EP0859827B1 - Method for preparing an amorphous alkali silicate with impregnation - Google Patents

Abstract

PCT No. PCT/EP96/03905 Sec. 371 Date Jun. 24, 1998 Sec. 102(e) Date Jun. 24, 1998 PCT Filed Sep. 5, 1996 PCT Pub. No. WO97/10325 PCT Pub. Date Mar. 20, 1997A process for producing a particulate amorphous alkali metal silicate having a molar ratio of M2O to SiO2 of 1:1.5 to 1:3.3 by a) spray-drying an aqueous mixture of amorphous alkali metal silicate, b) impregnating the spray-dried amorphous alkali metal silicate with an aqueous dispersion or solution of detergent composition components containing at least one organic component, and c) optionally drying the impregnated amorphous alkali metal silicate.

Description

The invention relates to a process for the production of free-flowing amorphous alkali silicates by spray drying, the alkali silicate then impregnated with ingredients from washing or cleaning agents becomes.

It is known that spray or roller drying of water glass solutions obtained hydrated water-soluble silicates in particle form leave, which still contain about 20 wt .-% water (see. Ullmanns Encyclopedia of technical chemistry, 4th edition 1982, volume 21, page 412). Such products are commercially available for various purposes. Such powder have a very loose structure due to spray drying; your Bulk weights are generally well below 700 g / l, for example at 300 g / l or even less.

Alkali silicates in granular form with higher bulk densities can according to the teaching of European patent application EP-A-0 526 978 can be obtained, whereby an alkali silicate solution with a solids content between 30 and introduces 53% by weight into a heated drum, one in the longitudinal axis Shaft with a variety of close to the inner surface of the drum Arms rotates, the drum wall having a temperature between 150 and 200 ° C and the drying process by a fed into the drum Supported gas with a temperature between 175 and about 250 ° C becomes. According to this process, a product is obtained, the middle one Particle size is in the range between 0.2 and 2 mm. A preferred one Drying gas is heated air.

European patent application EP-A-0 542 131 describes a process in which a product which is completely soluble in water at room temperature and has a bulk density of between 500 and 1200 g / l is obtained. Drying is preferably carried out using heated air. Here, too, a cylindrical dryer with a heated wall (160 to 200 ° C.) is used, in the longitudinal axis of which a rotor with blade-shaped blades rotates at such a speed that the silicate solution has a solids content of between 40 and 60% by weight pseudoplastic mass with a free water content between 5 and 12 wt .-% arises. Drying is supported by a hot air stream (220 to 260 ° C).

The older, unpublished German patent application DE-A-44 19 745 also describes a water-soluble, amorphous and granular alkali silicate, which is prepared in a similar manner to that described in EP-A-0 526 978, but contains silicic acid. The term "amorphous" means "X-ray amorphous". This means that the alkali silicates do not provide sharp reflections in X-ray diffraction images, but at most one or more broad maxima, the width of which is several degree units of the diffraction angle. However, this does not rule out the possibility that areas are found in electron diffraction experiments which give sharp electron diffraction reflections. This is to be interpreted in such a way that the substance has microcrystalline areas of a size up to approximately 20 nm (max. 50 nm).

Granular amorphous sodium silicates, which by spray drying aqueous water glass solutions, subsequent grinding and subsequent compacting and rounding with additional Dehydration of the regrind is obtained from the US patents 3,912,649, 3,956,467, 3,838,193 and 3,879,527. The water content of the products obtained is at about 18 to 20 wt .-% with bulk weights well above 500 g / l.

Other granular alkali silicates with secondary washing ability are from the European Patent applications EP-A-0 561 656 and EP-A-0 488 868 are known. It is about Compounds of alkali silicates with certain Q distributions and alkali carbonates.

In the American patent US 3,920,586 granular detergents are described which are composed of 2 granules. The basic granulate is a Spray-dried granules containing anionic surfactant, the detergent also contains Silicate granules on which nonionic surfactants are absorbed. The silicate granules can be made from aqueous slurries are produced, preferred granules by flash drying of the silicate slurries can be obtained.

The older, unpublished German patent application DE-A-44 46 363 describes an amorphous alkali silicate with secondary washability and a molar ratio of M ₂ O: SiO ₂ between 1: 1.5 and 1: 3.3, which contains ingredients of washing or Cleaning agent is impregnated and has a bulk density of 300 g / l. The silicate carrier grain to be impregnated is preferably in granular form and / or as a compound with alkali carbonates and can be produced by spray drying, granulation and / or compacting, for example roller compaction. In a preferred embodiment, the silicate is impregnated with surfactants and in particular with nonionic surfactants. The inclusion of the impregnating agent reduces the flowability of the silicate material, but this can be restored if the impregnated material is subsequently treated with an aqueous solution.

However, it has been found that spray-dried amorphous alkali silicates, which are free of additional alkali carbonates used, after impregnation and the subsequent Covering with an aqueous solution does not have sufficient flow properties.

The object of the invention was therefore to develop a method in which Application spray-dried amorphous silicates are made which - even if they do not Contain additional alkali carbonates used in the spray-dried batch - without one serious loss of flowability can be impregnated.

a) ein wäßriger Ansatz, enthaltend als Aktivsubstanz im wesentlichen ein amorphes Alkalisilikat der angegebenen Zusammensetzung, sprühgetrocknet wird, das dadurch gekennzeichnet ist, daß anschließend

b) mit einer wäßrigen Dispersion von Inhaltsstoffen von Wasch- oder Reinigungsmitteln imprägniert, wobei mindestens ein organischer Inhaltsstoff von Wasch- oder Reinigungsmitteln in Wasser oder einer wäßrigen Lösung dispergiert vorliegt, sowie

c) gegebenenfalls getrocknet wird.

The invention accordingly relates to a process for producing a particulate amorphous alkali silicate with a molar ratio M ₂ O: SiO ₂ (M = alkali metal) between 1: 1.5 and 1: 3.3, where

a) an aqueous mixture containing as the active substance essentially an amorphous alkali silicate of the specified composition is spray-dried , which is characterized in that subsequently

b) impregnated with an aqueous dispersion of ingredients of washing or cleaning agents, at least one organic ingredient of washing or cleaning agents being dispersed in water or an aqueous solution, and

c) optionally drying.

Amorphous alkali silicates used with preference have a molar ratio M ₂ O: SiO ₂ (M = alkali metal) between 1: 1.9 and 1: 3, in particular up to 1: 2.8. Sodium and / or potassium silicate are particularly suitable here. Sodium silicates are preferred for economic reasons. However, if, for reasons of application technology, a particularly high dissolution rate in water is important, it is advisable to replace sodium at least partially with potassium. For example, the composition of the alkali silicate can be chosen so that the silicate has a potassium content, calculated as K ₂ O, of up to 5% by weight. It is expressly pointed out that all amorphous alkali silicates of the specified module, in addition to the known water glasses, ie also commercially available granular silicates or carbonate-silicate compounds, are suitable starting materials for the purposes of this invention. These silicates can themselves have been produced by spray drying, granulation and / or compacting, for example by roller compaction, if such a preparation of the silicate starting products is also not always expedient, since these products have to be dissolved again in an aqueous batch.

The aqueous batch to be spray-dried essentially contains the aforementioned Alkali silicates as active substance, it being particularly preferred that a slurry is made that does not contain alkali carbonates or alkali carbonates only in weight ratios of alkali silicate (based on anhydrous Active substance): Contains alkali carbonate from 3: 1 to 20: 1. In a preferred one Embodiments of the invention are spray-dried silicate Compounds (a) produced, which 55 to 95 wt .-%, preferably 60 to 90 % By weight alkali silicate (based on anhydrous active substance), 0 to 15 % By weight, preferably 2 to 10% by weight of alkali carbonate and 5 to 22% by weight, preferably 10 to 20% by weight and in particular at least 15% by weight of water contain.

However, other ingredients, in particular ingredients of washing or cleaning agents incorporated become. Their content is based on the spray-dried silicate product of process stage (a), preferably 0.5 to 20 % By weight and in particular 1 to 15% by weight. It can be, for example surfactants, especially anionic surfactants such as alkylbenzenesulfonates, Alkyl sulfates, 2,3-alkyl sulfates, alkyl ether sulfates and soaps, however also about neutral salts like sodium or potassium sulfates, about graying inhibitors or nonionic surfactants such as alkyl polyglycosides or optionally alkoxylated Act polyhydroxy fatty acid esters. In a preferred embodiment of the invention are anionic surfactants in the spray-dried slurry and / or organic cobuilders (see description below), preferably in amounts of 1 to 15% by weight, based on the spray-dried silicate Product of process stage (a) used.

In contrast to granular products of equivalent composition, spray-dried products usually have a relatively low absorption capacity for liquid to waxy ingredients of detergents or cleaning agents at the usual processing temperatures due to the sintered surface of the spray-dried beads. So that such ingredients can be applied to the spray-dried beads, their surface structure must first be destroyed or the surface increased accordingly. The spray-dried silicate products (a) are preferably used in amounts of 3 to 40% by weight and in particular 5 to 35% by weight, based in each case on the impregnated and possibly finally dried silicate product, an aqueous dispersion of ingredients of Impregnated detergents or cleaning agents. Suitable impregnating agents are, for example, surfactants, silicone and / or paraffin-based foam inhibitors or textile-softening compounds such as cationic surfactants. Surfactants and foam inhibitors are particularly preferred. Particularly preferred impregnating agents are again nonionic surfactants, for example alkoxylated, preferably ethoxylated and / or ethoxylated and propoxylated, aliphatic C ₈ -C ₂₂ alcohols. These include in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be methyl-branched linearly or preferably in the 2-position or contain linear and methyl-branched radicals in the mixture can, as is usually present in oxo alcohol residues. 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 EO per mole of alcohol are also preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ alcohols with 3 EO or 4 EO, C ₉ -C ₁₁ alcohol with 7 EO, C ₁₃ -C ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -C ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₁₂ -C ₁₄ alcohol with 3 EO and C ₁₂ -C ₁₈ alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction 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 include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the Alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.

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

The nonionic surfactants mentioned can be used alone or in a mixture with them the other nonionic surfactants mentioned or in combination with other non-water-soluble organic components are used, advantageously as an organic dispersion component in addition to alkoxylated fatty alcohols, the alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters be used.

If foam inhibitors are used as impregnating agents, they contain the silicate products preferably 70 to 90% by weight of amorphous silicates, 0.1 to 2% by weight of foam-inhibiting oils and / or waxes on silicone and / or paraffin base and balance water. If necessary, these silicate products also have other ingredients, for example Anionic surfactants, especially alkylbenzenesulfonates and / or Alkyl sulfates, and / or cobuilders, in particular (polymeric) polycarboxylates, and / or phosphonates. The content of these further ingredients is preferably below 20 wt .-%, in particular below 15 wt .-%, with particular Even less than 10% by weight.

Surprisingly, it was found that spray-dried silicate Products made with organic ingredients from washing or cleaning agents are impregnated, only have sufficient free-flowing properties, if the impregnating agent in the form of an aqueous dispersion and is applied in particular in the form of an emulsion. It is in one preferred embodiment of the invention an emulsion of or several nonionic surfactants and water or an aqueous solution one or more inorganic salts used. In many cases a dispersion of nonionic surfactants with water alone is not sufficient to to achieve a satisfactory flowability of the products. In particular when using alkoxylated alcohols, especially fatty alcohols dispersions are used as impregnating agents include aqueous solutions of inorganic salts. It is believed that by using the aqueous salt solution, the viscosity of the dispersion is increased accordingly, so that an improved flowability of the finished product is effected.

In all cases where the dispersion is not due to inorganic salts dispersions of nonionic surfactant are sufficient and water out. The specialist can carry out a simple test (check the flowability) determine whether it is a should use aqueous salt solution or whether water as the sole inorganic component of the dispersion is sufficient. In a preferred one Embodiment is therefore used a dispersion, which as an organic Ingredient of washing or cleaning agents ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters of the specified type, as an inorganic component, however, no salt solutions, only water included, used.

However, salt solutions, in particular, are preferred in the aqueous dispersion of silicates, carbonates, bicarbonates and / or sulfates. Silicates and (bi-) carbonates are particularly preferred used, sulfates are used only in smaller quantities.

The sulfate content, based on the total dispersion, is preferably only 2 to 10 wt .-%, while the content of the dispersion of silicate and / or (bi-) carbonate up to 40 or even 50% by weight can be. In a further preferred embodiment of the invention a silicate product is used, either as a starting material served for process step (a) or as spray-dried Product was obtained according to process step (a). Especially is advantageous if in the aqueous dispersion a solution from the spray-dried product (a) in water, preferably in amounts of 10 to 40 wt .-% and in particular in amounts of 15 to 35 wt .-%, each based on the entire dispersion.

The water content of the dispersions is preferably in a range of 10 to 40 wt .-%, in particular from 15 to 35 wt .-%.

Dispersions used with preference preferably have at least 40 % By weight and in particular 50 to 85% by weight of dispersed organic ingredients of detergents or cleaning agents.

The amount of water can vary depending on the impregnating agent used and also depending on the water content of the spray-dried silicate product (a) a critical factor in terms point to the flowability of the finished product; preferably Therefore, water is not impregnated in quantities above 20 wt .-%, based on the impregnated and not finally dried Product used.

The water content of the finished silicate products is preferably not above 22 and in particular not above 20% by weight. So if through the water content of the spray-dried product and the after-treatment with the aqueous dispersion a water content above the above Limits in the product is reached in a preferred embodiment the invention a final drying of the two first process steps connected, this drying advantageously is involved in a continuous process.

The impregnation step (b) can be carried out, for example, in such a way that first the aqueous dispersion and preferably the aqueous dispersion of nonionic surfactant and water or aqueous inorganic salt solution by intensive mixing of the nonionic surfactant and water or the aqueous solution or the nonionic surfactant, the inorganic solid salt and water is produced. The actual impregnation process can, however, be carried out in conventional mixers / granulators of the high-speed mixer type, for example a CB30 ^(R) recycler from Lödige, Germany, a Flexomix ^(R) from Schugi, Germany, or a Fukae GS30 mixer also take place in slower running mixers, for example ploughshare mixers from Lödige, in a conventional manner.

In a particularly preferred embodiment of the invention, the process step (b) not only submitted the silicate product (a). Rather, the invention provides here that a spray-dried silicate Product (a) and at least one other solid, powdery or granular product, which is a single raw material or a compound from at least 2 different raw materials, together in the process step (b) be impregnated. It has proven to be particularly advantageous proved to be a compound containing an alkali carbonate compound, which also contains organic cobuilders of the type described above, to use. Preferably 60 to 80 parts by weight of the spray dried silicate product (a) and 5 to 20 parts by weight of at least one other solid powdery or granular product together according to Process step (b) impregnated.

The invention provides in a further embodiment that the according Process step (b) product obtained before an optionally final carried out drying with another liquid preparation form is treated. In this case, preferably 60 to 85 Parts by weight of a spray-dried silicate product (a) initially with 5 to 38 parts by weight of an aqueous dispersion (b) impregnated and then with 2 to 15 parts by weight of another liquid preparation, preferably an aqueous solution of organic cobuilders, aftertreated. Such organic cobuilder solutions preferably have at least 20% by weight of solids, preferably 25 to 50% by weight Solids in order not to increase the water content in the silicate product to increase sharply. In this case, too, the maximum water content applies preferably not more than 22% by weight and in particular not more than 20% by weight should go out if no drying should be connected. On Such a method is particularly useful if either in process step (b) a dispersion is used which has high Amounts, for example more than 50 wt .-%, of organic dispersed Ingredient and / or small amounts, for example less than 20 % By weight of water or if only relatively small amounts of the aqueous Dispersion, for example less than 25 wt .-% and in particular clearly less than 20% by weight, each based on the finished and not final dried product.

If desired or due to the higher amounts of water used during the impregnation with the aqueous dispersion or during the Impregnation with an aqueous dispersion and a further aftertreatment drying, preferably in a fluidized bed, is carried out. This is preferably done immediately after the ones described above Process steps without prior storage of the silicate product carried out. Drying is then preferably carried out, if the water content after the first two process steps and the optionally carried out further after-treatment as a sum of the spray-dried silicate, the aqueous dispersion and optionally the aqueous preparation form from the aftertreatment above 22% by weight, is in particular above 20% by weight.

The bulk density of the silicate products produced according to the invention is generally between 300 and 650 g / l and can by compacting Measures of a known type, for example by roller compaction or extrusion, can be further increased. The particle size distribution (sieve analysis) is generally so pronounced that no dust particles (particles with a diameter below 0.1 mm) can be obtained and preferably 60 to 100% by weight of the particles, in particular 80 to 100% by weight of the Particles with a particle diameter of at least 0.2 mm and a maximum of 1.6 mm.

If desired, the silicatic ones produced according to the invention can Products after process step (b), a further aftertreatment or (c) are obtained to further increase the bulk density with finely divided dry powders are treated. Here, in particular 1 to 5 parts by weight of the dry powder per 100 parts by weight of the silicate Product used. Examples of such dry powder are zeolite, silicas, salts of fatty acids such as calcium stearate, however also bleach activators and finely divided alkyl sulfates, or mixtures of Zeolite or silica with at least one other of the powders mentioned.

The amorphous and impregnated alkali silicates produced according to the invention can be used as an additive component in powdery to granular washing or cleaning agents or as a component in the manufacture of the granular Detergents or cleaning agents, preferably for granulation and / or compacting can be used. Such washing or cleaning agents can have a bulk density between 300 and 1200 g / l, preferably of 500 to 1000 g / l, have and contain the invention impregnated silicates produced, preferably in amounts of 5 to 50 % By weight, in particular in amounts of 10 to 40% by weight. Your manufacture can by any of the known processes such as mixing, spray drying, granulating, Compacting such as roller compaction and extrusion take place.

Processes in which several subcomponents, for example spray-dried components and granulated and / or extruded components are mixed together. It is it is also possible that other spray-dried or granulated components subsequent processing, for example with non-ionic Surfactants, especially ethoxylated fatty alcohols, according to the usual Proceedings are charged. Especially in granulation and Extrusion process, it is preferred, the anionic surfactants that may be present in the form of a spray dried, granulated or extruded Compounds either as an admixture in the process or as an additive to be used later for other granules. It is also possible and Depending on the recipe, it can be advantageous if further individual Components of the agent, for example carbonates, citrate or Citric acid or other polycarboxylates or polycarboxylic acids, polymers Polycarboxylates, zeolite and / or layered silicates, for example layered crystalline disilicates, subsequently spray-dried, granulated and / or extruded components, optionally with nonionic surfactants and / or others at processing temperature liquid to waxy ingredients are added become. A method is preferred in which the surface of Partial components of the agent or the entire agent for reducing the Stickiness of the granules rich in nonionic surfactants and / or for their improvement Solubility is treated afterwards. Suitable Surface modifiers are known from the prior art. Next further suitable are finely divided zeolites, silicas, amorphous silicates, fatty acids or fatty acid salts, for example Calcium stearate, but especially mixtures of zeolite and silica, in particular in the weight ratio of zeolite to silica of at least 1: 1, or zeolite and calcium stearate are particularly preferred.

Particularly preferred embodiments of the invention are extruded Detergents or cleaning agents with a bulk density above 600 g / l, which anionic and optionally nonionic surfactants and a Amorphous and impregnated alkali silicate of those produced according to the invention Type contained in the extrudate. Thereby, those produced according to the invention can particulate alkali silicates once - as with others Manufacturing process - serve as an additive component, but it is special preferred to incorporate these alkali silicates into the premix to be extruded and to coextrude these silicates.

To produce these extruded detergents or cleaning agents, the known processes for extrusion, in particular to the European Patent 486,592. This results in a solid and free-flowing premix at pressures up to 200 bar extruded, the strand after the Exit from the hole shape by means of a cutting device on the particular one Granulate dimension tailored as well as the plastic and if necessary raw extrudate still moist in a further shaping processing step fed and then dried, the invention prepared impregnated alkali silicates used in the premix become.

The finished washing or cleaning agents can be in addition to those according to the invention prepared impregnated alkali silicates the following Contain ingredients. The following list also contains more detailed descriptions for some of the silicates produced in the invention Additive occurring ingredients.

These include in particular surfactants, especially anionic surfactants and, if appropriate nonionic surfactants, but also cationic, amphoteric or zwitterionic surfactants.

Preferred anionic surfactants of the sulfonate type are C ₉ -C ₁₃ alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates, and disulfonates such as are obtained, for example, from C ₁₂ -C ₁₈ monoolefins with an end or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates obtained from C ₁₂ -C ₁₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates) are also suitable, for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids. Further suitable anionic surfactants are the α-sulfofatty acids obtainable by ester cleavage of the α-sulfofatty acid alkyl esters or their di-salts. The mono-salts of the α-sulfofatty acid alkyl esters are obtained in their industrial production as an aqueous mixture with limited amounts of di-salts. The disalt content of such surfactants is usually below 50% by weight of the anionic surfactant mixture, for example up to about 30% by weight.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which represent mono-, di- and triesters and their mixtures as they do in the production by esterification by a monoglycerol with 1 to 3 Moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2. mol Glycerin can be obtained.

Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin. As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid half esters of the C ₁₂ -C ₁₈ alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. C ₁₆ -C ₁₈ alk (en) yl sulfates are particularly preferred from the point of view of washing technology. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use C ₁₆ -C ₁₈ -alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and relatively low ones Washing temperatures of, for example, room temperature to 40 ° C. show a low tendency to crystallize. In a preferred embodiment of the invention, the agents therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C ₁₂ -C ₁₄ alkyl sulfates or C ₁₂ -C ₁₈ alkyl sulfates with C ₁₆ -C ₁₈ alkyl sulfates and in particular C ₁₂ -C ₁₆ -Alkyl sulfates with C ₁₆ -C ₁₈ -alkyl sulfates. In a further preferred embodiment of the invention, however, not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C ₁₆ to C ₂₂ are used. Mixtures of saturated sulfonated fatty alcohols predominantly consisting of C ₁₆ and unsaturated sulfated fatty alcohols predominantly consisting of C ₁₈ are particularly preferred, for example those derived from solid or liquid HD-Ocenol ^(R) fatty alcohol mixtures (commercial product of the applicant) . Weight ratios of alkyl sulfates to alkenyl sulfates from 10: 1 to 1: 2 and in particular from about 5: 1 to 1: 1 are preferred.

2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN ^(R) , are also suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C ₇ -C ₂₁ alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C ₉ -C ₁₁ alcohols with an average of 3.5 mol of ethylene oxide (EO) or C ₁₂ - C ₁₈ fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

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

In addition to the anionic surfactants, the agents can also contain soaps, preferably contained in amounts of 0.2 to 5 wt .-%. Saturated ones are suitable Fatty acid soaps, such as the salts of lauric acid, myristic acid, Palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid as well especially from natural fatty acids, e.g. Coconut, palm kernel or Tallow fatty acids, derived soap mixtures.

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.

In one embodiment of the invention, detergents or cleaning agents, especially preferred extruded washing or cleaning agents, which contain 10 to 30% by weight of anionic surfactants. Advantageously are preferably at least 3% by weight and in particular at least 5% % By weight of sulfate surfactants. In an advantageous embodiment, in the means - based on the total anionic surfactants - at least 15 wt .-%, in particular 20 to 100 wt .-% sulfate surfactants.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of 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 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ alcohols with 3 EO or 4 EO, C ₉ -C ₁₁ alcohol with 7 EO, C ₁₃ -C ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -C ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₁₂ -C ₁₄ alcohol with 3 EO and C ₁₂ -C ₁₈ alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction 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 include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may be suitable. The amount of this nonionic Surfactants are preferably no more than that of the ethoxylated ones Fatty alcohols, especially not more than half of them.

in der R²CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R³ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht.Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),

in the R ² CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ³ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands.

The polyhydroxy fatty acid amides are known substances that usually by reductive amination of a reducing sugar with Ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride can be obtained. Regarding the processes for their manufacture see U.S. Patent Nos. 1,985,424, 2,016,962 and US-A-2,703,798 and International Patent Application WO-A-92/06984 referred. The polyhydroxy fatty acid amides are preferably derived from reducing agents Sugars with 5 or 6 carbon atoms, especially from that Glucose.

Nonionic surfactants are preferred in the agents according to the invention in amounts of 0.5 to 15% by weight, in particular in amounts of 2 to 10 % By weight.

In addition to the amorphous and impregnated alkali silicates, the agents also contain additional builder substances and cobuilders. The latter include primarily the ingredients already mentioned above, for example polycarboxylates and polymeric polycarboxylates. These cobuilders are preferably in the compositions in amounts of 2 to 20 % By weight and in particular from 5 to 15% by weight.

However, conventional builders such as phosphates, zeolites and crystalline layered silicates can also be included in the agents. The synthetic zeolite used is preferably finely crystalline and contains bound water. Zeolite A, for example, but also zeolite X and zeolite P and mixtures of A, X and / or P are suitable. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. It is also possible to use zeolite suspensions and zeolite powder. Suitable zeolite powders have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

In a preferred embodiment of the invention, washing or Detergent 0 to 16% by weight zeolite (based on anhydrous active substance) and 10 to 40% by weight of an impregnated fabricated according to the invention Alkali silicate, in particular it should be ensured that the finished agent at least 15 wt .-% of these builder substances mentioned having.

In a further preferred embodiment of the invention, the washing or cleaning agent therefore 0 to 5 wt .-% zeolite (based on anhydrous Active substance) and 15 to 40 wt .-% of a prepared according to the invention impregnated additive containing alkali silicate or 10 to 30 % By weight of zeolite (based on anhydrous active substance) and 15 to 40 % By weight of a silicate-containing additive produced according to the invention. there it is possible that the zeolite is not only co-extruded, but that some or all of the zeolite subsequently, that is after the extrusion step is introduced into the detergent or cleaning agent. Especially detergents or cleaning agents which contain an extrudate are preferred contained, which is free of zeolite inside the extrudate grain.

Crystalline layered silicates can also be used as substitutes for the zeolite and / or conventional phosphates are used. However, it is preferred that phosphates only in small amounts, in particular up to a maximum 10% by weight, are contained in the washing or cleaning agents.

Crystalline layered silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, and are preferred as crystalline layered silicates Values for x 2, 3 or 4 are suitable. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred. However, these crystalline layered silicates are preferably contained in the extrudates according to the invention only in amounts of not more than 10% by weight, in particular less than 8% by weight, advantageously not more than 5% by weight.

Organic cobuilders that can be used are, for example, preferably in the form their sodium salts used polycarboxylic acids, such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, Nitrilotriacetic acid (NTA), provided such use ecological reasons are not objectionable, as well as mixtures of this. 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.

However, polymeric polycarboxylates are particularly preferred, for example the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are in particular those of acrylic acid with methacrylic acid and acrylic acid or Methacrylic acid with maleic acid. Copolymers have proven particularly suitable of acrylic acid with maleic acid, the 50 to 90 wt .-% acrylic acid and contain 50 to 10% by weight of maleic acid. Your molecular weight, based on free acids, is generally 5000 to 200000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. In particular biodegradable terpolymers are also preferred, for example those which according to DE-A-43 00 772 as monomers salts of Acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomer salts of acrylic acid and the 2-alkylallylsulfonic acid and sugar derivatives. More preferred Copolymers are those that are described in German patent applications DE 43 03 320 and DE 44 17 734 are described and preferably as monomers Acrolein and acrylic acid / acrylic acid salts or acrolein and Have vinyl acetate.

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 cellulose and methyl hydroxypropyl cellulose with a proportion on methoxyl groups from 15 to 30% by weight and on hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic Cellulose ether, as well as the polymers known from the prior art Phthalic acid and / or terephthalic acid or their derivatives, in particular Polymers made from ethylene terephthalates and / or Polyethylene glycol terephthalates or anionic and / or nonionic modified Derivatives of these.

The agents can also contain components which have solubility especially the heavy granules. Such components and the introduction of such components, for example in international patent application WO-A-93/02176 and in German patent application DE 42 03 031. Among the preferred ones Ingredients include in particular fatty alcohols with 20 to 80 Moles of ethylene oxide per mole of fatty alcohol, for example tallow fatty alcohol with 30 EO and tallow fatty alcohol with 40 EO, but also fatty alcohols with 14 EO as well Polyethylene glycols with a molecular weight between 200 and 2000.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid 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, with perborate monohydrate being advantageously used. Percarbonate is also preferred as an ingredient. However, percarbonate is preferably not co-extruded, but optionally mixed in subsequently.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below, bleach activators can be incorporated into the preparations. Examples of these are N-acyl or 0-acyl compounds which form organic peracids with H ₂ O ₂ , preferably N, N'-tetraacylated diamines, p- (alkanoyloxy) benzenesulfonates, furthermore carboxylic anhydrides and esters of polyols such as glucose pentaacetate.

Other known bleach activators are acetylated mixtures of sorbitol and mannitol, as for example in the European patent application EP-A-0 525 239. The content of bleach Bleach activators are preferably in the usual range between 1 and 10% by weight and in particular between 3 and 8 % By weight. Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN).

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 C ₁₈ -C ₂₄ fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes. The foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.

Enzymes come from the class of proteases, lipases, amylases, Cellulases or their mixtures in question. Are particularly well suited Bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens obtained enzymatic Active ingredients. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used. Enzyme mixtures, for example of 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, but especially mixtures containing protease and / or lipase of special interest. Also have peroxidases or oxidases proved to be suitable in some cases. The enzymes can on carriers adsorbed and / or embedded in enveloping substances around them protect against premature decomposition. The proportion of 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 salts of polyphosphonic acids come as stabilizers, in particular 1-hydroxyethane-1,1-diphosphonic acid (HEDP), diethylenetriaminepentamethylenephosphonic acid (DETPMP) or ethylenediaminetetramethylenephosphonic acid in Consideration.

The agents can also contain further enzyme stabilizers. For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. However, the use of boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H ₃ BO ₃ ), metaboric acid (HBO ₂ ) and pyrobic acid (tetraboric acid H ₂ B ₄ O ₇ ), is particularly advantageous.

Graying inhibitors have the task of removing the fiber Keep dirt suspended in the fleet and prevent 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 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. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful. However, cellulose ethers such as Carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methylhydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their Mixtures and polyvinylpyrrolidone, for example in amounts from 0.1 to 5 % By weight, based on the composition.

The agents can, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed connections that instead the morpholino group is a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type can also be used 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.

Examples Example 1:

In a 3-liter mixer from Lödige (Lödige FM), 70 parts by weight of a spray-dried granulate of 80% by weight of a sodium silicate with the module 2.4, 5% by weight sodium carbonate and 15% by weight were Water mixed with 30 parts by weight of an aqueous dispersion of 50% by weight of C ₁₂ -C ₁₈ alcohol with 7 EO, 25% by weight of water and 25% by weight of a spray-dried silicate granulate of the composition given above. The mixture was stirred for 1 minute. The bulk density was 550 g / l. The flow behavior was 67% (test method: see below).

For comparison, 70 parts by weight of the above-mentioned granular silicate were mixed with 15 parts by weight of a pure C ₁₂ -C ₁₈ alcohol with 7 EO. The product should then be mixed with 15 parts by weight of a 50% by weight aqueous solution of the spray-dried silicate granules. After mixing with the nonionic surfactant, however, the silicate granules presented were no longer free-flowing (not measurable!) And were already so sticky to pasty that further exposure to the aqueous solution could no longer be carried out.

Example 2:

Example 1 was carried out with 83 parts by weight of a spray-dried silicate granulate having the composition given in Example 1 with 10 parts by weight of an aqueous dispersion of 72% by weight of C ₁₂ -C ₁₈ alcohol with 7 EO, 24 parts by weight. % Water and 4 wt .-% sodium sulfate repeated. This was followed by an aftertreatment with 7 parts by weight of a 30% by weight aqueous solution of Sokalan CP5 ^(R) (copolymeric sodium salt of acrylic acid and maleic acid, commercial product from BASF, Federal Republic of Germany). The bulk density was 468 g / l. The trickle behavior was 79%.

For comparison, 83 parts by weight of the spray-dried silicate granules specified were mixed with 10 parts by weight of C ₁₂ -C ₁₈ alcohol with 7 EO. However, after mixing with the nonionic surfactant alone, the silicate granules were no longer free-flowing (not measurable!) And were already so sticky to pasty that further exposure to the aqueous Sokalan solution could no longer be carried out.

Also reducing the amount of nonionic surfactant with which the silicate Granules were mixed to 7.2 parts by weight did not result in a free-flowing product, which also does not continue with an aqueous solution could be treated.

Example 3:

The replacement of C ₁₂ -C ₁₈ alcohol with 7 EO by C ₁₂ -C ₁₈ fatty acid methyl ester with 12 EO in Examples 1 and 2 led to comparable results with regard to the flow behavior.

Method for determining the trickle behavior

To determine the flow behavior, 1 liter of the according to the Examples 1 to 3 according to the invention in one at its outlet opening first filled powder hopper and then the expiry time of the silicate products compared to dry sea sand. The Drainage time of the dry sea sand after opening the discharge opening (13 Seconds) was set to 100%.

Claims (16)

1. A process for the production of a particulate amorphous alkali metal silicate with a molar ratio of M₂O to SiO₂ (M = alkali metal) of 1:1.5 to 1:3.3,

   a) an aqueous mixture essentially containing an amorphous alkali metal silicate with the composition indicated above as active substance being spray-dried
   characterized in that

   b) the spray-dried mixture is subsequently impregnated with an aqueous dispersion of ingredients of detergents or cleaners, at least one organic ingredient of detergents or cleaners being present in the form of a dispersion in water or an aqueous solution, and

   c) is optionally dried.
2. A process as claimed in claim 1, characterized in that an aqueous mixture which contains no alkali metal carbonates or which only contains alkali metal carbonates in ratios by weight of alkali metal silicate (expressed as water-free active substance) to alkali metal carbonate of 3:1 to 20:1 is prepared.
3. A process as claimed in claim 1 or 2, characterized in that a spray-dried silicate-containing compound (a) containing 55 to 95% by weight and preferably 60 to 90% by weight of alkali metal silicate (expressed as water-free active substance), 0 to 15% by weight and preferably 2 to 10% by weight of alkali metal carbonate and 5 to 22% by weight, preferably 10 to 20% by weight and more particularly at least 15% by weight of water is prepared.
4. A process as claimed in any of claims 1 to 3, characterized in that other ingredients, particularly ingredients of detergents or cleaners, are incorporated in the mixture to be spray dried, their content - based on the spray-dried silicate-containing product of step (a) - preferably being from 0.5 to 20% by weight.
5. A process as claimed in any of claims 1 to 4, characterized in that anionic surfactants and/or organic co-builders are used in the mixture to be spray dried, preferably in quantities of 1 to 15% by weight, based on the spray-dried silicate-containing product of step (a).
6. A process as claimed in any of claims 1 to 5, characterized in that the spray-dried silicate-containing products are impregnated with an aqueous dispersion of ingredients of detergents or cleaners in quantities of 3 to 40% by weight and, more particularly, 5 to 35% by weight, based on the impregnated and optionally dried silicate-containing product.
7. A process as claimed in any of claims 1 to 6, characterized in that an emulsion of one or more nonionic surfactants and water or an aqueous solution of one or more inorganic salts is used as the aqueous dispersion.
8. A process as claimed in any of claims 1 to 7, characterized in that salt solutions of silicates, carbonates, bicarbonates and/or sulfates are used as the aqueous solution in the dispersion.
9. A process as claimed in any of claims 1 to 8, characterized in that a solution of the spray-dried product (a) in water is used in the aqueous dispersion, preferably in quantities of 10 to 40% by weight and more particularly in quantities of 15 to 35% by weight, based on the dispersion as a whole.
10. A process as claimed in any of claims 1 to 9, characterized in that ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters are used on their own or in combination with other water-insoluble organic components as the organic dispersion component.
11. A process as claimed in claim 10, characterized in that water only and not a salt solution is used as an inorganic component in the aqueous dispersion.
12. A process as claimed in any of claims 1 to 11, characterized in that a spray-dried silicate-containing product (a) and at least one other solid, powder-form or granular product, which is a single raw material or a compound of at least two different raw materials, are impregnated together in step (b) of the process.
13. A process as claimed in claim 12, characterized in that a compound containing alkali metal carbonate and organic co-builders is used as the other compound.
14. A process as claimed in any of claims 1 to 13, characterized in that 60 to 85 parts by weight of a spray-dried silicate-containing product (a) are first impregnated with 5 to 38 parts by weight of an aqueous dispersion (b) and then aftertreated with 2 to 15 parts by weight of another liquid preparation, preferably an aqueous solution of organic co-builders.
15. A process as claimed in any of claims 1 to 14, characterized in that a concluding drying step is carried out if the water content after the first two steps of the process and the optional aftertreatment (expressed as the total water content of the spray-dried silicate, the aqueous dispersion and optionally the aqueous preparation from the aftertreatment) is above 22% by weight and preferably above 20% by weight.
16. A process as claimed in any of claims 1 to 15, characterized in that the silicate-containing product obtained after step (b), another aftertreatment or step (c) of the process is aftertreated with fine-particle dried powders in order further to increase its bulk density.