyacylated alkylenediamines, more particularly tetraacetyl ethylenediamine (TAED), acylated triazine derivatives, more particularly 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycol-urils, more particularly 1,3,4,6-tetraacetyl glycoluril (TAGU), N-acylimides, more particularly N-nonanoyl succinimide (NOSI), acylated phenol sulfonates, more particularly n-nonanoyl or isononanoyloxybenzene-sulfonate (n- or iso-NOBS), carboxylic anhydrides, more particularly phthalic anhydride, isatoic anhydride and/or succinic anhydride, glycolide, acylated polyhydric alcohols, more particularly 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, acetylated sorbitol and mannitol and the mixtures thereof (SORMAN) described in European patent application EP 0 525 239, acylated sugar derivatives, more particularly pentaacetyl glucose (PAG), pentaacetyl fructose, tetraacetyl xylose and octaacetyl lactose, and acetylated, optionally N-alkylated glucamine and gluconolactone, triazole or triazole derivatives and/or particulate caprolactams and/or caprolactam derivatives, preferably N-acylated lactams, for example N-benzoyl caprolactam, which are known from International patent applications WO-A-94/27970, WO-A-94/28102, WO-A-94/28103, WO-A-95100626, WO-A-95/14759 and WO-A-95/17498.
The substituted hydrophilic acyl acetals 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 in 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 may also be used. Nitrite derivatives, such as cyanopyridines, nitrite quats and/or cyanamide derivatives may also be used. Preferred bleach activators are sodium-4-(octanoyloxy)-benzene sulfonate, undecenoyloxybenzenesulfonate (UDOBS), sodium dodecanoyl-oxybenzenesulfonate (DOBS), decanoyloxybenzoic acid (DOBA, OBC 10) and/or dodecanoyloxybenzenesulfonate (OBS 12). Bleach activators such as these are present in the usual quantities of 0.01 to 20% by weight, preferably in quantities of 0.1 % by weight to 15% by weight and more preferably in quantities of 1 % by weight to 10% by weight, based on the detergent as a whole.
The bleach activator may be coated in known manner with membrane materials or may be granulated or extruded/pelleted, optionally using auxiliaries, more particularly methyl celluloses and/or carboxymethyl celluloses, and if desired may contain other additives, for example dye, although the dye used should not have a coloring effect on the laundry to be washed. Corresponding granules preferably contain more than 70% by weight and, in one particular embodiment, from 90 to 99% by weight of bleach activator. A bleach activator which forms peracetic acid under washing conditions is preferably used.
In addition to or instead of the conventional bleach activators mentioned above, the sulfonimines known from European patents EP 0 446 982 and EP 0 453 003 and/or bleach-boosting transition metal salts or transition metal complexes may also be present as so-called bleach catalysts. Suitable transition metal compounds include, in particular, the manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen complexes known from German patent application DE-A-195 29 905 and the N-analog compounds thereof known from German patent application DE-A-196 20 267, the manganese-, iron-, cobalt-, ruthenium- or molybdenum-carbonyl complexes known from German patent application DE-A-195 36 082, the manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands described in German patent application DE-A-196 05 688, the cobalt-, iron-, copper-and ruthenium-amine complexes known from German patent application DE 196 20 411, the manganese, copper and cobalt complexes described in German patent application DE 44 16 438, the cobalt complexes described in European patent application EP-A-0 272 030, the manganese complexes known from European patent application EP-A-0 693 550, the manganese, iron, cobalt and copper complexes known from European patent EP 0 392 592 and/or the manganese complexes described in European patent EP-A-0 443 651 or in European patent applications EP-A-0 458 397, EP-A-0 458 398, EP-A-0 549 271, EP-A-0 549 272, EP-A-0 544 490 and EP-A-0 544 519. Combinations of bleach activators and transition metal bleach catalysts are known, for example, from German patent application DE-A-196 13 103 and from international patent application WO-A-95/27775. Bleach-boosting transition metal complexes, more particularly with the central atoms Mn, Fe, Co. Cu, Mo. V, Ti and/or Ru, are used in typical quantities, preferably in a quantity of up to 1 % by weight, more preferably in a quantity of 0.0025% by weight to 0.25% by weight and most preferably in a quantity of 0.01 % by weight to 0.1 % by weight, based on the detergent/cleaner as a whole.
Suitable enzymes are, in particular, enzymes from the class of hydrolases, such as proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures thereof. All these hydrolases contribute to the removal of stains, such as protein containing, fat-containing or starch-containing stains, and discoloration in the washing process. Cellulases and other glycosyl hydrolases can contribute towards color retention and towards increasing fabric softness by removing pilling and microfibrils. Oxidoreductases may also be used for bleaching and for inhibiting dye 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 are preferably used, proteases obtained from Bacillus lentus being particularly preferred.
Of particular interest in this regard are enzyme mixtures, for example of protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or of cellulase and lipase or lipolytic enzymes or of protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but especially protease- and/or lipase-containing mixtures or mixtures with lipolytic enzymes. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also been successfully used in some cases. Suitable amylases include in particular a-amylases, isoamylases, pullanases and pectinases. Preferred cellulases are cellobiohydrolases, endoglucanases and ~-glucosidases, which are also known as cellobiases, and mixtures thereof. Since the various cellulase types differ in their CMCase and avicelase activities, the desired activities can be established by mixing the cellulases in the appropriate ratios.

The enzymes may be adsorbed to supports and/or encapsulated in membrane materials to protect them against premature decomposition. The percentage content of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5% by weight and is preferably from 0.1 to about 3% by weight.
Other detergents ingredients which may be present include builders, cobuilders, soil repellents, alkaline salts and foam inhibitors, complexing agents, enzyme stabilizers, redeposition inhibitors, optical brighteners and UV absorbers.
A suitable builder is, for example, finely crystalline, synthetic zeolite containing bound water, preferably zeolite A and/or zeolite P. Zeolite MAP~ (Crosfield), for example, is a particularly preferred P-type zeolite.
However, zeolite X and mixtures of A, X and/or P are also suitable. Also of particular interest is the co-crystallized sodium/potassium aluminium silicate of zeolite A and zeolite X which is commercially available as VEGOBOND AX~ (a product of Condea). The zeolite may preferably be used as a spray-dried powder. If the zeolite is used in the form of a suspension, the suspension may contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C~2_~8 fatty alcohols containing 2 to 5 ethylene oxide groups, C12-14 fatty alcohols containing 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have a mean particle size of less than 10 ~.m (volume distribution, as measured by the Coulter Counter method) and contain preferably 18 to 22% by weight and more preferably 20 to 22% by weight of bound water. In addition, phosphates may also be used as builders.
Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline layer-form sodium silicates corresponding to the general formula NaMSiX02x+~AyH20, where M is sodium or hydrogen, x is a number of 1.9 to 4 and y is a number of 0 to 20, preferred values for x being 2, 3 or 4. Crystalline layer silicates such as these are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layer silicates corresponding to the above formula are those in which M is sodium and x assumes the value 2 or 3. Both Vii- and 8-sodium disilicates Na2Si205AyH20 are particularly preferred, ~i-sodium disilicate being obtainable for example by the process described in International patent application WO-A-91/08171.
Other preferred builders are amorphous sodium silicates with a modulus (Na20:Si02 ratio) of 1:2 to 1:3.3, preferably 1:2 to 1:2.8 and more preferably 1:2 to 1:2.6 which dissolve with delay and exhibit multiple wash cycle properties. The delay in dissolution in relation to conventional amorphous sodium silicates can have been obtained in various ways, for example by surface treatment, compounding, compacting or by overdrying.
In the context of the invention, the term Aamorphous= is also understood to encompass AX-ray amorphous-. In other words, the silicates do not produce any of the sharp X-ray reflexes typical of crystalline substances in X-ray diffraction experiments, but at best one or more maxima of the scattered X-radiation which have a width of several degrees of the diffraction angle. Particularly good builder properties may even be achieved where the silicate particles produce crooked or even sharp diffraction maxima in electron diffraction experiments. This may be interpreted to mean that the products have microcrystalline regions between 10 and a few hundred nm in size, values of up to at most 50 nm and, more particularly, up to at most 20 nm being preferred. So-called X-ray amorphous silicates such as these, which also dissolve with delay in relation to conventional waterglasses, are described for example in German patent application DE-A-44 00 024. Compacted amorphous sili-cates, compounded amorphous silicates and overdried X-ray-amorphous silicates are particularly preferred.
The generally known phosphates may of course also be used as builders providing their use is not ecologically problematical. The sodium salts of orthophosphates, pyrophosphates and, in particular, tripoly-phosphates are particularly suitable. Their content is generally no more than 25% by weight and preferably no more than 20% by weight, based on the final detergent. In some cases, it has been found that tri polyphosphates in particular, even in small quantities of up to at most 10%
by weight, based on the final detergent, produce a synergistic improvement in multiple wash cycle performance in combination with other builders.
Preferred quantities of phosphates are below 10% by weight and are preferably 0% by weight.
Organic builders useful as co-builders are, for example, polycarboxylic acids usable in the form of their sodium salts, polycarboxylic acids in this context being those carboxylic acids which carry more than one acid function. These include, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, malefic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA) and their derivatives and mixtures thereof. Preferred salts are the salts of the polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
The acids per se may also be used. Besides their builder effect, the acids also typically have the property of an acidifying component and, hence, also serve to establish a relatively low and mild pH value in detergents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and mixtures thereof are particularly mentioned in this regard.
Other suitable acidifiers are known pH regulators, such as sodium hydrogen carbonate and sodium hydrogen sulfate.
Other suitable builders are polymeric polycarboxylates such as, for example, the alkali metal salts of polyacrylic or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g/mole.
The molecular weights mentioned in this specification for polymeric polycarboxylates are weight-average molecular weights MW of the particular acid form which, basically, were determined by gel permeation chromatography (GPC) using a UV detector. The measurement was carried out against an external polyacrylic acid standard which provides realistic molecular weight values by virtue of its structural similarity to the polymers investigated. These values differ distinctly from the molecular weights measured against polystyrene sulfonic acids as standard. The molecular weights measured against polystyrene sulfonic acids are generally higher than the molecular weights mentioned in this specification.
Particularly suitable polymers are polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g/mole. By virtue of their superior solubility, preferred representatives of this group are the short-chain polyacrylates which have molecular weights of 2,000 to 10,000 g/mole and, more particularly, 3,000 to 5,000 g/mole.
Other suitable polymers are substances which consist completely or partly of units of vinyl alcohol or derivatives thereof.
Also suitable are copolymeric polycarboxylates, particularly those of acrylic acid with methacrylic acid and those of acrylic acid or methacrylic acid with malefic acid. Acrylic acid/maleic acid copolymers containing 50 to 90% by weight of acrylic acid and 50 to 10% by weight of malefic acid have proved to be particularly suitable. Their relative molecular weights, based on the free acids, are generally in the range from 2,000 to 70,000 g/mole, preferably in the range from 20,000 to 50,000 g/mole and more preferably in the range from 30,000 to 40,000 g/mole. The (co)polymeric polycarboxylates may be used either in the form of an aqueous solution or preferably in powder form In order to improve solubility in water, the polymers may also contain allyl sulfonic acids, such as allyloxybenzene sulfonic acid and methallyl sulfonic acid (cf. EP-B-727 448), as monomer.
Other particularly preferred polymers are biodegradable polymers of more than two different monomer units, for example those which contain salts of acrylic acid and malefic acid and vinyl alcohol or vinyl alcohol derivatives as monomers according to DE-A-43 00 772 or those which contain salts of acrylic acid and 2-alkylallyl sulfonic acid and sugar derivatives as monomers according to DE-C-42 21 381.
Other preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and which preferably contain acrolein and acrylic acid/acrylic acid salts or acrolein and vinyl acetate as monomers.
Other preferred builders are polymeric aminodicarboxylic acids, salts or precursors thereof. Particular preference is attributed to polyaspartic acids or salts and derivatives thereof which, according to German patent application DE-A-195 40 086, are also said to have a bleach-stabilizing effect in addition to their co-builder properties.
Other suitable builders are polyacetals which may be obtained by reaction of dialdehydes with polyol carboxylic acids containing 5 to 7 carbon atoms and at least three 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, terephthal-aldehyde and mixtures thereof and from polyol carboxylic acids, such as gluconic acid and/or glucoheptonic acid.
Other suitable organic builders are dextrins, for example oligomers or polymers of carbohydrates which may be obtained by partial hydrolysis of starches. The hydrolysis may be carried out by standard methods, for example acid- or enzyme-catalyzed methods. The end products are preferably hydrolysis products with average molecular weights of 400 to 500,000 g/mole. A polysaccharide with a dextrose equivalent (DE) of 0.5 to 40 and, more particularly, 2 to 30 is preferred, the DE being an accepted measure of the reducing effect of a polysaccharide by comparison with dextrose which has a DE of 100. Both maltodextrins with a DE of 3 to 20 and dry glucose sirups with a DE of 20 to 37 and also so-called yellow dextrins and white dextrins with relatively high molecular weights of 2,000 to 30,000 g/mole may be used. 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. Dextrins thus oxidized and processes for their production 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 and from International patent applications WO 92118542, WO 93108251, WO 93116110, WO 94128030, WO 95/07303, WO 95112619 and WO 95120608. An oxidized oligosaccharide corresponding to German patent application DE-A-196 00 018 is also suitable. A product oxidized at C6 of the saccharide ring can be particularly advantageous.
Other suitable co-builders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate. Ethylenediamine-N,N'-disuccinate (EDDS), of which the synthesis is described for example in US 3,158,615, is preferably used in the form of its sodium or magnesium salts. The glycerol disuccinates and glycerol trisuccinates described, for example, in US 4,524,009, in US 4,639, 325, in European patent application EP-A-0 150 930 and in Japanese patent application JP
931339896 are also particularly preferred in this connection. The quantities used in zeolite-containing and/or silicate-containing formulations are from 3 to 15% by weight.
Other useful organic co-builders are, for example, acetylated hydroxycarboxylic acids and salts thereof which may optionally be present in lactone form and which contain at least 4 carbon atoms, at least one hydroxy group and at most two acid groups. Co-builders such as these are described, for example, in International patent application WO-A-95/20029.

The detergents according to the invention may additionally contain components which have a positive effect on the removability of oil and fats from textiles by washing (so-called soil repellents). This effect becomes particularly clear when a textile which has already been repeatedly washed with a detergent according to the invention containing this oil- and fat-dissolving component is soiled. Preferred oil- and fat-dissolving components include, for example, nonionic cellulose ethers, such as methyl cellulose and methyl hydroxypropyl cellulose containing 15 to 30% by weight of methoxyl groups and 1 to 15% by weight of hydroxypropoxyl groups, based on the nonionic cellulose ether, and the polymers of phthalic acid and/or terephthalic acid known from the prior art or derivatives thereof, more particularly polymers of ethylene terephthalates and/or polyethylene glycol terephthalates or anionically and/or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic and terephthalic acid polymers are particularly preferred.
Other suitable ingredients of the detergents are water-soluble inorganic salts, such as bicarbonates, carbonates, amorphous silicates or mixtures thereof; alkali metal carbonate and amorphous alkali metal silicate, above all sodium silicate with a molar Na20:Si02 ratio of 1:1 to 1:4.5 and preferably 1:2 to 1:3.5, are particularly suitable.
Preferred detergents contain alkaline salts, builders and/or co-builders, preferably sodium carbonate, zeolite, crystalline layer-form sodium silicates and/or trisodium citrate, in quantities of 0.5 to 70% by weight, preferably 0.5 to 50% by weight and more preferably 0.5 to 30% by weight water-free substance.
Where the detergents are used in washing machines, it can be of advantage to add typical foam inhibitors to them. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin which have a high percentage content Of C~g_24 fatty acids. Suitable non-surface-active foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized, silica and also paraffins, waxes, microcrystalline waxes and mixtures thereof with silanized silica or bis-stearyl ethylenediamide. Mixtures of different foam inhibitors, for example mixtures of silicones, paraffins and waxes, may also be used with advantage. The foam inhibitors, more particularly silicone- and/or paraffin-containing foam inhibitors, are preferably fixed to a granular water-soluble or water-dispersible support. Mixtures of paraffins and bis-stearyl ethylenediamides are particularly preferred.
Suitable complexing agents or stabilizers, more particularly for per compounds and enzymes sensitive to heavy metal ions, are the salts of polyphosphonic acids, preferably the sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate, diethylenetriamine pentamethylene phosphonate or ethylenediamine tetramethylene phosphonate in quantities of 0.1 to 1.5% by weight.
The function of redeposition inhibitors is to keep the soil detached from the fibers suspended in the wash liquor and thus to prevent the soil from being re-absorbed by the washing. Suitable redeposition inhibitors are water-soluble, generally organic colloids, for example the water-soluble salts of (co)polymeric carboxylic acids, glue, gelatine, 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, for example degraded starch, aldehyde starches, etc., may also be used.
Polyvinyl pyrrolidone is also suitable. However, cellulose ethers, such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose, and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and polyvinyl pyrrolidone are also preferably used, for example in quantities of 0.1 to 5% by weight, based on the detergent.

The detergents may contain derivatives of diaminostilbene disulfonic acid or alkali metal salts thereof as optical brighteners. Suitable optical brighteners are, for example, salts of 4,4'-bis-(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)-stilbene-2,2'-disulfonic acid or compounds of similar structure which contain a diethanolamino group, a methylamino group and anilino group or a 2-methoxyethylamino group instead of the morpholino group. Brighteners of the substituted Biphenyl styryl type, for example alkali metal salts of 4,4'-bis-(2-sulfostyryl)-Biphenyl, 4,4'-bis-(4-chloro-3-sulfostyryl)-Biphenyl or 4-(4-chlorostyryl)-4'-(2-sulfostyryl)-Biphenyl, may also be present. Mixtures of the brighteners mentioned may also be used.
In addition, UV absorbers may also be used. UV absorbers are compounds with a pronounced absorption capacity for ultraviolet radiation which, as light stabilizers (UV stabilizers), both contribute towards improving the light stability of dyes and pigments and textile fibers and also protect the skin of the wearer of textile products against UV radiation penetrating through the textile. In general, the compounds in question, which act by "radiationless" deactivation, are derivatives of benzophenone of which the substituents, such as hydroxy and/or alkoxy groups, are generally in the 2 position and/or 4 position. Substituted benzotriazoles are also suitable, as are 3-phenyl-substituted acylates (cinnamic acid derivatives), optionally with cyano groups in the 2 position, salicylates, organic nickel complexes and natural substances, such as umbelliferone and the body's own urocanic acid. In one preferred embodiment, the UV
absorbers absorb UV-A and UV-B radiation and optionally UV-C radiation and reflect back with wavelengths of blue light, so that they additionally act as an optical brightener. Other preferred UV absorbers are the UV
absorbers disclosed 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, such as triazine derivatives, for example hydroxyaryl-1,3,5-triazine, sulfonated 1,3,5-triazine, o-hydroxyphenyl benzotriazole and 2-aryl-2H-benzotriazole and also bis-(anilinotriazinylamino)-stilbene disulfonic acid and derivatives thereof. UV-absorbing pigments, such as titanium dioxide, may also be used as UV absorbers.
Preferred liquid laundry detergents are pseudoplastic, i.e. they have the pseudoplastic or thixotropic flow described at the beginning as a rheological property.
The detergents may contain other conventional thickeners and antisedimenting agents and also viscosity regulators, such as polyacrylates, polycarboxylic acids, polysaccharides and derivatives thereof, polyurethanes, polyvinyl pyrrolidones, castor oil derivatives, polyamine derivatives, such as quaternized and/or ethoxylated hexamethylenediamines, and mixtures thereof. Preferred detergents have a viscosity below 10,000 mPa~s, as measured with a Brookfield viscosimeter at a temperature of 20°C and at a shear rate of 50 mint .
The detergents may contain other typical detergent ingredients, such as perfumes and dyes, preferred dyes having little or no coloring effect on the laundry to be washed. Preferred quantity ranges for all the dyes used are below 1 % by weight and preferably below 0.1 % by weight, based on the detergent. The detergents may also contain white pigments, for example Ti02.
Preferred detergents have densities of 0.5 to 2.0 g/cm3 and, more particularly, 0.7 to 1.5 g/cm3.
In another embodiment, the present invention relates to a process for the production of liquid laundry detergents and/or liquid dishwashing detergents containing activated layer silicate, characterized in that (a) in a first process step, layer silicates are activated by at least one structure activator, the percentage content of structure activators being at least 35% by weight, based on the optionally organically modified layer silicates, and the layer silicates optionally dispersed in a solvent or solvent mixture different from the structure activators are mixed with the structure activators, (b) the mixture obtained in process step (a) is mixed with other detergent ingredients and optionally ground, (c) other substances, preferably substances sensitive to or unwanted for process step (b), are optionally added.
Step (a) has already been described in detail in the foregoing as a process for activating the layer silicates. In step (a), the layer silicates are preferably dispersed in part of the solvent or solvent mixture different from the structure activators and the resulting dispersion is diluted after activation by addition of more of the solvent or solvent mixture different from the structure activators.
The other detergent ingredients and substances added in process steps (b) and (c) may be selected from any of the above-mentioned substances, such as surfactants, builders, co-builders, bleaching agents, bleach activators, enzymes, solvents, soil repellents, alkaline salts, foam inhibitors, complexing agents, enzyme stabilizers, redeposition inhibitors, optical brighteners, UV absorbers, thickeners, perfumes, dyes and other typical detergent additives.
Substances sensitive to process step (b) are, for example, enzymes which may be denatured, peracids, bleach activators and coated materials, such as percarbonate, which may be decomposed. Substances unwanted in process step (b) are, for example, dyes, brighteners, perfumes, etc.
which, for example, cause extra work when the plant/installation is cleaned in the event of product changes.
In one preferred embodiment, a grinding and/or size-reducing process is carried out in step (b), preferably in a ring-gap ball mill or in a roll mill. In another preferred embodiment, step (a) and step (b), preferably steps (a) to (c), are carried out simultaneously in a "one-pot" process.
After the grinding and/or size-reducing process, the particles obtained are between 5 and 200 Nm in size, preferably between 5 and 50 pm in size and more preferably between 10 and 30 pm in size.
Detergents containing layer silicates activated by this process have improved rheological properties, desirable pseudoplastic or thixotropic flow and a reduced tendency towards sedimentation of the solid particles dispersed in the gel phase.
Embodiments of the invention are described in the following examples which are not to be construed as limiting.
Examples Example 1 The formulation for a nonaqueous liquid laundry detergent is shown in Table 1 below.
Table 1:
Formulation for a nonaqueous liquid laundry detergent Raw material Content by weight [%]
Nonionic surfactants (C~2-C~4, 5 EO, 63.27 2 PO) Perborate monohydrate 14.0 Tetraacetyl ethylenediamine 5.5 Trisodium citrate (water-free) 10.0 Soil repellentb 0.2 Optical brightener 0.1 Silicone antifoam agent 0.2 Perfume oil 1.5 Dye +

Layer silicates 1.0 Propylene carbonate (structure activator)1.2 Water for propylene carbonate 0.03 1-Hydroxyethane-1,1-disphosphonic acid disodium salts 1.0 Protease 1.0 Amylase 1.0 _______________________________________________________________________________ __________________ a Dehypon LS 52 R~, a product of Henkel Chimica S.p.A.
b Polyethylene terephthalate ester, Velvetol 251 C~, a product of Rhone-Poulenc Tinopal CBS-X~, a product of Ciba-Geigy d Tixogel MP 250~, a product of Sud-Chemie a Fostex 2 NZ~, a product of Henkel France S.A.
Example 2 The formulation for another nonaqueous liquid laundry detergent is shown in Table 2 below.
Table 2:
Formulation for a nonaqueous liquid laundry detergent Raw material Content by weight [%]
Nonionic surfactants (C~2-C~4, 5 EO, 2 65.1 PO) Perborate monohydrate 12.0 Tetraacetyl ethylenediamine 4.0 Trisodium citrate (water-free) 9.3 Soil repellentb 0.2 Optical brightener~ 0.1 Silicone antifoam agent 0.2 Perfume oil 1.5 Dye +

Layer silicates 1.5 Propylene carbonate (structure activator) 2.0 Water from raw materials 0.1 1-Hydroxyethane-1,1-disphosphonic acid disodium salts 1.0 Redeposition inhibitorf 2.0 Protease 1.0 Amylase 1.0 a Dehypon LS 52 R~, a product of Henkel Chimica S.p.A.
b Polyethylene terephthalate ester, Velvetol 251 C~, a product of Rhone-Poulenc Tinopal CBS-X~, a product of Ciba-Geigy d Tixogel MP 250~, a product of Sud-Chemie a Fostex 2 NZ~, a product of Henkel France S.A.
f malefic acid/acrylic acid copolymer sodium salt (30:70), Sokalan CP 5~
powder, ca. 92%, molecular weight 70,000, a product of BASF
Two steps are crucial to the production of the formulations, namely:
activation of the layer silicate and the mixing and optionally grinding of the solids.
In the first process step, the layer silicate was mixed with part of the surfactant so that a ca. 3% by weight suspension of layer silicate in surfactant was obtained. For activation, this suspension was swollen together with a structure activator by intensive shearing in a Cavitron. The layer silicate used was Tixogel~ MP 250 (Siid-Chemie AG), an organically modified smectite product. Propylene carbonate was used as the structure activator. The stock paste produced in this way was then diluted with the rest of the surfactant.
In a second process step, the stock paste was mixed with other formulation ingredients (perborate, citrate, perfume, phosphonate, foam inhibitor, optical brightener, soil repellent, dyes, etc.) and the resulting mixture was subjected to grinding in a ring-gap ball mill for size reduction of the solid particles. Enzymes and bleach activator were not processed in this step because they would have been damaged by the grinding process.
The particles obtained were between 15 Nm and 30 Nm in size.
Finally, in a third step, enzymes and TAED were stirred in.
By virtue of their stabilization by the activated layer silicate, the detergents obtained by this process were distinguished by excellent physical properties, such as storage stability of the bleaching agents, bleach activators and enzymes and a reduced tendency towards sedimentation of the solid particles dispersed in the gel phase, after storage for 4 weeks at 5°C, 20°C and 40°C.

Claims (139)

1. The use of optionally organically modified layer silicates activated by at least one structure activator in liquid laundry detergents, in liquid dishwashing detergents and other fluid to high-viscosity media for improving the rheological properties of the medium or for preventing the sedimentation of solid particles dispersed in the medium, wherein the percentage content of structure activators is more than 35% by weight, based on the optionally organically modified layer silicates.

2. The use of layer silicates as claimed in claim 1, wherein silicates with a three-layer structure are used as the layer silicates.

3. The use of layer silicates as claimed in claim 2, wherein said silicates with three-layer structure are dioctahedral smectites.

4. The use of layer silicates as claimed in claim 3, wherein said silicates with three-layer structure are montmorillonites and bentonites and/or trioctahedral smectites.

5. The use of layer silicates as claimed in claim 4, wherein said silicates with three-layer structure are hectortites

6 The use of layer silicates as claimed in any one of claims 1 to 5, wherein the layer silicates are organically modified.

7. The use of layer silicates as claimed in claim 6, wherein said layer silicates incorporate quaternary ammonium compounds.

8. The use of layer silicates as claimed in any one of claims 1 to 7, wherein the layer silicates used have a specific gravity of 1.1 g/cm3 to 2.5 g/cm3.

9. The use of layer silicates as claimed in claim 8, wherein the layer silicates used have a specific gravity of 1.5 g/cm3 to 2.1 g/cm3.

10. The use of layer silicates as claimed in any one of claims 1 to 9, wherein the layer silicates used have a bulk density of 300 g/l to 600 g/l.

11. The use of layer silicates as claimed in claim 10, wherein the layer silicates used have a bulk density of 350 g/l to 500 g/l.

12. The use of layer silicates as claimed in any one of claims 1 to 12, wherein the layer silicates used have a sieve residue to 90 µm of at most 15% by weight and a moisture content of at most 5% by weight.

13. The use of layer silicates as claimed in any one of claims 1 to 12, wherein the structure activators are low molecular weight polar substances.

14. The use of layer silicates as claimed in claim 13, wherein the structure activators are polar organic solvents.

15. The use of layer silicates as claimed in claim 14, wherein the structure activators are methanol, ethanol, propylene carbonate, acetone, acetonyl acetone, diacetone alcohol, ethyl acetate, 2-propanol, dipropylene glycol monomethyl ether and dimethyl formamide or mixtures thereof with at most 30% by weight of water.

16. The use of layer silicates as claimed in claim 15, wherein said structure activators have at most 20% by weight of water.

17. The use of layer silicates as claimed in claimed 16, wherein said structure activators have at most 2 to 7% by weight of water based on the mixture of the polar organic solvents with water.

18. The use of layer silicates as claimed in any one of claims 1 to 17, wherein the percentage content of structure activators is more than 50% by weight based on the optionally organically modified layer silicates.

19. The use of layer silicates as claimed in claim 18, wherein the percentage content of structure activators is more than 60% by weight based on the optionally organically modified layer silicates.

20. The use of layer silicates as claimed in claim 19, wherein the percentage content of structure activators is more than 100% by weight based on the optionally organically modified layer silicates.

21. The use of layer silicates as claimed in claim 20, wherein the percentage content of structure activators is more than 120% by weight based on the optionally organically modified layer silicates

22. The use of layer silicates as claimed in any one of claims 1 to 22, wherein 100:0 to 70:30 mixtures of methanol and water in quantities of more than 35% by weight, ethanol and water in quantities of more than 50% by weight, acetone and water in quantities of more than 60% by weight, and/or propylene carbonate and water in quantities of more than 100% by weight based on the optionally organically modified layer silicates, are used as the structure activators.

23. The use of layer silicates as claimed in claim 22, wherein said mixture of methanol and water is used in quantities of more than 50% by weight as structure activator.

24. The use of layer silicates as claimed in claim 22 or claim 23, wherein said mixture of ethanol and water is used in quantities of more than 60% by weight as structure activator.

25. The use of layer silicates as claimed in any one of claims 22 to 24, wherein said mixture of proplene carbonate and water is used in quantities of greater than 120% by weight as structure activator.

26. The use of layer silicates as claimed in any one of claims 22 to 25, wherein 100:0 to 70:30 mixtures of methanol and water, ethanol and water, acetone and water and/or propylene carbonate and water in quantities of more than 100% by weight based on the optionally organically modified layer silicates are used as the structure activators.

27. The use of layer silicates as claimed in claim 26, wherein said mixtures are used in quantities of more than 120% by weight as structure activators.

28. The use of layer silicates as claimed in any one of claims 1 to 27, wherein the activated layer silicates are used in substantially nonaqueous liquid laundry detergents and/or substantially nonaqueous liquid dishwashing detergents.

29. The use of layer silicates as claimed in claim 28 for stabilizing solids in substantially nonaqueous, bleach-containing liquid laundry detergents and/or liquid dishwashing detergents.

30. The use of layer silicates as claimed in claim 29, wherein said solids are selected from bleaching agents, bleach activators, enzymes, optical brighteners, UV absorbers, inorganic and organic builders

31. The use of layer silicates as claimed in any one of claims 1 to 30, wherein the activated layer silicates are present in the form of mixtures with polyamide derivatives activated by at least one polyamide structure activator.

32. The use of layer silicates as claimed in claim 31, wherein the mixing ratio of the activated layer silicates and polyamide derivatives is 500:1 to 1:500.

33. The use of layer silicates as claimed in claim 32, wherein the mixing ratio of the activated layer silicates and polyamide derivatives is 50:1 to 1:50.

34. The use of layer silicates as claimed in claim 33, wherein the mixing ratio of the activated layer silicates and polyamide derivatives is 20:1 to 1:20.

35. Layer silicates activated by at least one structure activator, the layer silicates optionally being organically modified, wherein the percentage content of structure activators is more than 100% by weight, based on the optionally organically modified layer silicates.

36. Layer silicates as claimed in claim 35, wherein silicates with a three-layer structure are used as the layer silicates.

37. Layer silicates as claimed in claim 36, wherein said silicates with a three-layer structure are diotahedral smectites.

38. Layer silicates as claimed in claim 37, wherein said silicates with a three-layer structure are montmorillonites and bentonites, and/or trioctahedral smectities.

39. Layer silicates as claimed in claim 38, wherein said silicates with a three-layer structure are hectorites.

40. Layer silicates as claimed in any one of claim 36 to 39, wherein the layer silicates are organically modified.

41. Layer silicates as claimed in claim 40, wherein said layer silicates incorporated quaternary ammonium compounds.

42. Layer silicates as claimed in any one of claims 35 to 41, wherein the layer silicates used have a specific gravity of 1.1 g/cm3 to 2.5 g/cm3, a bulk density of 300 g/l to 600 g/l, a sieve residue to 90 Nm of at most 15% by weight and a moisture content of at most 5% by weight.

43. Layer silicates as claimed in claim 42, wherein said layer silicates have a specific gravity of 1.5 g/cm3 to 2.1 g/cm3.

44. Layer silicates as claimed in claim 43, wherein said layer silicates have a bulk density of 350 g/l to 500 g/l.

45. Layer silicates as claimed in any one of claims 36 to 44, wherein the structure activators are low molecular weight polar substances.

46. Layer silicates as claimed in claim 45, wherein said polar substances are polar organic solvents.

47. Layer silicates as claimed in claim 46, wherein said solvents are selected from the group of methanol, ethanol, propylene carbonate, acetone, acetonyl acetone, diacetone alcohol, ethyl acetate, 2-propanol, dipropylene glycol monomethyl ether and dimethyl formamide or mixtures thereof with at most 30% by weight of water based on the mixture of the polar organic solvents with water.

48. Layer silicates as claimed in claim 47, wherein said solvents have at most 10% by weight of water.

49. Layer silicates as claimed in claim 48, wherein said solvents have at most 2 to 7% by weight of water.

50. Layer silicates as claimed in any one of claims 35 to 40, wherein the percentage content of structure activators, based on the optionally organically modified layer silicates, is at least 120% by weight.

51. Layer silicates as claimed in any one of claims 35 to 50, wherein the layer silicates contain 100:0 to 70:30 mixtures of methanol and water, ethanol and water, acetone and water and/or propylene carbonate and water as structure activators.

52. Layer silicates as claimed in any of claim 51, wherein said mixtures are present in quantities of at least 120% by weight, based on the optionally organically modified layer silicates

53. A process for the production of activated layer silicates, wherein the percentage content of structure activators is more than 35% by weight, based on the optionally organically modified layer silicates, the layer silicates optionally dispersed in a solvent or solvent mixture different from the structure activators being mixed with the structure activators in the presence of shear forces.

54. A process as claimed in claim 53, wherein said silicates with a three-layer structure are used as the layer silicates.

55. A process as claimed in claim 54, wherein said silicates with a three-layer structure are dioctahedral smectites.

56. A process as claimed in claim 55, wherein said silicates with a three-layer structure are montmorillonites and bentonites, and/or trioctahedral smectites.

57. A process as claimed in claim 56, wherein said silicates with a three-layer structure are hectorites.

58. A process as claimed in any one of claims 54 to 57, wherein said layer silicates are organically modified.

59. A process as claimed in claim 58, wherein said layer silicates are quaternary ammonium compounds.

60. A process as claimed in any one of claims 53 to 59, wherein the layer silicates used have a specific gravity of 1.1 g/cm3 to 2.5 g/cm3, a bulk density of 300 g/l to 600 g/l, a sieve residue to 90 µm of at most 15% by weight and a moisture content of at most 5% by weight.

61. A process as claimed in claim 60, wherein said layer silicates have a specific gravity of 1.5 g/cm3 to 2.1 g/cm3,

62. A process as claimed in claim 60 or 61, wherein said layer silicates have a bulk density of 350 g/l to 500 g/l,

63. A process as claimed in any one of claims 53 to 62, wherein the structure activators are low molecular weight polar substances.

64. A process as claimed in claim 63, wherein said structure activators are polar organic solvents.

65. A process as claimed in claim 64, wherein said structure activators are methanol, ethanol, propylene carbonate, acetone, acetonyl acetone, diacetone alcohol, ethyl acetate, 2-propanol, dipropylene glycol monomethyl ether and dimethyl formamide or mixtures thereof with at most 30% by weight of water based on the mixture of the polar organic solvents with water.

66. A process as claimed in claim 65, wherein said solvents have at most 10% by weight of water.

67. A process as claimed in claim 66, wherein said solvents have at most 2 to 7% by weight of water.

68. A process as claimed in any one of claims 53 to 67, wherein the percentage content of structure activators is more than 50% by weight based on the optionally organically modified layer silicates.

69. A process as claimed in claim 68, wherein the percentage content of structure activators is more than 60% by weight based on the optionally organically modified layer silicates.

70. A process as claimed in claim 69, wherein the percentage content of structure activators is more than 100% by weight based on the optionally organically modified layer silicates.

71. A process as claimed in claim 70, wherein the percentage content of structure activators is more than 120% by weight based on the optionally organically modified layer silicates.

72. A process as claimed in any one of claims 53 to 71, wherein 100:0 to 70:30 mixtures of methanol and water in quantities of more than 35% by weight, ethanol and water in quantities of more than 50% by weight, acetone and water in quantities of more than 60% by weight and/or propylene carbonate and water in quantities of more than 100% by weight based on the optionally organically modified layer silicates, are used as the structure activators.

73. A process as claimed in claim 72, wherein said methanol and water mixture is used in quantities of more than 50% by weight.

74. A process as claimed in claim 72, wherein said ethanol and water mixture is used in quantities of more than 60% by weight.

75. A process as claimed in claim 72, wherein said acetone and water mixture is used in quantities of more than 100% by weight.

76. A process as claimed in claim 72, wherein said propylene carbonate and water mixture is used in quantities of more than 120% by weight.

77. A process as claimed in any one of claims 72 to 76, wherein 100:0 to 70:30 mixtures of methanol and water, ethanol and water, acetone and water and/or propylene carbonate and water in quantities of more than 100% by weight based on the optionally organically modified layer silicates, are used as the structure activators.

78. A process as claimed in claim 77, wherein said mixtures are used in quantities of at least 120% by weight as structure activators.

79. A process as claimed in any one of claims 53 to 78, wherein nonionic surfactants and/or organic solvents and optionally anionic surfactants, cationic surfactants, cationic surfactants and/or amphoteric surfactants are used as the solvents or the solvent mixtures different from the structure activators.

80. A process as claimed in claim 79, anionic surfactants are selected from ethoxylated and/or propoxylated alcohols.

81. A process as claimed in any one of claims 53 to 80, wherein the nonionic surfactants used are selected from C8-16 alcohol alkoxylates with a degree of ethoxylation of 1 to 12, and/or a degree or propoxylation of 1 to 10.

82. A process as claimed in claim 81, wherein said alkoxylates are ethoxylated and/or propoxylated C10-15 alcohol alkoxylates.

83. A process as claimed in claim 82, wherein said alkoxylates are C12-14 alcohol alkoxylates.

84. A process as claimed in any one of claims 81 to 83, wherein said alkoxylates have a degree of ethoxylation of 2 to 10.

85. A process as claimed in any claims 81 to 83, wherein said alkoxylates have a degree of ethoxylation of 3 to 8.

86. A process as claimed in any one of claims 81 to 85, wherein said alkoxylates have a degree of propoxylation of 1 to 10.

87. A process as claimed in any one of claims 81 to 85, wherein said alkoxylates have a degree of propoxylation of 1 to 6.

88. A process as claimed in claim 81 to 85, wherein said alkoxylates have a degree of propoxylation of 1.5 to 5.

89. A process as claimed in any one of claims 53 to 89 wherein the water content of the solvent or solvent mixture different from the structure activators does not exceed 5% by weight.

90. process as claimed in any one of claims 53 to 88, wherein (a) the components of the mixture are mixed in a stirring vessel, (b) the resulting mixture is intensively sheared by one or more toothed-disk stirrers and/or by one or more rotor/stator stirrers and/or (c) the mixture is intensively sheared in a dispersing machine or in a ball mill.

91 Liquid laundry detergent and/or liquid dishwashing detergent containing layer silicate activated by the process claimed in any of claims 53 to 90.

92 A detergent as claimed in claim 91 containing layer silicates in quantities of 0.01 to 20% by weight based on the detergent as a whole.

93 A detergent as claimed in claim 92 containing layer silicates in quantities of 0.1 % by weight to less than 10% by weight based on the detergent as a whole.

94. A detergent as claimed in claim 93, containing layer silicates in quantities of 0.5% by weight to 5% by weight based on the detergent as a whole.

95. A detergent as claimed in any one of claims 92 or 94, wherein the ratio by weight of structure activators to non-activated layer silicates is more than 0.35:1 to 1000:1.

96. A detergent as claimed in claim 95, wherein the ratio by weight of structure activators to non-activated layer silicates is more than 0.5:1 to 100:1.

97. A detergent as claimed in claim 96, wherein the ratio by weight of structure activators to non-activated layer silicates is more than 0.6:1 to 50:1.

98. A detergent as claimed in claim 97, wherein the ratio by weight of structure activators to non-activated layer silicates is more than 1:1 to 30:1.

99. A detergent as claimed in claim 98, wherein the ratio by weight of structure activators to non-activated layer silicates is more than 1.2:1 to 20:1.

100. A detergent as claimed in any one of claims 90 to 99, which is substantially water-free and contains organic solvents, surfactants and/or liquid bleach activators.

101. A detergent as claimed in claim 100, containing organic solvents in quantities of 0 to 90% by weight.

102. A detergent as claimed in claim 101, wherein said solvents are dipropylene glycol monomethyl ether, polydiols, ethers, alcohols and/or esters.

103. A detergent as claimed in claim 102, wherein said solvents are present in quantities of 0.1 to 70% by weight.

104. A detergent as claimed in claim 102, wherein said solvents are present in in quantities of 0.1 to 60% by weight.

105. A detergent as claimed in any one of claims 100 to 104, containing surfactants in quantities of 0.1 to 90% by weight.

106. A detergent as claimed in claim 105, wherein said surfactants are anionic surfactants, cationic surfactants, amphoteric surfactans and/or nonionic surfactants.

107. A detergent as claimed in claim 106, wherein said surfactants are ethoxylated and/or propoxylated alcohols.

108. A detergent as claimed in any one of claims 105 to 107, wherein said surfactants are present in quantities of 10 to 80% by weight.

109. A detergent as claimed in claim 108, wherein said surfactants are present in quantities of 20 to 70% by weight.

110. A detergent as claimed in any one of claims 100 to 109, containing liquid bleach activators, in quantities of 0.1 to 50% by weight.

111. A detergent as claimed in claim 110, wherein said bleach activators are selected from triacetin, triethyl-O-acetyl citrate, N-methyl diacetamide, isopropenyl acetate and/or N-acetyl caprolactam.

112. A detergent as claimed in claim 110 or 111, wherein said bleach activators are present in quantities of 0.1 to 40% by weight.

113. A detergent as claimed in claim 112, wherein said bleach activators are present in quantities of 0.1 to 20% by weight.

114. A detergent as claimed in any one of claims 91 to 113, containing bleaching agents and optionally other detergent ingredients.

115. A detergent as claimed in claim 114, containing particulate bleach activators.

116. A detergent as claimed in claim 115, containing enzymes.

117. A detergent as claimed in any one of claims 114 to 116, containing bleaching agents in quantities of 0.1 to 40% by weight.

118. A detergent as claimed in claim 117, wherein said bleaching agents are selected from organic peracids, alkali metal perborates and/or alkali metal percarbonates.

119. A detergent as claimed in claim 117 or 118, wherein said bleaching agents are present in quantities of 0.1 to 40% by weight.

120. A detergent as claimed in claim 119, wherein said bleaching agents are present in quantities of 5 to 25% by weight.

121. A detergent as claimed in any one of claims 114 to 120, containing particulate bleach activators in quantities of 0.01 to 20% by weight.

122. A detergent as claimed in claimed 121, containing particulate bleach activators selected from tetraacetyl ethylenediamine, pentacetyl glucose, particulate caprolactams and/or caprolactam derivatives, s odium-4-(octanoyloxy)-benzene sulfonate, undecenoyloxybenzenesulfonate, sodium dodecanoyloxybenzenesulfonate, decanoyloxybenzoic acid, dodecanoyloxybenzenesulfonate, 1,3,4,6-tetraacetyl glycoluril and/or nitrite derivatives.

123. A detergent as claimed in claim 122, wherein said bleach activators are present in quantities of 0.1 to 15% by weight.

124. A detergent as claimed in claim 123, wherein said bleach activators are present in quantities of 1 to 10% by weight.

125. A detergent as claimed in any one of claims 114 to 124, containing alkaline salts, builders and/or co-builders.

126. A detergent as claimed in claim 125, said alkaline salt are sodium carbonate, zeolite, crystalline layer-form sodium silicates and/or trisodium citrate.

127. A detergent as claimed in claim 125or 126 wherein said salts are present in quantities of 0.5 to 50% by weight.

128. A detergent as claimed in claim 125 wherein said salts are present in quantities of 0.5 to 30% by weight.

129. A detergent as claimed in any one of claims 91to 125 containing polyamide derivatives activated by polyamide structure activators in quantities of up to 20% by weight, based on the detergent as a whole.

130. A detergent as claimed in claim 129 wherein said polyamide derivatives are present in quantities of 15% by weight.

131. A detergent as claimed in claim 130, wherein said polyamide derivatives are present in quantities of 10% by weight.

132. A detergent as claimed in any one of claims 91to 131which is pseudoplastic.

133. A process for the production of the liquid laundry detergents and/or liquid dishwashing detergents claimed in any of one of claims 91 to 132, wherein (a) in a first process step, layer silicates are activated by the process claimed in any one of claims 53 to 89, (b) the mixture obtained in process step (a) is mixed with other detergent ingredients and optionally ground, (c) other substances, preferably substances sensitive to or unwanted for process step (b), are optionally added.

134. A process as claimed in claim 133, wherein step (a) and step (b) are carried out simultaneously as a one-pot process.

135. A process as claimed in claims 133 or 134, wherein steps (a) to (c) are carried out simultaneously as a one-pot process.

136. A process as claimed in any one claims 133 to 135, wherein step (a), the layer silicates are dispersed in part of the solvent or solvent mixture different from the structure activators and the resulting dispersion is diluted after activation by addition of more of the solvent or solvent mixture different from the structure activators.

137. A process as claimed in any one of claims 133 to 136, wherein step (b), a grinding and/or size-reducing process is carried out, preferably in a ring-gap ball mill or a roll mill, and the particles obtained after the grinding and/or size-reducing process are preferably between 5 and 200 µm in size.

138. A process as claimed in claim 137, wherein the particles obtained are between 5 and 50 µm in size.

139. A process as claimed in claim 137, wherein the particles obtained are between 10 and 30 µm in size.