WO1996028382A1

WO1996028382A1 - Silicate builders obtained by temper-hardening glass pieces

Info

Publication number: WO1996028382A1
Application number: PCT/EP1996/000944
Authority: WO
Inventors: Gerald Schreiber; Wolfgang Breuer; Berthold Schreck; Volker Bauer; Hans-Friedrich Kruse; Beatrix Kottwitz
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1995-03-15
Filing date: 1996-03-06
Publication date: 1996-09-19
Also published as: DE19509303A1

Abstract

Solid, X-ray amorphous alkaline metal silicates with a molar ratio (= modulus) between SiO2 and M2O (in which M stands for an alkaline metal) in a range from 1.5 to 3 are characterised in that they are obtained by temper-hardening molten solid potassium water glass comminuted by crushing or dividing up the molten mass in an aqueous atmosphere with a water steam partial pressure from 0.012 to 1 bar for 5 minutes to 4 hours at a temperature from 300 to 500 °C. Also disclosed is a process for producing these silicates and their use in washing and cleaning products.

Description

'Silicate builders through temperuno of piece glass'

The invention describes a radiopaque orphalous alkali metal silicate obtainable by tempering melted and crushed water glass in a water vapor atmosphere and a process for its production. The products can be used as builder substances and as anti-corrosion agents in washing and cleaning agents.

By Willgallis and Range, glass techn. Ber. 37 (4), pp. 194-200 (1964), the crystallization behavior of previously melted or unmelted amorphous sodium disilicate was examined at a temperature above 500 ^β C. Crystalline products were obtained in the temperature range between 500 and 820 ° C.

This finding coincides with the results of the process according to DE-A-4000705. The document states: For the production of crystalline sodium! ^" Licenses with a layer structure of the formula Na2Si _x 02χ ₊ ι, where x is between 2 and 3, are first melted sand and soda in a molar ratio (" module ") SiO 2 / Na 2 O from 2 to 3.5 at temperatures from 1200 to 1,400 ° C. The lumpy water glass obtained after the melt has cooled down is ground to particle sizes of less than 2 mm before being treated in an elongated reaction zone with mechanical agitation for 10 to 120 minutes at temperatures of 600 to 800 ° C. Finally, the material leaving the reaction zone is ground to a fineness of less than 1 mm.

EP-A-425 427 describes a process for the production of amorphous sodium silicates with a water content of 0.3 to 6% by weight, by first spray-drying a powdered amorphous sodium silicate with a water content (determined as loss on ignition) from a water glass solution at 700 ° C) of 15 to 23 wt .-% and this is then thermally treated in a rotary kiln at temperatures of 250 to 500 ° C for a period of between one and 60 minutes. The product swells strongly, so that it must then be crushed with the aid of a mechanical crusher. The resulting sodium silicates are X-ray amorphous. However, if the temperature is increased to the range between 500 and 850 ° C., crystalline sodium silicates with a layer structure are obtained with this procedure, as can be seen from EP-A-425 428.

German patent application P 44 01 527.5 describes the tempering of melted and crushed amorphous sodium water glass in a water-containing atmosphere with a water vapor partial pressure between 0.012 and 1 bar at temperatures between 500 and 740 ° C. Here, crystalline sodium silicates with a layer structure are obtained.

In contrast, the invention has as its object to provide new X-ray amorphous alkali metal silicates which can be used as builders or as corrosion protection components in detergents and cleaning agents, and to provide a process for their preparation. As The starting product is intended to use melted and crushed, practically anhydrous alkali metal silicate in order to avoid the energy-intensive steps of dissolving the melted water glass in water and then spray-drying it. In particular, the alkali metal licens to be made available are required to provide good secondary washing power as a builder component in detergents for textile washing, ie to result in a low tissue incrustation.

This object is achieved by solid, X-ray amorphous alkali metal silicates with a molar ratio (= modulus) SiO 2: M2O (M = alkali metal) in the range from 1.5 to 3, characterized in that they are obtainable by melting and grinding or solid water glass comminuted by dividing the melt in a water-containing atmosphere with a water vapor partial pressure between 0.012 and 1 bar for a period between 5 minutes and 4 hours at a temperature between 300 and 500 ° C.

"X-ray amorphous" is to be understood here to mean that the products in X-ray diffraction examinations do not provide sharp X-ray reflections, but at most provide a very wide diffraction maximum. In contrast, areas that an electron diffraction diagram can provide can be detected in electron diffraction experiments.

The solidification of the solidified melt of the amorphous water glass is preferably carried out by grinding. The common grinding units are suitable for this. For example, the lumpy water glass can be ground using a robust, slow-running beater mill, for example a hammer mill. The further fine grinding can be done with the help of a vibrating mill, a Ball mill or an air jet mill can be performed. If the method is to be used in the embodiment in which the ground amorphous water glass is moistened with a water glass solution or with sodium hydroxide solution, this moistening can already take place during the grinding process. In order to avoid contamination of the product with metal abrasion, it is recommended to use mills and grinding media that have a ceramic, in particular a licorceramic lining. Before the tempering process is carried out, the millbase should preferably have a maximum particle size of less than 1.0 mm, which can be ensured by suitable classification, for example sieving. Obviously, Öberkorn will be returned to the grinding process.

Alternatively, a water glass powder or granulate can be used, which was obtained directly by dividing and cooling the melt. For example, the liquid melt can be pressed through nozzles with, preferably, a maximum diameter of 1 mm and the solidified water glass threads can preferably be broken to a length of <1 mm, for example by means of a suitable grinding unit, a roller mill or a roller mill. The nozzle diameter is limited at the bottom by the viscosity of the water glass melt used. A cooling medium, for example an air or water vapor stream, is advantageously used to cool the molten threads.

For later use in detergents and cleaning agents, the product is preferably ground and classified so that the maximum particle size is between 0.01 and 0.5 mm.

During the tempering, the water content of the water-containing atmosphere is adjusted so that the water vapor partial pressure is between 0.012 and 1 bar, preferably between 0.02 and 0.7 bar. This can for example, by keeping the tempered material in contact with a gas stream, for example an air stream, during the tempering process, which has the corresponding water content. This water content can be adjusted, for example, by saturating the gas stream with water vapor by passing it through water of the appropriate temperature. The relationship between the saturation pressure of water and the water temperature is known, for example from Uli ann's Encyclopedia of Industrial Chemistry, 4th edition 1983, volume 24, page 170. The enrichment of the carrier gas with water vapor can be made more effective by increasing the exchange area become. This can take place, for example, in trickle chambers which may be filled with packing material and into which water of the appropriate temperature is sprayed. The water-containing gas stream can of course also be prepared by mixing pure water vapor obtained with the boiling of water with the carrier gas, for example with air.

In the sense of the invention, it is essential that the water content of the atmosphere is within the specified limits during the entire tempering process. As comparative experiments show, it is not sufficient to simply moisten the starting product with water before tempering. If the product dries during the tempering and the water vapor evaporates, no sufficient builder properties are formed. However, it would correspond to the idea of the present invention to heat a moist product in a closed container so that the evaporating water cannot escape. Because of the more difficult pressure and temperature control for tempering under water vapor atmosphere at temperatures between 300 and 500 ° C, this procedure is less preferred. The melted and shredded alkali metal silicate is practically water-free before the tempering and, if need be, superficially covered with adhering moisture. If the water content is determined as loss on ignition at 800 ° C., water contents of below about 0.5% by weight are found. In the heat treatment according to the invention in a water vapor atmosphere, the alkali metals absorb water, so that the heat-treated products have water contents, which can be determined as loss on ignition at 800 ° C., in the range from 0.5 to 3.5% by weight .

For economic reasons, sodium is preferably used as the alkali metal. In contrast, potassium silicates show an improved dissolving behavior and are also suitable for the intended use, but are less economically attractive. A compromise between dissolving behavior and price is to partially replace the sodium in potassium in sodium silicates, for example in such a way that the calculated content of K2O is in the range from 0.1 to 5% by weight, based on the total weight of the alkali metal silicate.

In a further aspect, the invention relates to a process for the production of solid, X-ray amorphous alkali metal licates with a molar ratio (module) S1O2: M2O (M = alkali metal) in the range from 1.5 to 3, characterized in that molten and by Grinding or crushing the melted solid water glass in a water-containing atmosphere with a water vapor partial pressure between 0.012 and 1 bar for a period between 5 minutes and 4 hours at a temperature between 300 and 500 ° C. The above explanations apply to the preferred water vapor partial pressures and their setting. The process is carried out in such a way that alkali metal silicates with a molar ratio (= module) S1O2: M2O (M = alkali metal) in the range from 1.5 to 3 are formed, since favorable washing properties are observed in this module range, particularly with regard to that Secondary washing ability. The module range from about 1.9 to about 2.5 is particularly preferred. The easiest way to set the module is that the starting product used for the tempering already has the corresponding module. The tempering according to the invention which leads to partial hydration can be accelerated if the tempered material is moistened before the tempering with a water glass solution with a module in the range from 1.5 to 3 and a solids content> 10% by weight to such an extent that the water content the mixture is between 3 and 30% by weight and the modulus of the total mixture is in the range 1.5 to 3. This opens up a possibility of setting the module to the desired value before the tempering if the crushed, melted water glass used does not have the desired module. If the modulus of the melting glass used is higher than the desired value, the solution is moistened with a water glass solution of less modulus and vice versa.

Furthermore, the process can be carried out in such a way that the amorphous comminuted melting glass is moistened with an alkali metal hydroxide solution having a solids content of> 10% by weight to such an extent that the water content of the mixture is between 3 and 30% by weight and the module of the total mixture is in the range 1.5 to 3. Instead of moistening with alkali metal hydroxide solution, the reduced melting glass can also be mixed with - preferably water-containing - alkali metal metasilicate from module 1 in such a way that the module of the total mixture is in the range 1.5 to 3. In particular, for this Use metasilicate hydrates with the composition M2Siθ3 • nH2Ü, for example in the form of pentahydrates or nonahydrates.

Both the moistening with alkali metal hydroxide solution and the mixing with metasilicate has the consequence that the module of the total mixture is reduced compared to the module of the melting glass used. As a result, a melting glass can be used, the module of which lies above the desired target range of 1.5 to 3 and preferably of 1.9 to 2.5, wherein the module of the melting glass can also be above 3.

If, for example, a melting glass with module 2.45 is assumed, this can be brought to a module of 2 before tempering if 100 g of melting glass are moistened with 17.2 g of 50% sodium hydroxide solution. Correspondingly, a melting glass with module 3.3 can also be used, which is brought to a module of 2 before tempering by moistening 100 g of the melting glass with 40 g of 50% sodium hydroxide solution. In this way, melting glass can be used up to a module of about 3.8.

As already stated above, the production of sodium silicates is preferred for economic reasons, but for reasons of improved solubility the sodium can be replaced by so much potassium that the calculated content of K2O is in the range from 0.1 to 5 % By weight is based on the end product. A potassium-containing sodium silicate can be produced, for example, in that the crushed melting glass used already contains the corresponding potassium components. However, since such products are usually not produced industrially, sodium silicates containing potassium can preferably be obtained by the process according to the invention by comminuting melted ones Sodium licate either, as described above, moistened with a potassium silicate solution or with potassium hydroxide solution or mixed with potassium metasilicate.

The actual annealing process can be carried out with a stationary or a moving product. Accordingly, the annealing can be carried out, for example, in a fixed bed, but also by mixing the tempered material, for example in a rotating rotary kiln or in a fluidized bed.

The annealing process described provides X-ray amorphous alkali metal silicate, which is suitable as a builder for detergents and cleaners. The products obtained by the process according to the invention have bulk densities in the range from 300 to 600 g / l and are suitable as raw materials for detergent extrudates. However, the bulk density is too low for use in the compact detergents currently used. Known agglomeration processes such as granulation, spray granulation in a fluidized bed or roller compaction can increase the bulk density to the currently desired range between approximately 700 and approximately 1000 g / l. Chapter 7 in Volume B2 of Ullmann's Encyclopedia of Industrial Chemistry, 5th edition 1988, provides an overview of such agglomeration processes. To increase the bulk density, it is also favorable to load the alkali metal silicates produced according to the invention with liquid detergent substances, for example with nonionic surfactants .

Finally, the invention relates to the use of the alkali metal silicates according to the invention, which can be obtained in the ways described above, as a corrosion protection and / or builder component in detergents and / or washing processes for the Textile laundry, in machine dishwashing detergents and / or cleaners for hard surfaces. The anti-corrosion effect of the agents according to the invention manifests itself particularly in relation to metallic surfaces. The use according to the invention takes place in the presence of further components required for washing and cleaning purposes. Such components include, in particular, surface-active substances such as nonionic and / or anionic surfactants of fat and / or oleochemical origin, and, depending on the application, additional auxiliaries required, such as bleaching agents, protein and / or starch-splitting enzymes, optical brighteners, complexing agents , further builder components such as phosphates and optionally further components known to the person skilled in the art.

The alkali metal silicates according to the invention are preferably used in such a way that a solid mixed product is produced which, in addition to the alkali metal silicates according to the invention, contains the further 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 by adding them separately from the other active ingredients and auxiliaries to the washing or cleaning solution.

In the following, information on mixture components that can be used in conjunction with the alkali metal silicates according to the invention is given without any claim to completeness. Basically, the entire range of valuable and auxiliary materials from the field of detergents and cleaning agents is available. In particular, there are surfactants of anionic, nonionic, cationic, amphoteric and / or zwitterionic structure as well as further inorganic and / or organic builder substances, Bleaching agents and bleach activators, enzymes and enzyme stabilizers, foam inhibitors, optical brighteners, inorganic alkaline and / or water-neutral salts, for example sulfates or chlorides, and dyes and fragrances.

The known Cg-Ci3-alkylbenzenesulfonates, olefin sulfonates and alkanesulfonates are preferred as surfactants of the sulfonate type. Esters of α-sulfofatty acids or the disalts of α-sulfofatty acids are also suitable. Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters as well as their mixtures, such as those produced 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 be preserved.

Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, in particular from fatty alcohols, for example from coconut oil alcohol, tallow alcohol, oleyl alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the Cιo-C2θ ^_ 0xoalcohols, and those secondary alcohols of this chain length. The sulfuric acid monoesters of alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched Cg-Cn alcohols with an average of 2 or 3.5 moles of ethylene oxide, are also suitable.

Preferred anionic surfactant mixtures contain combinations of alk (en) yl sulfates, in particular mixtures of saturated and unsaturated fatty alcohol sulfates, and alkylbenzenesulfonates, sulfated fatty acid glycerol esters and / or α-sulfofatty acid esters and / or alkyl sulfosuccinates. Mixtures which contain alk (en) yl sulfates and anionic surfactants are particularly preferred Contain alkylbenzenesulfonates and, optionally, α-sulfofatty acid methyl esters and / or sulfated fatty acid glycerol esters.

Other suitable anionic surfactants are, in particular, soaps, preferably in amounts below 5% by weight. Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures. Unsaturated fatty acid soaps, which are derived, for example, from oleic acid, may also be present, but their proportion of the soaps should not exceed 50% 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 surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts. The content of anionic surfactants in the compositions is generally between 5 and 40% by weight.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (E0) per mole of alcohol, in which the alcohol residue is linear or preferably in 2- Position may be methyl branched or may contain linear and methyl branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 E0 per mole of alcohol are preferred. Among the preferred ethoxylated Alcohols include, for example, Ci2-Ci4 alcohols with 3 EO or 4 EO, Cg-Cn alcohol with 7 EO, Ci3-Ci5 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci2-Ci8 alcohols with 3 EO , 5 EO or 7 EO and mixtures of these, such as mixtures of Ci2-Ci4 alcohol with 3 EO and Ci2-Ci8 ~ alcohol with 5 EO. The degrees of ethoxylation given represent statistical mean values which can be an integer or a fractional number for a specific product. Preferred alcohol ethoxylates 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 R0 (G) _x can also be used as further nonionic surfactants, in which R is a primary straight-chain or methyl-branched, in particular in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms 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 (I),

R3

I R2_ _C0 _N- [Z] (I)

in R2C0 for an aliphatic acyl radical with 6 to 22 carbon atoms, R ³ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] represents a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.

The proportion of nonionic surfactants in the compositions is generally 2 to 25% by weight.

All previous builder substances commonly used can be used as further inorganic builder substances. These include in particular sodium carbonate, zeolites, crystalline layered silicates, even phosphates, if their use should not be avoided for ecological reasons. Their content can vary within a wide range depending on the content of the alkali metal silicates according to the invention. The sum of customary builder substances and the silicates according to the invention is usually 10 to 60% by weight. When using sodium carbonate as an additional builder component, a close spatial contact between the carbonate and the silicate can be advantageous. This can be achieved, for example, by spraying the alkali metal silicates produced according to the invention with a sodium carbonate solution and then, if desired, drying them. The content of sodium carbonate in the compositions can be, for example, up to about 20% by weight, preferably between 5 and 15% by weight, and is in the range from above 20% by weight of the compositions of the silicates according to the invention, in particular to about 10% by weight. According to the teaching of DE-A-43 19578, alkali metal carbonates can also be replaced by sulfur-free amino acids and / or their salts having from 2 to 11 carbon atoms and optionally a further carboxyl and / or amino group. In the context of this invention, it is preferred that the alkali metal carbonates are partially or completely replaced by glycine or glycinate. Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons. and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 200,000 (based on acid). Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. Biodegradable terpolymers, for example those which are salts of acrylic acid and maleic acid and vinyl alcohol as monomers, are particularly preferred or vinyl alcohol derivatives (P 4300 772.4) or the salts of acrylic acid and 2-A1-alkylallylsulfonic acid as monomers and sugar derivatives (P 42 21 381.9).

Other suitable builder systems are oxidation products of carboxyl group-containing polyglucosans and / or their water-soluble salts, as are described, for example, in international patent application WO-A-93/08251 or the like Production is described for example in the international patent application WO-A-93/16110 or the older German patent application P 43 30 393.0.

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

Of the compounds which provide H2O2 in water and serve as bleaching agents, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other usable bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H2O2-providing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid. The bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, advantageously using boron monohydrate.

In order to achieve when washing at temperatures of 60 C and below a ^β ver¬ improved bleaching effect, bleach activators may be used in the preparations are incorporated. Examples of these are N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetra-acylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate. Other known bleach activators are acetylated mixtures of sorbitol and mannitol, as described, for example, in European patent application EP-A-0 525 239. The bleach activators contain bleach activators 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'-tetraacetylethylenediamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol mannitol Mixes (SORMAN).

When used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of Cιg-C24 fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes. The foam inhibitors, in particular silicone or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred. Usual amounts are in the range from 1 to 5% by weight. Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Of particular interest here are enzyme mixtures, for example from protease and alylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase . Peroxidases or oxidases have also proven to be suitable in some cases. The enzymes can be adsorbed on carriers and / or embedded in Hü11 substances in order to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

The salts of polyphosphonic acids, in particular 1-hydroxyethane-l, l-diphosphonic acid (HEDP), come as stabilizers, in particular for per-compounds and enzymes,

Diethylenetria inpentamethylenphosphonic acid (DETPMP) or ethylenediaminetetramethylenephosphonic acid (EDTMP) into consideration.

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

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

As optical brighteners, the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similar compounds, instead of the morpholino group carry a diethanolamino group, a methylinino group, an anilino group or a 2-methoxyethylamino group. In addition, brighteners of the substituted diphenylstyryl type may be present, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-

Bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used. Usual amounts are in the range from 0 to 0.3% by weight.

The bulk density of the preferred granular detergents or cleaners which contain the silicates according to the invention is generally 300 to 1200 g / cm ³ , but preferably 500 to 1100 g / cm ³ . Washing and cleaning agents with bulk densities of at least 700 g / cm ³ are very particularly preferred. They can be produced by any of the known processes, such as mixing, Spray drying, granulation and extrusion take place, the silicates according to the invention advantageously being mixed with the other components of the composition. Processes in which a plurality of subcomponents, for example spray-dried components and granulated and / or extruded components, are mixed with one another are particularly suitable. In granulation and extrusion processes in particular, it is preferred to use the anionic surfactants, if any, in the form of a spray-dried, granulated or extruded compound, either as an additive component in the processes mentioned or as an additive to other granules. It is also possible and, depending on the recipe, to be advantageous if further individual constituents of the agent, for example carbonates, citrate or citric acid or other polycarboxylates or polycarboxylic acids, polymeric polycarboxylates, zeolite and / or layered silicates, for example layered crystalline disilicates subsequently mixed into spray-dried, granulated and / or extruded components.

Execution examples

To carry out the tests, amorphous sodium water glass with a module SiO 2: a 2 O = 2.0, which was obtained by melting quartz sand with soda, was ground in a cross-beat mill and the sieved fraction with a particle size <0.2 mm was used. The powder obtained was examined for comparative experiment 1 without tempering. For comparative experiment 2, the powder was moistened with 15% by weight of water and tempered at 450 ° C. for 60 minutes. As a comparative product 3, the commercially available product Na-SKS-6 (crystalline anhydrous sodium disilicate) from Hoechst, which consists primarily of the delta phase, was without further processing examined. As a comparative product 4 a spray dried sodium silicate (Porti1 ^R A, Henkel KGaA) having a modulus of 2 and a water content of 19 wt .-% was used. In the exemplary embodiments and the comparative examples, the annealing was carried out in such a way that the powders with a filling height of about 3 cm were placed in porcelain crucibles and these were placed in heated Simon-Müller ovens under the conditions specified in the table. The water vapor atmosphere in the furnaces was adjusted in such a way that a nitrogen flow at a speed of 60 l / h. was blown into the oven, which was previously bubbled with water of different temperatures. The corresponding water vapor partial pressure of this nitrogen stream is entered in the table. In Examples 1 and 2 and 7 to 9, the ground amorphous water glass was filled dry into the crucible. In Examples 3, 4 and 6, the powder was moistened with sodium hydroxide solution or potassium hydroxide solution before the tempering under a steam atmosphere. The total water content of the mixture was between 5 and 20% by weight.

The washing tests were carried out in Miele 918 machines under standard test conditions. A combined universal detergent compact formulation without zeolite and co-builders with 34% licensed builder was used for the test. The measurement conditions were: 25 washes, 3.5 kg filling wash, 4 test fabrics, 23 ° d hardened tap water (Ca / Mg mixed hardness 5: 1), 98 g dosage, 20 l water in the main wash. After the washes, tissue samples were ashed and their residue was determined. The mean values of the 4 test fabrics are listed in the table. Table of test substances, their production and secondary washing results (residue after ashing)

No. starting product mixed with total H2θ vapor temperature time residue module pressure, bar ° £ minutes%

Compare l melting glass 2.0 4.1 module 2.0

Compare 2 melting glass H 0 (15 wt. 450 60 3.9 module 2.0

Compare 3 Na-SKS-6 module 2.0 - 2.0 - - 3.0

Compare 4 Porti1 A module 2.0 - 2.0 - - 4.0

Ex. 1 melting glass - 2.0 0.02 400 60 3.0 module 2.0

Ex. 2 melting glass - 2.45 0.02 450 120 2.9 module 2.45

Ex. 3 melting glass 50% NaOH 2.0 0.02 450 120 2.8 module 2.45

Ex. 4 melting glass 50% K0H 2.0 0.02 450 120 2.8 module 2.45

Example 5 melting glass Na2Siθ3 x 91 2.0 0.02 450 120 2.9 module 2.45

Table (continued)

No. output product mixed with total H2θ vapor temperature time residue module pressure, bar ° j | Minutes%

Beisp.6 molten glass 50% NaOH 2.45 450 120 0.02 ^3, 1

Module 3.3

Ex. 7 melting glass 2.0 0.07 400 60 ³ , 2

Module 2.0

Ex. 8 melting glass 2.0 0.3 400 60 3.0

Module 2.0

Ex. 9 melting glass 2.0 0.7 400 60 2.9

Module 2.0

Claims

claims

1. Solid, X-ray amorphous alkali metal silicates with a molar ratio (= module) SiO 2: M2O (M = alkali metal) in the range from 1.5 to 3, characterized in that they can be obtained by melting and by grinding or by dividing the Melt crushed solid water glass in a water-containing atmosphere with a water vapor partial pressure between 0.012 and 1 bar for a period between 5 minutes and 4 hours at a temperature between 300 and 500 ° C.

2. alkali metal silicates according to claim 1, characterized in that they have a water content, determinable ^' as loss on ignition at 800 ° C, in the range of 0.5 to 3.5 wt .-%.

3. alkali metal silicates according to one or both of claims 1 and 2, characterized in that the alkali metal represents sodium.

4. alkali metal silicates according to one or both of claims 1 and 2, characterized in that the alkali metal represents sodium, but so much sodium is replaced by potassium that the calculated content of K2O in the range of 0.1 to 5 wt .-% with respect to the total weight of the alkali metal silicate.

5. alkali metal silicate according to one or more of claims 1 to 4, characterized in that the module SiO 2: M2O is in the range from 1.9 to 2.5.

6. Process for the preparation of solid, X-ray amorphous alkali metal silicates with a molar ratio (module) S1O2: M2O (M = alkali metal) in the range from 1.5 to 3, characterized in that molten solid water glass crushed by grinding or by breaking up the melt in a water-containing atmosphere with a water vapor partial pressure between 0.012 and 1 bar for one Time between 5 minutes and 4 hours at a temperature between 300 and 500 ° C.

7. The method according to claim 6, characterized in that the water content of the atmosphere is adjusted so that the water vapor partial pressure is between 0.02 and 0.7 bar.

8. The method according to one or both of claims 6 and 7, characterized in that the amorphous water glass before annealing with a water glass solution with a module in the range 1.5 to 3 and a solids content> 10 wt .-% is moistened to the extent that the water content of the mixture is between 3 and 30% by weight and the modulus of the total mixture is in the range 1.5 to 3.

9. The method according to one or both of claims 6 and 7, characterized in that the amorphous water glass is moistened before the tempering with an alkali metal hydroxide solution with a solids content> 10% by weight to such an extent that the water content of the mixture is between 3 and 30 % By weight and the modulus of the total mixture is in the range 1.5 to 3.

10. The method according to one or both of claims 6 and 7, characterized in that the amorphous water glass is mixed with alkali metal metasilicate (module 1) prior to tempering, so that the module of the total mixture is in the range 1.5 to 3.

11. The method according to claim 10, characterized in that water-containing alkali metal metasilicate is used.

12. The method according to one or more of claims 6 to 11, characterized in that the solid amorphous alkali metal silicate is comminuted to a maximum particle size below 1 mm before annealing.

13. The method according to one or more of claims 6 to 12, characterized in that sodium is present as the alkali metal, but can be replaced by so much potassium that the calculated content of K2O in the range of 0.1 to 5 wt .-% % is in relation to the end product.

14. The method according to one or more of claims 6 to 13, characterized in that the annealing is carried out in a fixed bed.

15. The method according to one or more of claims 6 to 13, characterized in that the annealing is carried out by mixing the tempered material.

16. Use of the solid, X-ray amorphous alkali metal silicates according to one or more of claims 1 to 5 or of the product obtained by the process according to one or more of claims 6 to 15 as a builder or anticorrosive agent in washing and cleaning agents.