DE4418846A1 - Water-sol. amorphous alkali metal silicate modified with organo-silicon gps., - Google Patents

Abstract

Discosed are organosilicon modified, water-soluble, amorphous alkali metal silicates with a bulk density of more than 450 g/l and a carbon content, due to organic groups, of 0.03 to 5 wt %, compounds thereof with other builder substances, methods of preparation and use as builder components in detergents and cleaners.

Description

The invention relates to the field of valuable materials and mixtures of materials the area of washing and cleaning agents for textiles and hard surfaces surfaces. Described are water-soluble silicates that form a framework substances ("Builder") and anti-corrosion agents. You are with Organo modified silicon groups, whereby the distribution of the polysilicate Anio NEN and thus the builder properties are influenced.

Work equipment of the specified type and in particular corresponding Solid concentrates together with the wash-active surfactant compound the so-called builders or builder systems as main components in addition to other usual auxiliaries and additives. The builders or builder systems fulfill a multitude in detergents and cleaning agents of tasks that deal with the constant change in composition, the form of supply and the production of detergents in recent years and decades have also changed significantly. Modern detergents today contain approx. 20 to 50% by weight builder substances. These belong there with the most important substance classes for the construction of washing and cleaning agents.

Because of the variety and evolution of detergent systems indicated here the tasks of the builders are varied and neither complete nor defined quantitatively. However, the main requirements are well described. The water softening, the strengthening of the Washing effect, graying inhibition and dirt dispersion. Builders are said to contribute to the alkalinity necessary for the washing process, a high absorption capacity for surfactants show the effectiveness of the surfactants improve, positive contributions to the properties of solid products  deliver in powder form, for example, and thus have a structure-forming effect or lower the dust problem. These different requirements can usually not be with just one builder component meet, so that usually a system of builders and co-builders is used.

For ecological reasons - please refer to the keywords of the waters eutrophication or the remobilization of heavy metals - are today Builders or builders containing phosphorus and / or nitrogen systems come under criticism as detergent components. On a large scale ge has today in particular in textile detergent formulations three-dimensionally cross-linked, water-insoluble sodium aluminosilicate zeolite NaA enforced. To a considerable extent, especially in the context of the Textile detergent, however, the use of so-called co- Builder needed, especially to counter unwanted incrustations Act. To a large extent, polymers are now being used together with zeolite NaA Polycarboxylates, especially copolymers based on acrylic acid and Ma flax acid used together with soda for this purpose. In addition often used complexing agents.

In recent times, purely silicate systems, such as the crystalline, have also become available Linen disilicate - the so-called SKS types - or combinations of such Components described with soda for use as a builder or co-builder ben. In this context, reference is made to the following, for example The following publications: EP-A-0 205 070, EP-A-0 320 770, EP-A-0 425 428, EP-A-0 502 325 and EP-A-0 548 599, in which the production of crystalline sodium silicates is described. There is still reference to be made to EP-A-0 488 868 and EP-A-0 561 656. Here are described as Builders Substance combinations of amorphous alkali metal silicates and soluble inorganic salts such as sodium carbonate, sodium sulfate, Sodium borate or perborate and other compounds of these Type, the proportion of soluble salts between 5 and 55% of the total Solids content of the batch is.

Neither zeolite A nor the crystalline layered silicates are sufficient for everyone manure requirements. With zeolite A, there are some application tech  due to the insolubility of this class of substances, which with increasing technical changes to washing machines decreasing fleet volumes to dispersion and rinsing problems to lead. The magnesium binding capacity is also insufficient. The crystalline Disilicates are only able to absorb a small amount of non-ionic surfactants. Beyond that the crystalline disilicate in atomization processes in the washing powder production at risk. Furthermore, the production of defined disilicate phases comparatively complex.

Simultaneously with the development of the zeolite NaA as a builder was featured suggest selected water-soluble amorphous sodium silicate compounds to be used as builder substances in washing and cleaning agents. Ver reference is made, for example, to US Pat. Nos. 3,912,649, 3,956,467, 3,838,193 and 3,879,527. Amorphous natri are described here umsilicatverbindungen as builder substances, which by spray drying aq water glass solutions, subsequent grinding and subsequent compression and rounding off with additional dehydration of the ground material be, cf. see, for example, FIG. 3 of US 3,912,649. The what The content of the products used is around 18 to 20 % By weight at bulk densities well above 500 g / l.

According to EP-A-0 444 415, detergents are at least 5 to 50 wt .-% of a surfactant, 0.5 to 60 wt .-% of a builder and usual washing auxiliaries proposed, the characteristic being that as An amorphous, low-water sodium disilicate with a water ge hold from 0.3 to 6 wt .-% is used. The amorphous Na is preferred trium disilicate contain 0.5 to 2 wt .-% water. The making of this highly dehydrated amorphous disilicate is carried out in a multi-stage process, the first is the production of a powdered amorphous sodium silicate provides with a water content of 15 to 23 wt .-%. This material will in a rotary kiln with flue gas at temperatures from 250 to 500 ° C in Countercurrent treated. The amorphous natri emerging from the rotary kiln umdisilicat with the help of a mechanical crusher to grain sizes of 0.1 to 12 mm crushed and then with a grinder to grain sizes grind from 2 to 400 µm.  

In contrast, the teaching of EP-A-0 542 131 aims to be a builder component usable dried crystalline sodium silicate in one Prepare process step in that a 40 to 60 wt .-% aqueous Solution of sodium silicate in a striking tool Turbo dryer is treated with hot air. The product to be dried passes through a pseudoplastic state with a free what content between 5 and 12% by weight, which is required to form a product in Granular form is used. The drying of this granulate is under Working conditions carried out that embrittlement of the granules outside casing and the associated breakage of the granulate structure eat. In this way - avoiding the so-called "popcorn" Effects "- possible, water-soluble sodium silicates with specific Ge Weights in the range between 0.5 and 1.2 to establish themselves Characterize complete solubility in water at ambient temperature.

It is known that the action of water vapor on amorphous alkali metal cate whose water solubility improves. For example, the DE-A-23 60 502 describes a process for the production of solid, water-containing Alkali silicates with improved water solubility, characterized net that one on spray or roller-dried, granular sodium or Ka Apply lium silicate water vapor at a temperature of 100 to 150 ° C leaves. It is recommended that the granular silicates be in front of the water vapor preheat effect to a temperature above 100 ° C. The W091 / 13026 describes that the treatment of sodium silicate granules with a module between 1.5 and 3.3 with water vapor the abrasion resistance of the particles increased while reducing the insoluble content.

It has already been suggested before by adding reactive silanes or during the spray drying of alkali metal silicate solutions, the pul to influence the properties of the solid products obtained favorably. At for example, US-A-4,297,163 teaches that by adding hydrophilic Silanes to a potassium silicate solution before spray drying the fluidity improve the powder obtained and bake it on the container can prevent walls. The hydrophilic silanes that can be used are said to be so contain hydrolyzable as well as non-hydrolyzable groups. In the examples are gamma-glycidoxypropyltrimethoxysilane and beta-3,4-  Cyclohexylethyldimethoxysilan used. The amounts of silanes used are 0.05 to 2.5 wt .-% based on the solids content of the solution.

EP-A-91 555 describes the production of hollow microspheres from Al potassium metal silicates and "polysalts" by spray drying, the surface of which Chen structure by spraying reactive organosilanes during the spray drying is modified. Under "Polysalzen" salts are like in understood for example sodium pentaborate and sodium hexametaphosphate. Of the The organosilicon content of these hollow spheres is between 0.01 and 4.0 % By weight. The silanes which can be used have 1 to 3 alkyl-, alkenyl- or aryl groups, with the remaining bonds of the silicon atoms by halo genes or saturated by alkoxy groups. Through the silicon organi surface modification of the hollow microspheres is intended to bring them together baking can be prevented.

DE-A-41 37 593 describes organosilicon-modified aqueous alkali silicate solutions from which transparent hydrogels can be produced, which can be used, for example, as fire protection compositions. The alkali silicate solution used to prepare the hydrogels is characterized in that it contains 3 to 70% by weight, preferably 10 to 50% by weight, of one or more water-soluble silanols of the general formula Y _y Si (OH) _x R _{4 - (x + y)} exists, optionally in precondensed form, in which the radicals Y and R are identical or different and have the following meaning: R = alkyl, alkenyl, aryl, alkylaryl or arylalkyl, Y = an organic ligand, one represents polyhydric alcohol, an amino alcohol, an aminothiol, a mercapto alcohol, a diamine, a triamine or a dithiol, or which is derived from an optionally substituted oxirane, thiirane or azirine by hydrolytic ring opening. y = 1, 2 or 3, x = 1, 2 or 3, with x + y <4.

Builders in detergents and cleaning agents have at least a double on The task to be fulfilled: On the one hand, they should have water hardness as quickly as possible bind, which is mainly in the form of calcium and magnesium ions. Secondly, they should prevent incrustations from tearing on the Some substrate, for example on the textile fibers, form an own shaft, which is also referred to with the term "secondary washing ability".  

The so-called as a measure of the incrustation on textile fibers "Ash content" used, which is obtained by ashing the fibers can. Binding of water hardness and prevention of incrustations are two different tasks due to different mechanisms are to be solved. A builder material that binds water hardness quickly, but together with the hardness forming ions as an incrustation on the fiber would be completely useless as a detergent ingredient.

Alkali metal silicates with a module (= molar ratio SiO₂: M₂O) of 1 and above and especially those with a module of 2 and above Solutions in which the silicate anions are monomeric, linear and in particular cyclic oligomers and as polymers, colloidal polyanions available. The interaction of the polyanions with the cations of water hardness depends on the structure of the polyanions, which u. a. through the module being affected. (Compare, for example, J.S. Falcone Jr. (editor): "Soluble Silicates", ACS Symposium Series 194, American Chemical Society (1982), Chapters 7 and 9.). Measures the structure of the polyanions can influence, for example in the sense of an end group closure therefore lead to changed builder properties.

EP-A-4 112 also has the task of determining the structures of the poly to influence silicate anions in alkali metal silicates. this happens in that the growth of the polysilicate chains by end group closure by reaction with carboxylates of selected metals (Al, Ti, Zn, Zr, Sn, V, Mo, W, Se, Ge) is restricted. The use of these "end groups sealed "alkali metal silicates in detergents is also bean speaks.

It is the object of the present invention to provide a water-soluble build to provide the system based on alkali metal silicates, its builder properties both in terms of water softening as well are optimized with regard to incrustation inhibition.

This object is achieved by organically modified water-soluble amorphous alkali metal silicates with a bulk density of more than 450 g / l and one caused by organic groups bound to silicon  Carbon content from 0.03 to 5 wt .-%.

The term "amorphous" means "X-ray amorphous". This means that the Alkali metal silicate powder not sharp in X-ray diffraction experiments X-ray reflections, which are typical for crystalline substances, but at most one or more maxima of the scattered x-ray lung, which is a width of several degree units of the diffraction angle point. However, it is very possible and can even be particularly good Builder properties cause the organosilicon modified to X-ray genamorphic alkali metal silicate particles of the present invention Electron diffraction experiments blurred or even sharp diffraction deliver xima. This is to be interpreted as meaning that the products are microcritical stalline ranges from size 10 to a few hundred nm.

As a parameter for the organosilicon modification, the by Silicon-bonded organic groups caused the carbon content of the Al potassium silicates can be used. This is by usual analyti techniques such as combustion analysis can be determined. For the purpose of The invention has carbon contents of 0.03 to 5% by weight Lich the total mass of the amorphous alkali, which is usually still water-containing metal silicates proved to be particularly favorable. With lower carbon no noticeable effect occurs while significantly higher coals content negatively influences the dissolving behavior of the alkali silicate powder sen. The groups bonded to silicon are preferably selected from Alkyl, alkenyl, aryl, alkylaryl or arylalkyl groups, given if can be substituted.

Alkali metal silicates with a modulus <1 provide strongly alkaline aqueous Solutions that can be disadvantageous when washing delicate fabrics. Therefore, in the sense of the present invention, less alkaline systems me preferred. In contrast, silicates with a module <3.5 have an unfavorable Solution behavior, so that such alkali metal silicates are preferred at which the module is in the range between 1.0 and 3.5. Particularly preferred are alkali metal silicates with a modulus in the range 1.4 to 2.5.

Sodium and / or potassium silicas are preferably used as alkali metal silicates  cate used. Because of the lower price of sodium silicates, they are preferred for economic reasons. In contrast, potassium silicates have the advantage of increased solubility, so that for applications in which a particularly good solubility an application-technical advantage brings, potassium silicates are preferred. For example, the silica te have a potassium content, calculated as K₂O, of up to 5% by weight.

Spray-dried water glasses usually fall with a residual amount of water hold (determined by expelling the water at 800 ° C) from about 18 to about 25% by weight. By means of suitable measures, for example heating in a fluidized bed or in a rotary kiln, the water content can be reduced to ge lower values can be reduced. You evaporate a water glass solution Use of a so-called turbo dryer, such as in the EP-A-542 131 described, products with water contents between about 5% and about 12% by weight. It has been shown that X-ray amor phe powdered or granulated alkali metal silicates with water content below 15% by weight and especially in the range from 5 to 12% by weight have favorable washing properties. Accordingly, in the For the purposes of the present invention, alkali metal silicates are preferred which have a average water content below 25% by weight, preferably below 15 Have wt .-% and in particular in the range of 5 to 12 wt .-%.

For use in ready-made detergent and cleaning agent powders it is desirable that the particle size of the metal silicate particles un corresponds to that of the other powder components to demix to avoid symptoms of appearance. Therefore, such are according to the invention Alkali metal silicates are preferred which consist of at least 50% by weight of particles with a diameter in the range between 0.1 and 2 mm and preferably exist between 0.5 and 1.5 mm.

Preferred alkali metal silicates are those whose bulk density is in the range that of contemporary compact detergents. So you control it Preparation of the alkali metal silicates according to the invention preferably so that the products have a bulk density between 0.5 and 1.2 kg / l and in particular which have between 0.7 and 1.1 kg / l. If necessary, this can Product can be further compressed by suitable measures, for example  through granulation, roller compaction and / or extrusion.

It is known that beneficial effects in terms of water softening and Incrustation inhibition can be observed when using a builder compound sets, in which the closest possible spatial proximity solvable ches silicate and soluble carbonate coexist, for example se in the form of sodium silicate-soda compounds. As a mechanism of action for this it can be assumed that the carbonate ions together with the Calcium ions lead to the formation of germs, their further growth and / or prevented from being drawn onto the fiber by the polysilicate anions becomes. Such effects are also found in the silicon organ according to the invention nisch modified alkali metal silicates observed. Accordingly, it is in the Within the scope of the present invention that the organosilicon modified Alkali metal silicates are combined with other builder substances and / or adjusting agents, preferably selected from alkali metal carbonate or bicarbonate, alkali metal oligo- or polyphosphate and / or Alkali metal sulfate, preferably as sodium and / or potassium salts, wherein the proportion of the other builder substances and / or adjusting agents based on the dry matter content of the alkali metal silicate components between 5 and is 120% by weight.

If there is any mention in this context of actuating means, then this is the case to understand such substances that influence the powder structure, but do not actively intervene in the washing process. In particular, as a means of adjustment special sodium sulfate known. However, it cannot be ruled out that the Installation of adjusting agents, especially sodium sulfate, in the inventions alkali metal silicate particles according to the structure of the Si licate polyanions and thereby indirectly affects the builder effect. Indications of such an influence are, for example, in the US-A-3,879,527 included.

At what proportions of silicate to soda optimal properties with regard to primary and secondary washing ability depends among other things from the existing water hardness and from the other Be components of the wash liquor. Generally is from the state of the art known to use silicate-soda compounds in which the soda content between  is 5 and 120 wt .-% of the alkali metal silicate components. Spe Compounds are described in the prior art, in which the Soda content on the one hand between 7.5 and 25% by weight with respect to the Alkali metal silicate components, on the other hand between 55 and 95 % By weight based on the alkali metal silicate components. Analogously to this these quantity ranges are also for the silicon organ according to the invention nisch modified alkali metal silicates preferred.

The modified alkali metal silicates according to the invention can by Ver set aqueous alkali metal silicate solutions with organosilicon compounds gene, the at least one hydrolysis-stable organic group and one to carry three reactive groups, followed by different drying processes drive, be preserved.

An example of this is the following process sequence:

• a) adding an solid to an aqueous alkali metal silicate solution substance content between 25 and 55% by weight with an organosilicon compound dung, the at least one hydrolysis-stable organic group and a up to three reactive groups,
• b) drying this mixture by evaporation of water under the action of vacuum and / or thermal energy and / or electromagnetic Radiation such as microwaves,
• c) if desired, compacting the product from step b) by milling len, by compacting or mechanical processing in a turbo dryer, each optionally followed by or associated with a Drying.

For the organosilicon-modified alkali metals according to the invention Licenses and for the processes for their production can be found in the above step a) generally one or more organosilicon compounds of the general Formula (I)

X _a Si (OH) _b R _4-ab (I)

are used, whereby
X represents halogen, preferably chlorine, and / or a hydrolytically removable or a hydrophilic organic ligand,
R represents one or more alkyl, alkenyl, aryl, alkylaryl or arylal kylgruppen, which may optionally be substituted
and a and b can mean 0, 1, 2 or 3 with the restriction that a + b = 1, 2 or 3.

The implementation of alkali silicate solutions with such organosilicon ver bindings for the production of transparent hydrogels is in the prior art Technology known (DE-A-41 37 593). The present invention distinguishes differs from this teaching in that products in the form of free-flowing particles be obtained and that to maintain the water solubility of these particles shaped products the degree of modification is limited so that the carbon content caused by organic groups bonded to silicon of the products does not exceed 5% by weight.

The organosilicon compounds mentioned in the aforementioned DE-A-41 37 593 are also suitable for the present invention.

The radical R in the general formula (I) can be alkyl, alkenyl, aryl, alkyl be aryl or arylalkyl. The alkyl radicals are e.g. B. straight chain, ver branched or cyclic radicals with 1 to 20, preferably with 1 to 10 Koh len atoms, and particularly preferred are lower alkyl radicals with 1 up to 6 carbon atoms. Specific examples are methyl, ethyl, n-pro pyl, i-propyl, n-butyl, s-butyl, t-butyl, i-butyl, n-pentyl, n-hexyl, Cyclohexyl, 2-ethylhexyl, dodecyl and octadecyl.

The alkenyl residues are e.g. B. straight-chain, branched or cyclic radicals with 2 to 20, preferably with 2 to 10 carbon atoms, and especially lower alkenyl radicals having 2 to 6 carbon atoms, such as e.g. B. vinyl, allyl or 2-butenyl.  

Aryl radicals are preferably phenyl, biphenyl and naphthyl. The alkoxy, Acyloxy, alkylcarbonyl, alkoxycarbonyl and amino radicals are derived preferably from the alkyl and aryl radicals mentioned above. Special case games are methoxy, ethoxy, n- and i-propoxy, n-, i-, s- and t-butoxy, Methylamino, ethylamino, dimethylamino, diethylamino, N-ethylanilino, Ace tyloxy, propionyloxy, methylcarbonyl, ethylcarbonyl, methoxycarbonyl, eth oxycarbonyl, benzyl, 2-phenylethyl and tolyl.

The radicals mentioned can optionally have one or more substituents wear, e.g. B. halogen, alkyl, hydroxyalkyl, alkoxy, aryl, aryloxy, alkyl carbonyl, alkoxycarbonyl, furfuryl, tetrahydrofurfuryl, amino, alkylamino, Dialkylamino, trialkylammonium, amido, hydroxy, formyl, carboxy, mercapto, Cyano, isocyanato, nitro, epoxy, SO₃H and PO₄H₂. Among the halogens are Fluorine, chlorine and bromine preferred.

The radical X in the general formula (I) is a halogen or a hydro lytically cleavable or a hydrophilic ligand, which one or polyhydric alcohol, an amino alcohol, an aminothiol, a mercapto represents alcohol, a diamine, a triamine or a dithiol. X can also an optionally substituted oxirane, thiirane or azirine or a thereof can be obtained by hydrolytic ring opening. Preferred X is usually a monovalent alkoxy radical with one to four C atoms, i.e. a methoxy, ethoxy, propoxy or butoxy group.

It is further preferred if X is derived from a glycidoxymethyl, 2-gly cidoxyethyl, 3-glycidoxypropyl, 4-glycidoxybutyl, glycidylmethyl, Derives 2-glycidylethyl, 3-glycidylpropyl or 4-glycidylbutyl radical, where glycidoxy is the grouping  

and glycidyl the grouping

means.

Drying according to sub-step b) is preferably carried out by spray drying tion using a gaseous drying medium, preferably heated air or superheated steam, with a gas inlet temperature between 150 and 300 ° C and collecting the powdery drying product.

Alternatively, drying the modified aqueous silicate solution using a so-called turbo dryer. This dry Process used for the silicates of the present invention can be detected is described in EP-A-526 978 and EP-A-542 131. Accordingly, the drying in sub-step b) can be carried out by entering the Solution from sub-step a) in a granulation dryer (= turbo dryer) in Shape of a drum in which one is equipped with a multitude of arms Shaft at a speed of 400 to 1200 revolutions per minute rotates, the wall of the dryer preferably a temperature in the loading has rich 150 to 250 ° C and the drying process preferably through Supply of a gas mixture heated to 200 to 400 ° C is supported.

Furthermore, it is known in the prior art to granulate silicate particles and thereby increase their bulk density by using the silicate particle in a fluidized bed with a silicate solution and here brought about by particle enlargement. Such a procedure will described for example in DE-A-22 30 158. In a similar way can with the organosilicon modified silicate solution according to the invention  Solution are moved, this silicate solution on preformed silicate particles of the same or different composition with regard to Mo dul and / or organosilicon modification sprayed as the solution can be. The modified alkali metal silicates according to the invention can NEN can also be obtained by spraying the solution from sub-step a) on a moving bed of a germ material in the form of amorphous alkali tall silicate particles with the same module as the sprayed solution or with a module different from this, the seed material in turn sili ciumorganically modified. Excess water is evaporated by supplying energy, preferably by supplying heat.

Compounds made from alkali metal silicates and at least one of the first there are other builder substances and / or adjusting agents mentioned, can be most easily obtained by adding these additional buil dersubstanzen and / or adjusting means in that produced in sub-step a) Alkali metal silicate solution before or after reaction with the organosilicon dissolves connection and this solution one of the above dry processes. Such a method using a silicate solution not modified with organosilicon is, for example, in DE-A-22 29 985. Analog can with an alkali metal silicate Solution process that are silicon in the sense of the present invention was organically modified. The other builder substances and / or Adjusting agents are preferably selected from sodium carbonate or hydrocarbon gene carbonate, sodium percarbonate, sodium perborate, sodium phosphate, penta contain sodium triphosphate, sodium citrate, sodium glycinate, the Proportion of other adjusting agents and / or builder substances related to the Dry matter content of the alkali metal components between 5 and 120 % By weight.

Alternatively, particles of the other builder substances and / or Adjusting agent with an organically modified alkali metal silicate solution coated and / or granulated. This creates compounds of a type described, for example, in EP-A-561 656. Erfin Products according to the invention differ from this in that the silicate component is organosilicon modified.  

Accordingly, the invention also includes methods of making compounds from the organically modified alkali metal silicates and others Builder substances and / or adjusting agents, taking the solution from part step a) on a moving bed of a germ material consisting of a water-soluble inorganic or organic alkali metal salt, preferred wise sodium carbonate or hydrogen carbonate, sodium percarbonate, sodium perborate, sodium phosphate, pentasodium triphosphate, sodium citrate, natri umglycinate, sprayed and excess water by energy supply, before preferably evaporated by supplying heat.

Units for spraying a solution onto a moving bed of a Keimma terials are known to the person skilled in the art. For example, are particularly suitable Granulating plate that rotates about an axis inclined relative to the vertical ren, or rotating drums, the axis of rotation preferably a Nei have horizontal and preferably with mixing A buildings are provided. Agglomeration can also advantageously be carried out in one fluidized fluidized bed gas flow. It is preferable that the material to be agglomerated has a temperature between 20 and 130 ° C, in particular between 60 and 120 ° C.

Finally, the invention relates to the use of the invention organosilicon-modified alkali metal silicates based on the previous described ways are available, as corrosion protection and / or Builder component in detergents and / or washing processes for textiles laundry, in automatic dishwashing detergents and / or hard detergents Surfaces. The anti-corrosion effect of the agents according to the invention eats particularly against metallic surfaces. The fiction appropriate use takes place in the presence of further, for washing and cleaning required components. Such components include in particular special surface-active substances such as nonionic and / or anionic Surfactants of fat and / or oliochemical origin, and depending on the application other auxiliary substances required for the purpose, such as bleaching agents, Proteins and / or starch-splitting enzymes, optical brighteners, complex image ner, other builder components such as phosphates and gelebe if necessary, other components known to the person skilled in the art.  

The use of the organosilicon-modified alkali according to the invention metal silicate is preferably carried out in such a way that a solid Mischpro product that, in addition to the alkali metal silicates according to the invention contains other active and auxiliary components. The ready-to-use washing or cleaning liquor is created by dissolving this solid mixed product in Water. Of course, the agents according to the invention can also be used as so-called modular components are used by separating them of the other active ingredients and auxiliary substances in the washing or cleaning solution gives.

If desired, the organosilicon can be modified according to the invention alkali metal silicates for use as a component in washing and cleaning detergent with other liquid or easily meltable detergents tel ingredients, preferably nonionic surfactants, are loaded.

In the following, information on Mi Research components made in connection with the invention Alkali metal silicates can be used. Basically it says here the entire range of valuable and auxiliary materials from the field of washing and detergents available. Anio surfactants in particular come here African, non-ionic, cationic, amphoteric and / or zwitterioni structure and other inorganic and / or organic buildersub punches, bleaches and bleach activators, enzymes and enzyme stabilizers foam inhibitors, optical brighteners, inorganic alkaline and / or salts reacting neutral in water, for example sulfates or Chlorides, and colors and fragrances.

The surfactants of the sulfonate type are preferably the known C₉-C₁₃-Al kylbenzenesulfonates, olefinsulfonates and alkanesulfonates. Appropriate Also net are esters of α-sulfo fatty acids or the disalts of α-sulfo fatty acids. Other suitable anionic surfactants are sulfated fatty acid glycols rinesters, which are mono-, di- and triesters and their mixtures, as in the preparation by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol can be obtained.  

Suitable surfactants of the sulfate type are the sulfuric acid monoesters from pri ferment alcohols of natural and synthetic origin, in particular from Fatty alcohols, e.g. B. from coconut oil alcohol, tallow oil alcohol, oleyl alcohol, Lauryl, myristyl, cetyl or stearyl alcohol, or the C₁₀-C₂₀ oxoalko pick, and those secondary alcohols of that chain length. Also the Sulfuric acid monoesters of Al. Ethoxylated with 1 to 6 moles of ethylene oxide alcohols, such as 2-methyl-branched C₉-C₁₁ alcohols with an average of 2 or 3.5 moles of ethylene oxide are suitable.

Preferred anionic surfactant mixtures contain combinations of alk (en) yl sulfates, especially mixtures of saturated and unsaturated fatty alcohol sulfates, and alkylbenzenesulfonates, sulfated fatty acid glycerin esters and / or α-sulfofatty acid esters and / or alkyl sulfosuccinates. Ins Mixtures which are preferred as anionic surfactants are particularly preferred Alk (en) yl sulfates and alkyl benzene sulfonates and optionally α-sulfo fatty acid contain methyl esters and / or sulfonated fatty acid glycerol esters.

Soaps, in particular, are particularly suitable as further anionic surfactants Amounts below 5% by weight. Saturated fatty acids are suitable soap, such as the salts of lauric acid, myristic acid, palmitic acid or Stearic acid, and in particular from natural fatty acids, e.g. B. coconut, Palm kernel or tallow fatty acids, derived soap mixtures. Unsaturated Fatty acid soaps, which are derived from oleic acid, for example also be present, however their share of the soaps is said to be 50 Do not exceed% by weight.

The anionic surfactants and soaps can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, Di- or triethanolamine. The anionic are preferably located Surfactants in the form of their sodium or potassium salts, especially in the form of Sodium salts. The content of anionic surfactants in the agent is generally between 5 and 40% by weight.

Preferred nonionic surfactants are alkoxylated, advantageous generally ethoxylated, especially primary alcohols with preferably 8 up to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole  Alcohol used in which the alcohol residue is linear or preferably in 2- Position can be methyl branched or linear and methyl branched radicals can be contained in the mixture, as is usually the case in oxo alcohol residues available. In particular, however, are alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, e.g. B. from coconut, Palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per Mole of alcohol preferred. Preferred ethoxylated alcohols include for example C₁₂-C₁₄ alcohols with 3 EO or 4 EO, C₉-C₁₁ alcohol with 7 EO, C₁₃-C₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C₁₂-C₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C₁₂- C₁₄ alcohol with 3 EO and C₁₂-C₁₈ alcohol with 5 EO. The specified ethoxy The degrees of lation represent statistical averages that are required for a special Product can be an integer or a fractional number. Preferred alcohol holethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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

Other suitable surfactants are polyhydroxy fatty acid amides of the formula (II),

in the R²CO for an aliphatic acyl radical with 6 to 22 carbon atoms men, R³ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 Carbon atoms and [Z] for a linear or branched polyhydro  xyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands.

The proportion of nonionic surfactants in the agents is generally NEN 2 to 25 wt .-%.

As other inorganic builder substances, all previous übli usually used builder substances are used. Too tough len in particular zeolites, crystalline layered silicates, even phospha if their use should not be avoided for ecological reasons te. Their content can vary depending on the content of the invention Alkali metal silicates vary in a wide range. The sum of usual builder substances and the silicates according to the invention usually 10 to 60% by weight.

Useful organic builder substances are preferred, for example polycarboxylic acids, such as lemons, used in the form of their sodium salts acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, Aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such an is not objectionable for ecological reasons, as well as mixtures from these. Preferred salts are the salts of polycarboxylic acids such as Ci tronic acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

Suitable polymeric polycarboxylates are, for example, the sodium salts polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 800 to 200,000 (based on acid). Ge Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with malein have proven particularly suitable proven acid, the 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% Ma contain linseic acid. Their relative molecular mass, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. Organic are also particularly preferred Degradable terpolymers, for example those which are salts of the monomers Acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol deri  vate (P 43 00 772.4) or the monomers as salts of acrylic acid and Contain 2-alkylallylsulfonic acid and sugar derivatives (P 42 21 381.9).

Other suitable builder systems are oxidation products from carboxylgrup pen-containing polyglucosans and / or their water-soluble salts, such as them for example in international patent application WO-A-93/08251 be written or their production, for example, in the internatio Nalen patent application WO-A-93/16110 or the older German patent message P 43 30 393.0 is described.

In addition, the agents can also contain components which and grease washability from textiles positively. This effect becomes particularly clear when a textile that is already soiled is soiled previously several times with a detergent according to the invention that this oil and contains fat-dissolving component, is washed. Among the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl hydroxypropyl cellulose with a proportion of methoxyl group pen from 15 to 30 wt .-% and hydroxypropoxyl groups from 1 to 15 % By weight, based in each case on the nonionic cellulose ether, and polymers of phthalic acid and / or of known from the prior art Terephthalic acid or its derivatives, in particular polymers of ethyl lenterephthalates and / or polyethylene glycol terephthalates.

In addition to the silicates, the agents can also be water-soluble inorganic salts such as bicarbonates and carbonates, preferably in their Alkali metal salt form included. The content of sodium carbonate in the agent can, for example, up to about 20% by weight, preferably between 5 and 15 wt .-% and is a content of the inventions Silicates according to the invention of above 20% by weight, in particular at values up to about 10% by weight. According to the teaching of the older German patent application P 43 19 578.4 can also alkali carbonates through sulfur-free, 2 to 11 coals Substance atoms and optionally a further carboxyl and / or amino group having amino acids and / or their salts are replaced. As part of In this invention, it is preferred that a partial to complete replacement of the alkali carbonates by glycine or glycinate.  

Among the serving as bleach, H₂O₂ in water supplying verb have sodium perborate tetrahydrate and sodium perborate mono hydrate special meaning. Other useful bleaches are in for example sodium percarbonate, peroxypyrophosphates, citrate perhydrates so such as H₂O₂ supplying peracidic salts or peracids such as perbenzoates, per oxophthalates, diperazelaic acid or diperdodecanedioic acid. The salary of the Bleaching agent is preferably 5 to 25% by weight and in particular especially 10 to 20 wt .-%, advantageously perborate monohydrate is set.

To improve when washing at temperatures of 60 ° C and below To achieve bleaching effects, bleach activators can be incorporated into the preparations be worked. Examples of this are organic peracids with H₂O₂ forming N-acyl or O-acyl compounds, preferably N, N'-tetra-acy gelled diamines, also carboxylic anhydrides and esters of polyols such as Glucose pentaacetate. Other known bleach activators are acetylated Mixtures of sorbitol and mannitol, such as those found in the euro European patent application EP-A-0 525 239. The salary of the Bleach-containing agents on bleach activators are in the usual Range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight. Particularly preferred bleach activators are N, N, N ', N'-tetra acetylethylenediamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN).

When used in machine washing processes, it can be an advantage Add usual foam inhibitors. Suitable as foam inhibitors soaps of natural or synthetic origin, for example have a high proportion of C₁₈-C₂₄ fatty acids. Suitable non-surfactant Like foam inhibitors are, for example, organopolysiloxanes and their Mixtures with microfine, possibly silanized silica and paraffins, Waxes, microcrystalline waxes and their mixtures with silanized pebbles acid or bistearylethylenediamide. Mixtures are also advantageous various foam inhibitors used, e.g. B. those made of silicone, Pa refined or waxing. The foam inhibitors are preferred, in particular their silicone or paraffin-containing foam inhibitors, to a granular, water-soluble or dispersible carrier substance bound. In particular  others are mixtures of paraffins and bistearylethylenediamides prefers.

Enzymes come from the class of proteases, lipases, amylases, Cellulases or their mixtures in question. Are particularly well suited Strains of bacteria or fungi such as Bacillus subtilis, Bacillus lichenifor mis and Streptomyces griseus enzymatic substances obtained. Preferential Proteases of the subtilisin type and in particular proteases that are obtained from Bacillus lentus. There are enzyme mixtures gene, for example from protease and amylase or protease and lipase or Protease and cellulase or from cellulase and lipase or from protease, Amylase and lipase or protease, lipase and cellulase, especially each but cellulase-containing mixtures of particular interest. Peroxi too In some cases, these or oxidases have proven to be suitable. The enzymes can be adsorbed on carrier substances and / or in coating substances embedded to protect them against premature decomposition. The An Part of the enzymes, enzyme mixtures or enzyme granules can for example about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

The stabilizers come in particular for per-compounds and enzymes Salts of polyphosphonic acids, especially 1-hydroxyethane-1,1-diphosphone acid (HEDP), diethylenetriaminepentamethylenephosphonic acid (DETPMP) or Ethylenediaminetetramethylenephosphonic acid (EDTMP) into consideration.

Graying inhibitors have the task of removing the fiber To keep dirt suspended in the fleet and thus turn graying prevent. For this purpose, water-soluble colloids are mostly organic in nature suitable, for example the water-soluble salts of polymeric carboxylic acids, Glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids Starch or the cellulose or salts of acidic sulfuric acid esters Cellulose or starch. Also water-soluble containing acidic groups Polyamides are suitable for this purpose. Furthermore, soluble ones Use starch preparations and other starch products than those mentioned above, e.g. B. degraded starch, aldehyde starches etc. Polyvinylpyrrolidone is also useful. However, cellulose ethers such as carboxymethyl cellu are preferred loose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as  Methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxy methyl cellulose and mixtures thereof, and polyvinyl pyrrolidone, for example as used in amounts of 0.1 to 5 wt .-%, based on the agent.

The agents can, as optical brighteners, derivatives of the diaminostilbene contain sulfonic acid or its alkali metal salts. Are suitable for. B. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) style ben-2,2'-disulfonic acid or similar compounds, which replace the morpholino group with a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type can also be used be essential, e.g. B. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4′-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 ′ - (2- sulfostyryl) diphenyls. Mixtures of the aforementioned brighteners can also be used.

The bulk density of the preferred granular washing or cleaning agents, which contain the silicates according to the invention is in general 300 to 1200 g / cm³, but preferably 500 to 1100 g / cm³. Most notably washing and cleaning agents with bulk densities of are preferred at least 700 g / cm³. They can be manufactured according to any of the known Ver drive like mixing, spray drying, granulating and extruding, the silicates according to the invention advantageously to the others Components of the agent are added. Are particularly suitable such processes in which several sub-components, for example spray dried components and granulated and / or extruded components be mixed together. Especially in granulation and extrusion tion process, it is preferred to use any anions present side in the form of a spray-dried, granulated or extruded Com pounds either as an admixture in the processes mentioned or as Additive additive to other granules. It is also possible Lich and can be advantageous depending on the recipe, if white tere individual components of the agent, for example carbonates, citrate or citric acid or other polycarboxylates or polycarboxylic acids, po polymeric polycarboxylates, zeolite and / or layered silicates, for example layered crystalline disilicate, subsequently spray-dried, granulated and / or extruded components are added.

Embodiments Manufacturing Examples 1-19

For the production of organically modified water-soluble amorphous Sodium silicates became technical water glass solutions with different Module (SiO₂: Na₂O molar ratio) and different solids contents reacted with silanes that both hydrolyzable groups X and not hydrolyzable residues R contributed. In Table 1 are the water glass output solutions, their composition, the silane component and their amount as well the analytically determinable carbon content is listed. Relate the amounts given in the table per 1,000 g of water glass starting solution.

Water glass solutions were used to prepare the modified silicates gene with the specified amount of silane components and at 60 ° C. stirred for 4 hours. After that, the solutions, if necessary after dilution with water to a pumpable consistency, in a laboratory Spray dryer (Büchi company, air inlet temperature 190 ° C, air outlet temperature 105 ° C) dried to a free-flowing powder. The powder had bulk densities of around 450 g / l. By heating samples to 800 ° C the sum of water content and organic load was determined. The values obtained are given in Table 1. This gives the what sergehalt the powder, if one analytically from the given in Table 1 Determinable carbon content is the proportion by weight of the non-hydrolysable ren organic groups R calculated [conversion factor = (molar mass R ge together): (molar mass C in R)] and this from the loss on ignition at 800 ° C pulls.

Preparation example 20 Silicate-soda compound

A solution prepared according to Example 9 was after the reaction with the silane components with 350 g of anhydrous soda per 1 000 g of solution added so that a weight ratio of soda to sodium silicate of 1: 1 resulted. The solution was diluted to 3 liters with water and as before  spray dried standing. The bulk density of the powder obtained was 550 g / l.

Manufacturing Example 21 Silicate-soda compound

According to Example 2, 1,000 g of the water glass solution with the silane components implemented. After the end of the reaction, the solution was dissolved in water Diluted 3 liters and mixed with 218 g of anhydrous soda, see above that a weight ratio of soda to sodium silicate of 1: 2 resulted. The solution was spray dried as above. The powder obtained has a bulk density of 510 g / l.

Preparation example 22 Silicate-soda compound

On a turntable, the axis of rotation of which is 55 ° relative to the horizontal 500 g of anhydrous soda (bulk density 550 g / l, average rer particle diameter 95 µm) applied. During the turntable at 30 Revolutions per minute became 1,000 g in the course of 30 minutes a reaction solution according to Example 2 at a temperature of 60 ° C. the soda sprayed. After the end of the jet, the turntable was still for Rotated for 15 minutes. The moist powder obtained was converted into a Mixing drum transferred, the walls of which were heated to 90 ° C and for 30 Dried minutes with the drum spinning.

The powder obtained had a bulk density of 820 g / l and an average ren particle diameter of 0.7 mm. The weight ratio of soda: sodium silicate was 1.15: 1.

Production Example 23 "Turbo dryer"

A reaction solution prepared according to Example 2 was placed in a turbo dryer / granulator from VOMM (Italy), which is described in EP-A-542 131 nä is described here, registered. The rotor of the turbo dryer was rotating  with 980 revolutions per minute, the wall temperature was 180 ° C, the tem temperature of the hot gas (air) used 250 ° C. The dwell time of the pro product in the turbo dryer was about 90 seconds. The product obtained had a loss on ignition (800 ° C) of 7.3%, a bulk density of 890 g / l and an average particle size between 0.8 and 1 mm.

Preparation example 24 "Turbo dryer"

A reaction solution according to Example 9 was among the ge in Example 23 named conditions in the turbo dryer dried / granulated. Get that The product had a bulk density of 910 g / l, an average particle Size in the range 0.8 to 1 mm and a loss on ignition (800 ° C) of 6.9%.

Preparation example 25 Drying / roller compaction

The spray-dried product of Example 4 was in a to 180 ° C. heated kneader with counter-rotating sigma blades for 30 mi grooves dried and then at a pressure of 17 kN per cm on a WR 50 N / 75 roller press (Alexanderwerk AG, Germany) pressed at room temperature into scales of approx. 1 mm thickness. After the Zer reduction to a granulate with an average grain spectrum of 0.1 to 1.6 mm was a product with a bulk density of 900 g / l and a Obtained loss on ignition (800 ° C) of 9.5%.

Application tests

A selection of the above products as well as a comparison product was subjected to application tests, with which the prin partial suitability of the products as builder substances for washing and cleaning agents could be determined. The exams are as follows described in more detail, their results are summarized in Table 2.  

Dissolving behavior

500 mg of the sample are placed in 1 l of water heated to 25 ° C. Of the The conductivity curve and the pH value are recorded in parallel. When Na-SKS-6® (crystalline sodium disilicate with layer structure tur, commercial product from Hoechst, Germany). Its conductivity after 10 minutes it is set as a 100% value.

Calcium binding capacity

The Ca binding capacity was determined by adding a defined amount of the sample to be examined to a Ca ²⁺ solution of 30 ° d, which had been adjusted to pH 10 with dilute sodium hydroxide solution. The mixture was stirred for 10 minutes at room temperature and then filtered through a membrane filter (<0.45 μm). The content of Ca ²⁺ ions in the filtrate was determined complexometrically by titration against EDTA and converted into the calcium binding capacity in mg CaO / g active substance.

Deposits on the heating element

10 l of process water (hardened to 30 ° d Ca / Mg 5: 1 mixed hardness) are in a stainless steel vessel filled with a heating rod and with 1.67 g of the test appropriate sample. The mixture is heated to 90 ° C. within 30 minutes and held at this temperature for a further 30 minutes. After cooling and Draining the water is repeated four more times.

The deposits on the heating element are removed with an alkaline citrate solution and analyzed analytically for Ca, Mg and SiO₂.  

Claims (14)

1. Siliconically organically modified water-soluble amorphous alkali metalsi licate with a bulk density of more than 450 g / l and one through Silicon-bonded organic groups caused carbon content of 0.03 to 5% by weight. 2. Organically modified silicon alkali metal silicates according to claim 1, characterized in that the alkali metal is selected from natri um, potassium or a mixture thereof and preferably sodium represents, the molar ratio (= module) SiO₂: M₂O (M = alkali tall) is between 1.0 and 3.5, preferably between 1.4 and 2.5. 3. Silicon organically modified alkali metal silicates according to one or both of claims 1 and 2, characterized in that the Sili cium-bonded organic groups are selected from alkyl, alkene nyl, aryl, alkylaryl or arylalkyl groups, which are optionally sub can be substituted. 4. Silicon organically modified alkali metal silicates according to one or several of claims 1 to 3, characterized in that they have a Bulk density between 500 and 1200 g / l, preferably between 700 and Have 1100 g / l. 5. Silicon organically modified alkali metal silicates according to one or several of claims 1 to 4, characterized in that they have a Water content below 20% by weight, preferably below 15% by weight and in particular have in particular in the range of 5 to 12 wt .-%. 6. Silicon organically modified alkali metal silicates according to one or several of claims 1 to 5, characterized in that they consist of Particles exist that besides the alkali metal silicates what water-soluble adjusting agents and / or builder substances, preferably from selected from sodium carbonate or hydrogen carbonate, sodium percarbo nat, sodium perborate, sodium phosphate, pentasodium triphosphate, Na  trium citrate, sodium glycinate, the proportion of the further Adjusting agents and / or builder substances based on the dry substance Punch content of the alkali metal components between 5 and 120 wt .-% be wearing. 7. Process for the preparation of organosilicon-modified alkali metal silicates according to one or more of claims 1 to 5, characterized by the process sequence:

• a) adding an aqueous alkali metal silicate solution with a solids content between 25 and 55 wt .-% with an organosilicon compound, which carries at least one hydrolysis-stable organic group and one to three reactive groups, as organosilicon compound one or more compound (s) of the general For mel (I) X _a Si (OH) _b R _4-ab (I) can be used, where
  X represents halogen, preferably chlorine, and / or a hydrolytically cleavable or a hydrophilic organic ligand,
  R represents one or more alkyl, alkenyl, aryl, alkylaryl or arylalkyl groups, which may optionally be substituted
  and a and b can mean 0, 1, 2 or 3 with the restriction that a + b = 1, 2 or 3.
• b) drying this mixture to a powder product by evaporating water under the action of vacuum and / or thermal energy and / or electromagnetic radiation, in particular microwaves,
• c) if desired, compressing the product from step b) by milling, by compacting or mechanical processing in a turbo dryer, in each case optionally followed by or combined with post-drying.

8. The method according to claim 7, characterized in that the drying in step b) is carried out by spray drying this mixture with Ver Use of a gaseous drying medium, preferably heated Air or superheated steam, with a gas inlet temperature between 150 and 300 ° C and collecting the powdery drying product. 9. The method according to claim 7, characterized in that the drying in step b), this mixture is introduced into a granule lier dryer (= turbo dryer) in the form of a drum in which one with a variety of arms equipped shaft at one speed rotates from 400 to 1200 revolutions per minute, the wall of the Dryer preferably at a temperature in the range of 150 to 250 ° C. and the drying process preferably by supplying one to 200 up to 400 ° C heated gas mixture is supported. 10. The method according to claim 7, characterized in that the drying in step b) is carried out by spraying the solution onto a moving Bed of seed material in the form of amorphous alkali metal silicate particles with the same module as the sprayed solution or with ver different module, the seed material being modified organosilicon and evaporation of water, preferably by applying heat. 11. Process for the preparation of organosilicon-modified alkali metals tall silicates according to claim 6, characterized in that one according to claim 7, sub-step a) solution obtained on a moving bed a germ material consisting of a water-soluble inorganic or organic alkali metal salt, preferably sodium carbonate, Na trium percarbonate, sodium perborate, sodium phosphate, pentasodium tri phosphate, sodium citrate, sodium glycinate, sprayed on and excess Water evaporates, preferably by applying heat.   12. The method according to claim 10 or 11, characterized in that the moving bed of the germ material by moving the germ material on a pelletizing plate which is inclined relative to the vertical Axis rotates, possibly inclined relative to the horizontal th and preferably with rotating internals provided rotating Drum or by fluidizing with a gas stream in the form of a Fluid bed is generated, the spraying of the solution on the be moved bed of the germ material at a temperature between 20 and 130 ° C, in particular between 60 and 120 ° C. 13. Process for the preparation of organosilicon-modified alkali metals tall silicates according to claim 6, characterized in that at Implementation of one of the methods of claims 7 to 12 in the alkali metal silicate solution prepared in each sub-step a) or further water after reaction with an organosilicon compound soluble adjusting agents and / or builder substances are preferably used selects from sodium carbonate or hydrogen carbonate, sodium percarbonate, Sodium perborate, sodium phosphate, pentasodium triphosphate, sodium ci occurred, sodium glycinate is added, the proportion of further Stellmit tel and / or builder substances based on the dry substance content the alkali metal components is between 5 and 120% by weight. 14. Use of organosilicon-modified alkali metal silicates according to one or more of claims 1 to 6 or of claims Chen 7 to 13 available products, if desired after loading with other liquid or easily meltable detergent ingredients, preferably nonionic surfactants, as a component in washing and Detergents.