EP0748369B1 - Multi-substance mixtures based on water-soluble alkali silicate compounds and their use - Google Patents

Abstract

PCT No. PCT/EP95/00604 Sec. 371 Date Oct. 10, 1996 Sec. 102(e) Date Oct. 10, 1996 PCT Filed Feb. 20, 1995 PCT Pub. No. WO95/23841 PCT Pub. Date Sep. 8, 1995The invention relates to a solid material (primary drying product) containing alkali metal silicate with a modulus (molar ratio of SiO2 to M2O, M=alkali metal) of 0.8 to 4 in homogeneous admixture with other inorganic and/or organic useful materials and/or auxiliaries, which has been dried from a finely sprayed aqueous preparation of mixtures of the alkali metal silicates and the inorganic and/or organic useful materials and/or auxiliaries by means of a hot gas stream. The solid material according to the invention is characterized in that, as a primary drying product in homogeneous admixture with the alkali metal silicate, it contains at least 10% by weight of water-soluble inorganic and/or organic salts, has apparent densities of at least 150 g/l, possesses a microporous absorbent internal structure and has been dried with superheated steam as the hot gas stream. The invention also relates in particular to detergent builder systems based on multicomponent systems containing this overdried alkali metal silicate and to their use for subsequent impregnation with other free-flowing useful materials and mixtures thereof from the field of detergents and to the detergents obtained.

Description

The teaching according to the invention relates to the field of solid materials and mixtures of materials based on water-soluble alkali metal silicate compounds, which are also referred to in the specialist literature as water glasses. This term includes the soluble silicates of the alkalis, in particular corresponding sodium and / or potassium compounds, which correspond to the composition xSiO ₂ · yM ₂ O · zH ₂ O (M = alkali metal) in oxide notation. The ratio of x: y is called the module. Module ranges of water-soluble alkali metal silicate compounds of the type concerned according to the invention are in the range from about 0.8 to 4.

Water glasses of the type affected here find the most varied in practice Use. The following are only examples: adhesives for paper and cardboard; Binder for the production of refractory Kitte, in the enamel and building materials industry as well as in the Foundry as core binder; Corrosion protection agents, in particular to inhibit the alkaline attack on aluminum and zinc; Plasticizer to lower the viscosity of ceramic slurry cores; Stabilizers in the peroxide bleaching of paper and textiles; Binder as part of soil and rock consolidation in the House, tunnel and mining as well as the humusless greening of Dunes and debris piles or flocculants in water treatment. One of the most important areas of application for water glasses is their use as components in detergents and cleaning agents. They have a wide range of functionality to fulfill here which will be discussed in more detail below.

This is only a partial list of technical areas of application for water glasses makes the following basic requirements understandable: the water glasses should be stored in a dry place transportable form of supply are available and at the same time in practical use but easy to solve. In numerous Areas of application also play the rapid cold water solubility a crucial role. The task according to the invention is based - among other things - on this basic requirement. A new technical instruction is given, as in cost-saving and on an industrial scale, aqueous water glass solutions of the type described to be sufficient for dry products Bulk weights can be worked up, which nonetheless through excellent and spontaneous water solubility even in cold Mark water.

These are for numerous applications of this new offer form considerable progress already. The teaching of the invention goes Furthermore. It describes in preferred embodiments Water glass-based materials and mixtures of materials from the area of detergents and cleaning agents. This affects in particular the area of appropriate work equipment for cleaning of textiles.

Work equipment of the specified type and in particular corresponding Solid concentrates together with the detergent contain Surfactant compounds the so-called builders respectively Builder systems as main components in addition to other usual auxiliary and Additives. The builders or builder systems meet in Detergents and cleaners perform a variety of tasks with the constant change of the composition, the form of the offer and the production of detergents in recent years and Decades also change significantly. Modern detergents today contain approx. 20 to 50% by weight builder substances. These belong making it one of the most important classes of substances for building Detergents and cleaning agents.

Because of the variety and evolution of detergent systems indicated here the tasks of the builders are varied and neither fully defined quantitatively. The main requirements are however well described. Above all, water softening should be mentioned here, the strengthening of the washing effect, a Graying inhibition and dirt dispersion. Builders are supposed to contribute to the alkalinity necessary for the washing process high absorption capacity for surfactants show the effectiveness of Improve surfactants, positive contributions to the properties of Deliver solid products, for example in powder form, and thus have a structure-building effect or reduce the dust problem. This Different requirements can usually only be met with a builder component alone, so that usually a system of builders and co-builders is used.

For ecological reasons - please refer to the keywords of Reutrophication of water or the remobilization of heavy metals builders containing phosphorus and / or nitrogen today, respectively Builders systems as detergent components in the criticism devices. There has been a great deal today in particular in textile detergent formulations the three-dimensionally networked water-insoluble sodium aluminosilicate zeolite NaA prevailed. In considerable extent, especially in the context of textile detergents, However, the so-called CoBuilder is also used here necessary, especially to counteract unwanted incrustations. To a large extent, today together with zeolite NaA polymeric polycarboxylates, in particular copolymers based on Acrylic acid and maleic acid are used together with soda for this purpose. In addition, complexing agents are often used.

In recent times, purely silicate systems such as the crystalline disilicates - the so-called SKS types - or combinations such components with soda for use as a builder or co-builder. Please be referred in this context for example on the following publications: EP-A-o 205 070, EP-A-0 320 770, EP-A-0 425 428, EP-A-0 502 325 and EP-A-O 548 599, which consistently produce crystalline Sodium silicate is described. Please continue to refer to EP-A-0 488 868 and EP-A-0 561 656. Described here as Builders substance combinations of silicates and soluble inorganic salts such as sodium carbonate, sodium sulfate, sodium borate or perborate and other compounds of these Art.

Simultaneously with the development of the zeolite NaA as a builder proposed selected water-soluble amorphous sodium silicate compounds as builder substances in washing and cleaning agents to use. Reference is made, for example, to the US patents 3,912,649, 3,956,467, 3,838,193 and 3,879,527. Described here are amorphous sodium silicate compounds as Builder substances that are produced by spray drying aqueous water glass solutions, subsequent grinding and subsequent compacting and rounding produced with additional dehydration of the regrind be, cf. see, for example, FIG. 3 of US Pat. No. 3,912,649. The water content of the products used is approx. 18 to 20% by weight with bulk densities well above 500 g / l.

According to EP-A-0 444 415, detergents with 5 to 50 wt .-% at least one surfactant, 0.5 to 60 wt .-% of a builder as well as usual washing aids are proposed, with the mark lies in the fact that an amorphous water-poor as a builder Sodium disilicate with a water content of 0.3 to 6% by weight is used becomes. The amorphous sodium disilicate should preferably 0.5 to 2 Wt .-% water. The production of this highly dewatered Amorphous disilicates are made in a multi-stage process, initially the production of a powdered amorphous sodium silicate provides with a water content of 15 to 23 wt .-%. This Material is in a rotary kiln with flue gas at temperatures treated from 250 to 500 ° C in countercurrent. That from the rotary kiln escaping amorphous sodium disilicate is with the help of a mechanical Crushed to grain sizes of 0.1 to 12 mm and then grind to a particle size of 2 to 400 µm with a mill.

In contrast, the teaching of EP-A-0 542 131 wants to be considered a Builder component useful dried Sodium silicate containing water of crystallization with a free water content produce between 5 and 12% by weight in one process step, that a 40 to 60 wt .-% aqueous solution of sodium silicate in a turbo dryer equipped with striking tools is treated with hot air. The drying product passes through thereby a pseudoplastic state, which leads to the formation of a Product in granular form is used. The drying up of this Granules are carried out under working conditions, the one Embrittlement of the outer shell of the granules and a related breakage exclude the granulate structure. That way it will - while avoiding the so-called "popcorn effect" - possible, water soluble sodium silicates with specific weights in the range to produce between 0.5 and 1.2, which is characterized by complete Characterize solubility in water at ambient temperature.

The teaching according to the invention is essentially based on the example of the builder or builder mixed components described for detergents and cleaning agents. As introduced in the introduction is the area of action according to the invention not on restricted to this particular area of application, but it is special suitable, the characteristic of the teaching of the invention To summarize elements.

The teaching of the present invention is based on the task in a large-scale accessible and inexpensive process Water glasses or water glass-based multi-substance mixtures to win in an offer form that meets the varied requirements the product properties in practice. The In particular, the invention aims to create the possibility of an improved one Access to highly effective builders respectively Finding builder systems for detergents and cleaning agents. Here there should be the possibility of direct or indirect combinations with other auxiliary and recyclable materials from the one affected here To be able to realize subject area already in the solid mixture.

Subject of the invention

Accordingly, the invention relates in a first embodiment to a solid material, the alkali metal silicates with a molar ratio of SiO ₂ : M ₂ O, where M is an alkali metal, from 0.8 to 4 in homogeneous mixture with further inorganic and / or organic value and / or auxiliary substances, characterized in that it contains at least 10% by weight of water-soluble inorganic and / or organic salts as inorganic and / or organic valuable substances and / or auxiliary substances, a bulk density of at least 150 g / l and a BET surface area of has at least 5 m ² / g, the alkali metal silicate content has a water content of below 15% by weight and the alkali metal silicates are present in at least 50% by weight in a Q ₂ and / or Q ₃ structure.

In a further embodiment, the invention relates to the use of the Solid goods as a builder in detergents and cleaning agents.

In this context, the invention also relates in particular Detergent and cleaning agent in solid preparation form, especially textile detergent, based on a mixture of surfactants, builder components and other usual valuable and / or auxiliary substances, which are characterized are that they contain a solid material - as described above.

The subject of the invention is finally a process for the production of a solid material, the alkali metal silicates with a molar ratio SiO ₂ : M ₂ O, where M = alkali metal, from 0.8 to 4 in homogeneous mixture with further inorganic and / or organic valuable and / or auxiliary substances contains and which contains at least 10% by weight of water-soluble inorganic and / or organic salts, has a bulk density of at least 150 g / l, the alkali metal silicate component has a water content of below 15% by weight, the alkali metal silicates contain at least 50% by weight present in Q ₂ and / or Q ₃ structure and the solid has a BET surface area of at least 5 m ² / g, by spray and / or fluidized-bed drying of a finely sprayed aqueous preparation of mixtures of the alkali metal silicates and the inorganic and / or organic valuable and / or auxiliary substances by means of superheated steam.

In the text below, the solid material according to the invention is often also referred to as "primary dry good" or dry good ".

Details of the teaching according to the invention

In the following, for a simplified understanding - without any claim for completeness - essential basic ideas presented, from their summary the inventive step is determined and becomes understandable.

A crucial core idea lies in the application of the principle drying, in particular spray drying and / or fluidized bed drying, aqueous preparations of valuable materials and Recyclable materials with superheated steam as a hot gas stream Feeding the evaporation energy into the material to be dried and the simultaneous absorption of the evaporated water portion in the stream of superheated steam and the removal of this evaporated water together with the one withdrawn from the drying zone superheated steam flow. The amount of water discharged is condensed and worked up while the rest of the overheated Steam is returned to the drying zone in a closed circuit after the amount of energy removed by drying has been fed again.

The applicant describes this working principle of drying in particular of materials and mixtures of materials from the field of Wetting, washing and cleaning agents published in a series Publications and older registrations. Referred is particularly referred to the following publications: DE-A 40 30 688 as well as the further publications according to DE-A 42 04 035; 42 04 090; 42 06 050; 42 06 521; 42 06 495; 42 08 773; 42 09 432 and 42 34 376.

The teaching according to the invention is based on the knowledge that, particularly in the field of drying water-containing preparations of water glasses of the type described at the outset, this technology of superheated steam drying allows access to a summation and multifunctionality of advantages which have hitherto not been known. The following applies without any claim to completeness: The closed circulation system of the superheated steam enables CO ₂ -free drying and thus avoids undesired secondary reactions in the material to be dried. The drying conditions can be controlled as required with regard to the residual water content. Dry products with residual water contents in the range of the equilibrium value of monomeric alkali silicate compounds can be obtained, but in particular the additional removal of water with simultaneous condensation of the silica residues to form oligomer and / or polymer compounds is possible. Practically any degree of drying in the silicate material can be set without adversely affecting the spontaneous and easy solubility of the dried product in water. Taking into account the tendency of the silica residue to three-dimensionally crosslink and thus to form sparingly soluble to insoluble fractions in the dry material, there is a very decisive advantage for the use of the superheated steam as a drying medium. Furthermore, the following applies: The primary dry material of the process according to the invention is obtained in the form of a free-flowing granular material of considerable bulk weights, which are desirable today for a variety of reasons. Nevertheless, this dry material has suitable BET surfaces for covering with other valuable and / or auxiliary substances, which go far beyond the outer shells of the grain structure to be calculated. The reason is that the primary dry material is a material with a microporous, absorbent internal structure, which can be filled with sufficiently flowable components in a subsequent work step. This microporous inner structure is also of decisive importance for the dissolving behavior of the dry material according to the invention.

It is immediately understandable that the advantages presented here in the broad area of application for soluble Water glasses are usable. Of particular importance for that important area according to the invention of washing and cleaning agents for textiles in particular come to those defined according to the invention Alkali silicate based builder components a variety of benefits. The following applies in particular: controllability of the drying result in the direction of targeted drying optimization without impairing water solubility the builder function in terms of both primary and of the secondary washing capacity in the respective detergent and cleaning agent for sure. The measure provided according to the invention, the water glasses in admixture with other auxiliary and / or valuable materials from preferably homogeneous solution - but possibly also from appropriate dispersions - processing leads to Recyclable materials, in which those in practical use interact kicking components from the start in an intimate mixture available. Interactions from, for example, builder and Cobuilder components possible in practical use that optimize are. The availability of the internal structure of the primary Dry goods with other detergent components are more advanced Advantages. For example, the dispersibility can be comparatively more water soluble or miscible Detergent components are facilitated in that these components in a flowable state in the inventive microporous solid bodies are absorbed and distributed therein.

In the first embodiment described above, the subject matter the invention a solid material also referred to as primary dry material, the alkali metal silicates of the specified module range from 0.8 to 4 in homogeneous mixture with at least 10 wt .-% - based on compound dry weight - further inorganic and / or contains organic valuable and / or auxiliary substances and from a finely divided sprayed aqueous preparation of mixtures of Alkali metal silicates and the other valuable and / or auxiliary substances has been dried using superheated steam. The preferred Alkali metal silicates are those of sodium and potassium. Corresponding comes especially in the field of detergent builders Sodium silicates become paramount while for example, potassium silicate compounds in technical fields may be the preferred compounds.

The alkali metal silicates are preferably present in the primary dry material in amounts of at least 25% by weight and in particular in amounts of at least 30% by weight,% by weight here based on the weight of the primary dry good. Particularly important embodiments of the invention contain the alkali metal silicate in quantities of at least 40% by weight and in particular in quantities of at least 50% by weight. Quantity ranges from 45 to 80% by weight, in particular 50 to 75% by weight of alkali metal silicate in the dry product can be particularly useful be important. The recyclable or auxiliary materials used are used in amounts of at least 10% by weight. Depending on the application, these second components can at least 15, make up at least 20 or at least 25% by weight, frequently 20 to 50% by weight and in particular 30 to 45% by weight of these second components relate to practically important embodiments. Here, too, the numerical value of the% by weight is determined on the Weight of the primary dry material.

The as auxiliary and / or valuable substances together with the alkali metal silicates Second components can be used from a specific selected second component exist, but can also also - taking into account the knowledge of possible interactions and in particular for the intended technical purpose - any combination of two or more auxiliary and / or Recyclable materials mixed with the silicate compounds for Come into play.

An essential element for the teaching according to the invention is in the sufficient density of the dry material without losing the abandon microporous basic structure. Here is a peculiarity which will be discussed below. First of all, the apply here following numerical values: lower limit for the invention target bulk weights is 150 g / l respectively at 200 g / l. In practice, bulk densities are often as high as possible desired, which - based on primary dry goods - at at least 250g / l or even higher at at least 300 g / l. Particularly preferred values are at least 350 g / l and especially at least 400 g / l. If this comparatively increased bulk weights especially in the field of spray-dried silicate compounds are not insignificant the following also applies here: Through the secondary allocation of the primary dry goods with further in particular flowable, components can be practically any Increase in bulk densities in the desired end product areas respectively. Compression is of course also possible of the primary dry material in a manner known per se in the context of a Post-treatment, for example by roller compaction, granulation and the same.

The previously mentioned lower limit values for the bulk weights nonetheless is of importance for the invention. The following applies: It it is known that in the spray drying of water-containing water glasses without the addition of second components as primary dry goods hollow spherical, extremely light powder are obtained, the Bulk densities are, for example, in the range from 50 to 100 g / l. It is known and described to carry out such a hollow spherical structure to destroy mechanical force and thus to a certain Increase in bulk density in the "secondary" dry material come. Work carried out in parallel by the applicant has shown that even when using superheated steam as Drying gas aqueous alkali silicate solutions without the addition of second components to such a hollow spherical light dry powder dry up. For the use of superheated steam as a drying medium, this is surprising in itself, in detail is thereupon in the context of the previously published parallel patent application WO-A-9523 763 (DE-A-44 06 591) of the applicant. The one affected here In contrast, the teaching according to the invention is based on the knowledge that that in the formation of water glass-based compounds in the sense of acting according to the invention already the bulk densities of the primary Dry goods rise to comparatively high values, as in are often required in practice. Nevertheless one remains microporous gut structure with extremely enlarged surface receive. The granular material obtained according to the invention is therefore already seen in its physical nature quite different formed as the hollow spherical structure of the dry products pure or practically pure water glass solutions.

In an important embodiment, the teaching according to the invention envisages practically complete exclusion of access or in-situ formation of CO ₂ to or in the drying zone. For this purpose, on the one hand, the circulation flow of the superheated steam is reheated by indirect energy input, as is described in the literature cited for hot steam drying. In a particular embodiment of the teaching according to the invention, however, the selection of the starting materials also ensures that no or no significant amounts of CO ₂ can be formed by in-situ conversion, as is possible, for example, if alkali metal bicarbonates are used. In any case, it can be ensured that no or no significant amounts of water-insoluble or sparingly soluble material are formed even in the modification of the formation of an "over-dried" water glass, which is discussed below. The proportion of insoluble material in the product dried according to the invention is preferably <3% by weight and in particular <1% by weight. As a rule, the complete solubility of at least the proportion of alkali silicate is ensured. The solubility of the dry material formed in its entirety is of course also determined by the solubility parameters of the second and third components, the nature of which will be discussed in detail.

The inventive step of drying the aqueous Water glass-based active ingredient mixtures looks important Embodiment the so-called "overdrying" of the alkali silicate material in front. Based on sodium silicates of the usual in detergents Module range from about 1.3 to 4, this means that the Residual water content in the sodium silicate portion below 18 % By weight and in particular below 15% by weight. These dry products with water contents are suitable according to the invention of the silicate content of at most 15% by weight, the Range of about 1 to 13 wt .-%, and again the range from about 3 to 10 wt .-% water in sodium silicate, special importance can come. Come in an important embodiment "Over-dried" X-ray amorphous alkali silicates and especially sodium silicates of the specified module range with water content in the primary dry goods in the range of about 6 to 13% by weight into consideration.

The setting of these drying results is in the expert known way through the process parameters of the drying stage with the superheated steam and here in particular the temperature level of the supplied water vapor, its amount and / or the dwell time of the goods in contact with the superheated Determined water vapor. The stronger the drying conditions chosen become, the stronger is usually the degree of "overdrying" in the process product. An important and very easy to control The process parameter in this context is the temperature of the superheated steam flow, determined at its inlet temperature and its outlet temperature. Depending on the sensitivity of the goods to be dried and the intended drying result the inlet temperature of the superheated steam within a wide temperature range can be selected. For example in Range of 120 to 450 ° C, preferably in the range of about 150 to 380 ° C. The outlet temperature of the evaporated amount of water loaded superheated steam is then correspondingly lower, preferred outlet temperatures can range, for example from about 115 to 220 ° C and in particular in the range from 130 to 200 ° C. The selection and adjustment of the respective working conditions is - as already mentioned - especially determined by the temperature sensitivity, especially that with the alkali silicates sprayed further auxiliary and / or recyclable materials as well through the desired drying result in the dry process product. Becomes a substantial "over-drying" of the alkali silicate desired as an immediate result of spray drying, then it will usually be appropriate to have relatively high inlet temperatures of superheated steam - for example in the area from 280 to 380 ° C - to choose and also the steam outlet temperatures to keep relatively high - for example in Range from 180 to 240 ° C. It is immediately clear that the invention but also allows drying to become the primary Dry goods under comparatively mild conditions with only limited "To overdry the alkali silicate and in a subsequent thermal stage - for example tempering elevated temperatures - the condition of the over-dried alkali silicate to train.

In this context, it can be of particular importance also the maximum temperature of the goods under the drying conditions come, for example in the range of 100 to 200 ° C and in particular can be in the range of about 110 to 150 ° C. The dwell time of good at such high temperatures but in the range of seconds, so product damage with certainty can be excluded, even if as mixed components temperature-sensitive components can also be used. Such As a rule, concerns are ruled out from the outset, if as mixed components for example temperature stable inorganic salts of the type of sodium sulfate or sodium carbonate for use come. Especially for the area of application of the invention Products as detergent builder compounds are important embodiments here in front. Here the temperature load can be harmless of the purely inorganic material in the drying zone towards an optimized "overdrying" of the alkali silicate can be set.

As a result of the "overdrying" of at least a substantial proportion of the alkali metal silicate, oligomer or polymer structures of the silica residues form in the "overdried" material. Due to the good water solubility of the dry products according to the invention, it can be assumed that these oligomeric or polymeric silica residues essentially correspond to the so-called Q ₂ and / or the Q ₃ structure, that is to say they have a chain-like or ring-shaped or sheet-like structure, but are not three-dimensionally cross-linked (Q ₄ state). The solid material of the teaching according to the invention contains at least 50% by weight, preferably at least 80% by weight, of the alkali metal silicate component as such an “over-dried” material with an oligomer or polymer structure of the silica residues. The term “Q structure” is also explained in EP-A-0488 868.

As mixture components in the sense of the teaching according to the invention dried together with the water glasses are such Preferred components that are at least partially water-soluble are so that the drying process really homogeneous mixtures accumulate with the microporous dry goods structure. Understandably can at least partially but also finely divided insoluble mixing components in the resulting dry material be incorporated.

These second components of the substance mixtures according to the invention can be both inorganic and organic in nature. Your selection and quality depends on the intended Purpose of the dry product. This is understandable to the following exemplary representations, which in turn without claim to be understood for completeness:

It may be desirable in the finished product or at its redissolution practically the pure alkali metal silicate component available as an active ingredient. Here can then for the Step of drying according to the invention in superheated Water vapor, for example an inorganic or an organic, preferably water-soluble, neutral salt is used become, that no own function in the stage of the employment of the developed redissolved dry products. A typical example for this are the alkali sulfates, especially sodium sulfate.

In many cases, however, it will be desirable to do just that Mixing components additional effects for the intended purpose of dry products. For example for the builder's work area for detergents and cleaning agents, that in addition to the main builder component - the alkali silicate - other in the same direction and possibly acting synergistically Cobuilder components can also be used. In the simplest In case this means, for example, the sharing of Alkali carbonates, especially sodium carbonate. The synergistic Increasing the effectiveness of builder combinations from dried Mixtures of sodium silicates of suitable module ranges - on which will be discussed below - and soda as multifunctional mixture in detergents and cleaning agents is, for example, in the publications already mentioned at the beginning EP-A-04 88 868 and EP-A-05 61 656. There will be corresponding active ingredient mixtures after a comparative time-consuming and labor-intensive processes that still exist as a compact system with a limited surface area, the complex one Offer active ingredient mixture in detergents and cleaning agents. The Design of corresponding builder / cobuilder mixtures according to the invention on the other hand, it is not just simple on an industrial scale Possible way, the microporous dry material gives the additional Advantage of the microporous inner structure and thus the Possibility of substantial proportions of other detergent components to be entered in the dry goods as an additional load.

The situation presented here with soda as a second component is equally traceable with organic cobuilder components, for example on the type of sodium citrates or other alkali salts, especially polyfunctional ones Carboxylic acids. Joint use is also possible of inorganic and organic cobuilder components in homogeneous Mix with the water glass. Such dry products can in turn as a carrier bead for the order of others active components - for example for the application of Nonionic surfactants and the like - serve.

In general, inorganic mixture components can be found under Consideration of the respective application water-soluble inorganic Salts are used, in particular corresponding ones Carbonates, bicarbonates, sulfates, halides, borates, Phosphates and / or polyphosphates are to be mentioned, in particular in Form of the corresponding sodium and / or potassium salts are.

The use of organic, preferably at least partly water-soluble, blend components will be in adjustment determined to the purpose. For the area of Detergent builder systems apply here: Usable organic builders are, for example, preferred in the form of 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), if such Use is not objectionable for ecological reasons, and mixtures of these. Salts are preferred Polycarboxylic acids such as citric acid, adipic acid, succinic acid, Glutaric acid, tartaric acid, sugar acids and mixtures of these.

Polymeric polycarboxylates are also suitable, for example the sodium salts of polyacrylic acid or methacrylic acid, in particular those with a molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are especially those of acrylic acid with methacrylic acid and Acrylic acid or methacrylic acid with maleic acid. As particularly suitable copolymers of acrylic acid with maleic acid have proven to be the 50 to 90% by weight acrylic acid and 50 to 10% by weight Contain maleic acid. Their relative molecular mass, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and especially 50,000 to 100,000. Especially biodegradable terpolymers are also preferred, for example those which are salts of acrylic acid and monomers of maleic acid and vinyl alcohol or vinyl alcohol derivatives (not before published international application WO-A-9415978 (DE-A-4300772)) or the as Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid as well Sugar derivatives (German patent DE-C-42 21 381) contain.

Other suitable builder systems are oxidation products from carboxyl-containing polyglucosans and / or their water-soluble salts, such as those found in international Patent application WO-A-93/08251 can be described or their Manufacturing, for example, in the international patent application WO-A-93/16110.

In addition to or instead of the previously mentioned second components but also other known materials from the field of Builder systems are used, for example crystalline ones Layered silicates or limited quantities of the water-insoluble ones Zeolites in detergent quality, especially zeolite NaA. Alkali carbonates can be used according to the teaching of the older international patent application WO-A-9429419 (DE-A-43 19 578) also describes sulfur-free 2 to 11 Carbon atoms and optionally a further carboxyl and / or Amino acids and / or their amino groups replaced become. So, for example, an at least partial exchange of alkali carbonates by glycine or glycinate be made.

But also completely different active ingredient components from the area of Detergents and cleaning agents are potential additional candidates for mixing with the main builder components based on water glass for subsequent drying with superheated Steam in the sense of the teaching according to the invention. So additionally Components are used, which the oil and fat washability made of textiles. This effect becomes particularly clear when a textile that is already soiled is soiled previously several times with a detergent according to the invention, the contains this oil and fat-dissolving component, is washed. To 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 wt .-% and Hydroxypropoxyl groups from 1 to 15 wt .-%, each based on the nonionic cellulose ethers, as well as those from the prior art known polymers of phthalic acid and / or terephthalic acid or from their derivatives, in particular polymers Ethylene terephthalates and / or polyethylene glycol terephthalates.

The alkali silicate-based components, which are dried and in particular “overdried” according to the invention, are generally characterized as dry products by their X-ray amorphous nature. Amorphous alkali silicates have been used in detergents for a long time, their function is essentially to provide the alkalinity necessary for the washing process. In commercially available detergents, amorphous sodium silicates are used as spray-dried water glasses with the module (SiO ₂ / Na ₂ O molar ratio) of approx. 2 to 3.5. These solid powders usually contain about 18 to 20% by weight of water and are distinguished, inter alia, by the fact that they have only a very small specific surface area according to BET (DIN 66131), which is significantly less than 5 m ² / g. Their cumulative volume, which can be determined using mercury porosimetry measurements (based on DIN 66133), is also very low and usually reaches values of up to 50 mm ³ / g. The absorption capacity of these spray-dried water glasses compared to liquid components, for example nonionic surfactants, is extremely low. Even when 5% by weight of the nonionic surfactant is added, the solids lose their powder properties and stick to one another. The microporous solid builders that are now used according to the invention can overlap in a number of material parameters with the corresponding values of the commercially available water glasses in solid form, but they differ fundamentally in the sum of their properties.

The builder components according to the invention are X-ray amorphous sodium silicates usually in the area mentioned here Coming module range from 1 to 4, especially within in the range from 1.3 to 3.7. Module values are of particular importance of at least 1.5 and in particular the range of 1.5 to 3.3 too. Preferred further lower limit values for the module range are at 1.7 and especially at 1.9 while still preferred upper limits for module values of 3.0 and in particular 2.7 lie. In previous practice of use amorphous water glasses in solid form in detergents can have module values around 2 - the disilicate compounds - a special meaning get. According to the invention, water glasses are also these Suitable module value. In important embodiments of the invention However, are sodium silicate builders or builder mixtures used, which differ at least partially from this module value and otherwise lie in the specified number range. Here preferred embodiments are characterized in that at least 5% by weight and in particular at least 10 to 20% by weight of the X-ray amorphous sodium silicate builders differ from module value 2.

The form of supply of the microporous valuable material grain with its alkali silicate content according to the invention is characterized by high BET surfaces (DIN 66131) and by high numerical values for the cumulative volume (DIN 66133). The BET surface area of the solid material according to the invention (primary dry material) is at least 5 m ² / g, lower limit values for this BET surface area of at least 7.5 m ² / g and in particular of at least 10 m ² / g being of particular importance. The cumulative volume of the primary dry material is generally at least 50 mm ³ / g, preferably at least 100 m ³ / g, and in special cases can also reach higher values, for example 150 mm ³ / g.

In practical use as a textile detergent builder stand out Mixtures defined according to the invention by improved application properties. It is particularly striking - in addition to improving the primary washing power - the Enhancement of incrustation inhibition and thus the improvement the so-called secondary washing power of, for example, textile detergents.

The rate of dissolution of the primary dry good is admittedly the second and third components used as mixture components co-determined, but it is usually in the higher range Dissolution rates. So the primary release rates Items to be dried for a maximum of about 2 minutes Standard conditions, preferably at most about 1 minute below Standard conditions - 95% by weight / 40 ° C in each case.

The absorption capacity of the primary dry goods for liquid components is surprisingly high. In suitable mixing units or by simply spraying on, for example, at least 40 to 50 % By weight - based on primary dry goods - of liquid components, such as corresponding nonionic surfactants. With important Embodiments can also liquid components in higher amounts recorded and essentially in the interior of the grain structure to be built in.

Characteristic of the X-ray amorphous dry products in the sense The definition according to the invention is that with the help of electron diffraction usually found microcrystalline fractions can be. This applies in particular to comparatively strong "over-dried" products, for example in the temperature range up to maximum 500 ° C, preferably in the temperature range from 120 to 450 ° C have been dried. As part of the description of the invention microcrystallinity means that short-range orders of the individual There are building blocks, but comprehensive long-range orders are absent, so that no reflections occur in the X-ray diffraction spectrum and the silicates can thus be characterized as X-ray amorphous.

Embodiments designed according to the invention fall within the scope of the invention Builder components in the form of the primary dry material, which in one secondary step with other particularly flowable components from the area of wetting, washing and cleaning agents have been. The microporous can be of particular importance Builders in the binding and absorption of liquid components to the mentioned area. Examples here are at room temperature or moderately elevated liquid non-surfactant temperatures Compounds, water-containing anionic surfactant pastes respectively Preparations, but also melts or plasticized highly concentrated anionic surfactants, foam inhibitors such as silicones and / or paraffins but also fabric softener formulations for Use in detergents and cleaning agents for household and commercial use named. The intimate mixing of the flowable components with the inorganic carrier component with a large surface area and the Possibility of this given mixture state also in the frame maintain the full packaging of detergents and cleaning agents, not only ensures the initially desired consolidation of the mixture of recyclables, in particular the functional protection the respective recyclable component when mixed into the aqueous wash liquor with a large surface area and high water solubility present builder component instead. The invention consistently used builder components high calcium and magnesium binding capacity, usually of at least 4 meq / g product (calculated on anhydrous alkali silicate substance). The functionality is thus optimized and ensured also of active substances sensitive to water hardness upon first contact with the surrounding aqueous phase in the wash liquor. It immediately makes sense that this is for the following Steps of the washing and cleaning process important Initial aids are given. But it becomes understandable just an essential core, in which the inventive State-of-the-art teaching distinguishes: The particulate Form of supply of the builder components described according to the invention based on sodium silicate is characterized by the Large, accessible surface that connects the microporous material structure. For the reaction sequence of dissolving the detergent and cleaning agent mixture in the wash liquor and the primary reactions of the Interaction between aqueous liquor and mixture of active ingredients leads this has important advantages over comparable mixtures, in which the builder component is largely in shape rounded small particles with a greatly reduced overall Surface.

The mixing of the builder components according to the invention on the basis of the microporous and highly absorbent multicomponent mixtures in the form of the primary dry material enables the loadable finished product which is ultimately obtained to be largely freely adjustable. By incorporating the valuable and / or auxiliary materials in a flowable state, the bulk weight of the combined material can be varied largely freely. The builder components can thus also be used in modern detergents with bulk densities of at least about 0.7 g / cm ³ .

In the following, information is given without any claim to completeness made into mixture components that are part of the Multi-substance mixtures according to the invention also used or can be applied to the primary dry material. Basically here is the entire area of valuable and auxiliary materials from the Area of detergents and cleaners available. Especially here come surfactants of anionic, nonionic, cationic, amphoteric and / or zwitterionic structure and other inorganic and / or organic builders, bleaches and Bleach activators, enzymes and enzyme stabilizers, foam inhibitors, optical brighteners, inorganic alkaline and / or in Water-neutral salts, for example sulfates or Chlorides, and colors and fragrances.

Suitable surfactants of the sulfonate type are preferably the known C ₉ -C ₁₃ alkylbenzenesulfonates, olefin sulfonates and alkanesulfonates. 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 fatty alcohol, oleyl alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C ₁₀ -C ₂₀ oxo alcohols, and those secondary alcohols of this chain length. The sulfuric acid monoesters of the alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C ₉ -C ₁₁ alcohols with an average of 2 or 3.5 mol of ethylene oxide, are also suitable.

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

Soaps are particularly preferred as further anionic surfactants in amounts below 5% by weight. Are suitable saturated fatty acid soaps, 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 that are deriving from oleic acid, for example, may also be present However, their proportion of soaps should not be 50% by weight exceed.

The anionic surfactants and soaps can be in the form of their sodium, Potassium or ammonium salts as well as organic organic salts Bases, such as mono-, di- or triethanolamine, are present. Preferably are the anionic surfactants in the form of their sodium or potassium salts, especially in the form of the sodium salts. The salary of the The average of anionic surfactants is between 5 and 40% by weight.

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 (E0) 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 E0 per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ alcohols with 3 E0 or 4 E0, C ₉ -C ₁₁ alcohol with 7 EO, C ₁₃ -C ₁₅ alcohols with 3 E0, 5 E0, 7 E0 or 8 E0, C ₁₂ -C ₁₈ alcohols with 3 E0, 5 E0 or 7 E0 and mixtures thereof, such as mixtures of C ₁₂ -C ₁₄ alcohol with 3 EO and C ₁₂ -C ₁₈ alcohol with 5 E0. 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 E0 can also be used. Examples include tallow fatty alcohol with 14 E0, 25 E0, 30 E0 or 40 E0.

In addition, alkyl glycosides of the general formula R0 (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; x is preferably 1.2 to 1.4.

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

All previous builders can be used as further inorganic builder substances usually used builder substances are used. To these include in particular zeolites, crystalline layered silicates, even phosphates, if not used for ecological reasons should be avoided. Your salary can vary depending on the salary on the X-ray amorphous and "over-dried" Silicates with body structure vary in a wide range. The sum of customary builder substances and those according to the invention Silicates are usually 10 to 60% by weight.

Usable organic builders, which are also separated from the Alkali silicates and / or in combination with corresponding ones Compounds that can be used are, for example previously mentioned, preferably used in the form of their sodium salts Polycarboxylic acids, such as citric acid, adipic acid, succinic acid, Glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA).

Suitable polymeric polycarboxylates are those already mentioned above Groups of substances, for example the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative Molecular mass from 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. In detail, the previous one Reference is made to these classes of substances.

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.

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 0 ₂ , 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'-tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN).

When used in machine washing processes, it can be 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 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. Particularly good are suitable from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus enzymatic agents. Proteases are preferably from Subtilisin type and especially proteases derived from Bacillus lentus won, used. There are enzyme mixtures, for example from protease and amylase or protease and lipase or Protease and cellulase or from cellulase and lipase or from protease, Amylase and lipase or protease, lipase and cellulase, but especially cellulase-containing mixtures of particular Interest. Peroxidases or oxidases have also been found in some Cases proved to be suitable. The enzymes can on carriers adsorbed and / or embedded in enveloping substances to counter them to protect premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-%.

As stabilizers, especially for per-compounds and enzymes come the salts of polyphosphonic acids, especially 1-hydroxyethane-1,1-diphosphonic acid (HEDP), Diethylenetriaminepentamethylenephosphonic acid (DETPMP) or Ethylenediaminetetramethylenephosphonic acid (EDTMP) into consideration.

Graying inhibitors have the task of keeping the dirt detached from the fibers 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. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, strong aldehydes, 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, methyl carboxymethyl cellulose and mixtures thereof, and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the detergent, are preferred used.

The agents can be used as optical brighteners Contain diaminostilbenedisulfonic acid or its 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 similar connections, which instead of the morpholino group is a diethanolamino group, a Methylamino group, an anilino group or a 2-methoxyethylamino group carry. Brighteners of the type of the substituted diphenyl styrenes, e.g. the alkali salts 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 be used.

The bulk density of the preferred granular washing or cleaning agents, which contain the silicates according to the invention and with the other components of common washing and cleaning agents are applied, is generally 300 to 1200 g / l, preferably however 500 to 1100 g / l. Are very particularly preferred washing and cleaning agents with bulk densities of at least 700 g / l. They can be produced by any of the known processes such as mixing, spray drying, granulating and extruding take place, the X-ray amorphous and "over-dried" according to the invention Silicate compounds and preferably those with flowable Recyclable materials from the field of detergents and cleaning agents, in particular with nonionic surfactants, loaded silicate compounds advantageously be added to the other components of the agent. Processes in which several are particularly suitable Sub-components, for example spray-dried components and granulated and / or extruded components mixed together become. Especially in granulation and extrusion processes it is preferred to form any anionic surfactants present a spray-dried, granulated or extruded compound either as an admixture in the processes mentioned or as Additive additive to other granules. Likewise it is possible and can be beneficial depending on the recipe be if further individual components of the agent, for example Carbonates, citrate or citric acid or others Polycarboxylates or polycarboxylic acids, polymeric polycarboxylates, Zeolite and / or layered silicates, for example layered crystalline disilicates, subsequently spray-dried, granulated and / or extruded components are added.

In particular, the way of compiling applies washing and cleaning agents according to the invention the general specialist knowledge. For example, temperature-sensitive components such as enzymes, volatile fragrances or fragrances, but possibly also temperature sensitive Percarbonate compounds mixed in under working conditions that exclude damage to such components. Crucial for the washing and cleaning agents in the sense of the invention Teaching is the use of alkali silicate builders respectively corresponding builder compounds which are used in the sense of the invention Procure definition and have been produced.

Examples example 1

In a pilot spray tower on a pilot scale of the "Minor Production" type The company Niro-Atomizer produces an aqueous solution of water glass and soda spray dried with superheated steam. The aqueous solution of the The mixture of recyclable materials to be dried is added via a 2-component nozzle superheated steam sprayed as a propellant.

To mix the valuable substances, the sodium carbonate was dissolved in distilled water at about 80 ° C. to give a clear solution and mixed with the water glass present as an aqueous preparation. In the feed mixture, a mixing ratio of 1: 1 - based on dry substance (TS) - is set for the two components water glass and soda as Na ₂ CO ₃ x 10H ₂ O. TS content of the feed solution 37% by weight pH of the aqueous preparation 12.2

The water glass in the aqueous preparation to be sprayed is characterized by the following characteristics: Density kg / m ³ 1,690 - 1,710 Water glass module 2.00 - 2.06 Viscosity mPas / 20 ° C > 10,000 % By weight of water 44.6 - 46.2 % By weight SiO ₂ 36.0 - 37.0 % By weight Na ₂ O 17.8-18.4

The following operating parameters were set for hot steam drying: Steam inlet temperature 315 ° C Steam outlet temperature 200 ° C Tower vacuum (mm WS) 40-80 Feed pump pressure 0.6 bar Feed temperature 75 ° C Feed quantity 12 kg / h Amount of steam 500 m ³ / h Propellant (superheated steam) the 2-substance nozzle quantity 6.5 kg / h print 0.3 bar

A free-flowing, fine-grained white product is obtained as a process product, which is characterized by the following material parameters: Residual moisture at 140 ° C 1.0% by weight Bulk density 420 g / l Solubility in water (90% / 20 ° C) 30 sec

Example 2

In the system of Example 1, an aqueous preparation of water glass, soda and sodium citrate is spray-dried with superheated steam as the drying gas. The following mixing ratio (calculated as TS) is set:
45% by weight water glass, 10% by weight Na ₂ CO ₃ x 10 H ₂ O and
45% by weight C ₆ H ₅ O ₇ Na ₃ x 2 H ₂ O

For the preparation of the aqueous preparation to be sprayed, the Sodium carbonate together with the trisodium citrate in distilled water dissolved at approx. 80 ° C to a clear solution and added to the water glass.

The following characteristic data apply to the aqueous preparation to be sprayed: TS content of the feed solution 53% by weight PH value 12.2 Water glass module 2.00 - 2.06

The following operating parameters were set for hot steam drying: Steam inlet temperature 320 ° C Steam outlet temperature 203 ° C Tower vacuum (mm WS) 80 Feed pump pressure 0.8 bar Feed temperature 75 ° C Feed quantity 14 kg / h Amount of steam 500 m ³ / h Propellant (superheated steam) of the 2-substance nozzle quantity 6.5 kg / h print 0.4 bar A free-flowing granular material is obtained with a residual moisture (140 ° C.) of 1.2% by weight and a bulk density of 155 g / l. The solubility in water (90 wt .-% / 20 ° C) is 98 sec.

Claims (14)

1. A solid material containing alkali metal silicates with a molar ratio of SiO₂ to M₂O (M = alkali metal) of 0.8 to 4 in homogeneous admixture with other inorganic and/or organic useful materials and/or auxiliaries, characterized in that it contains at least 10% by weight of water-soluble inorganic and/or organic salts as the inorganic and/or organic useful materials and/or auxiliaries, has an apparent density of at least 150 g/l and a BET surface of at least 5 m²/g, the alkali metal silicate component has a content below 15% by weight and at least 50% by weight of the alkali metal silicates are present in the Q₂ and/or Q₃ structure.
2. A solid material as claimed in claim 1, characterized in that the alkali metal silicate component has a water content of 1 to 13% by weight.
3. A solid material as claimed in one or both of claims 1 and 2, characterized in that the alkali metal silicate makes up at least 25% by weight, preferably at least 40% by weight and more preferably at least 50% by weight, the other useful materials and/or auxiliaries present in homogeneous admixture being present in quantities of at least 15% by weight, preferably in quantities of at least 20% by weight and more preferably in quantities of at least 25 % by weight.
4. A solid material as claimed in one or more of claims 1 to 3, characterized in that compounds of sodium and/or potassium are present as the alkali metal silicates and preferably as homogeneously incorporated salts.
5. A solid material as claimed in one or more of claims 1 to 4, characterized in that at least the alkali metal silicate component
      is distinguished by such solubility in water, even at ambient temperature, that its percentage content of insoluble material is less than 3% by weight and, in particular, less than 1% by weight.
6. A solid material as claimed in one or more of claims 1 to 5, characterized in that the alkali metal silicate is X-ray amorphous.
7. A solid material as claimed in one or more of claims 1 to 6, characterized in that the water-soluble inorganic and/or organic useful materials and/or auxiliaries present in admixture with the alkali metal silicates are alkali metal salts in the form of the corresponding carbonates, sulfates, halides, phosphates, polyphosphates, borates and/or salts of lower, preferably polybasic carboxylic acids and/or polymeric polycarboxylic acids or copolymers thereof.
8. The use of the solid material claimed in one or more of claims 1 to 7 as a builder in detergents.
9. The use claimed in claim 8, characterized in that the solid material is impregnated with free-flowing other useful materials typically used in detergents, particularly laundry detergents, or with mixtures thereof.
10. The use claimed in claim 9, characterized in that the solid material is impregnated with free-flowing useful materials selected from nonionic surfactants, liquid formulations of anionic surfactants, plasticized highly concentrated anionic surfactants, free-flowing fabric softener formulations and/or foam inhibitors, preferably from the class of silicones and/or paraffins, or with mixtures of such useful materials.
11. Detergents in solid form, more particularly laundry detergents based on a mixture of surfactants, builder components and other typical useful materials and/or auxiliaries, characterized in that they contain the solid material claimed in claims 1 to 7.
12. A process for the production of a solid material which contains alkali metal silicates with a molar ratio of SiO₂ to M₂O (M = alkali metal) of 0.8 to 4 in homogeneous admixture with other inorganic and/or organic useful materials and/or auxiliaries and at least 10% by weight of water-soluble inorganic and/or organic salts and has an apparent density of at least 150 g/l, the alkali metal silicate component has a water content below 15% by weight, at least 50% by weight of the alkali metal silicates are present in the Q₂ and/or Q₃ structure and the solid material has a BET surface of at least 5 m²/g, by spray drying and/or fluidized-bed drying of a finely sprayed aqueous formulation of mixtures of the alakli metal silicates and the inorganic and/or organic useful materials and/or auxiliaries wirth superheated steam.
13. A process as claimed in claim 12, characterized in that the spray drying or fluidized bed drying is carried out in the absence of CO₂ in the drying zone, the drying gas stream being a circulated stream of the superheated steam removed from the drying zone which has been reheated by the indirect input of energy.
14. A process as claimed in one or both of claims 12 and 13, characterized in that the superheated steam has a temperature on entering the drying zone of 280 to 380°C and a temperature on leaving the drying zone of 180 to 240°C.