WO1997009269A1 - Solid multicomponent mixtures containing stable-in-storage hydrogen peroxide, method of preparing them and their use - Google Patents

Abstract

The invention describes an at least partially water-soluble solid multicomponent compound, especially for use in detergents and cleaners, bleaches and/or disinfectants, containing absorbed and/or bound hydrogen peroxide (H2O2) and optionally per compounds formed under the influence thereof, contained in a mixture of (K1) solid alkali silicates of an 0.8 to 10 module range (molar ratio of SiO2:M2O, M being an alkali metal) and (K2) at least one other, preferably at least partially water-soluble inorganic and/or organic solid component which is capable of taking in H2O2 and optionally H2O. The teaching of the invention is characterized in that the amount of K1 in the multicomponent compound is at least 3 to 5 wt.% and that of K2 is at least 5 to 10 wt.%, percentage by weight being in each case relative to the sum of K1 + K2, the multicomponent compound taking the form of an agglomerate of a number of adhesively bonded fine particles of component (K2) and optionally (K1), whose fine particulate substance has at least partially been agglomerated in suitable solid form, and that H2O2 is introduced during and/or preferably at least partially after the agglomerated multicomponent compound has been formed. The invention further pertains to corresponding solid multifunctional multicomponent compounds for use in detergents and/or cleaners, the method of preparing the multicomponent compounds as well as their use in detergents and cleaners.

Description

LagerstabU Multi-material mixtures containing fixed hydrogen peroxide in solid form, process for their production and their use.

Use (II) "

The teaching according to the invention is based on the old idea of converting the highly effective hydrogen peroxide as a blending and / or disinfectant as a mixing component into a solid form, which provides sufficient storage stability even under difficult operating conditions with the release of the desired oxidation effect Access of water and, in particular, in aqueous liquors is also connected in the region of room temperature or only slightly elevated temperatures of, for example, 40 ° C. Adequate storage stability should be ensured, in particular, under difficult conditions, such as are present in practice, for example, when mixed with liquid and / or solid ingredients of detergents and cleaning agents. The teaching according to the invention is described below with reference to this last-mentioned application area of solid detergent and cleaning agent mixtures, but it is not restricted to this. General technical knowledge applies to the applicability of the principles disclosed within the scope of the invention. Hydrogen peroxide or peroxo compounds obtained therefrom, which release the H2O2 as an active ingredient when water enters, are an important raw material in the large-scale sector. The sodium perborate is of outstanding importance today as a detergent component with a bleaching effect. The reason for this is the sufficient storage stability of this per-compound under the difficult conditions of mixing with the other ingredients of detergents and cleaning agents. A disadvantage of this form of supply is the comparatively high temperature stability of the perborate, which, in practical use, necessitates comparatively elevated temperatures of the wash liquor and / or the use of bleach activators. For today's low-temperature washing, not inconsiderable amounts of bleach activators in the detergent mixture are necessary. Their content is, for example, between 3 and 10% by weight.

The relevant industry has made numerous attempts to develop other peroxo compounds in storage-stable form instead of the perborate, which in particular could also be used at low application temperatures instead of the perborate. For the relevant literature, reference is made, for example, to F. Beer et. al. "Hydrogen peroxide and peroxo compounds in inorganic chemistry", Chemiker-Zeitung, 1975, 120-125. In the relevant patent literature, as possible alternatives to perborate, for example, percarbonates, perpyrophosphates, pertripolyphosphates, persilicates and peroxomonosulfates of alkali metals and especially sodium and potassium are proposed, see for example EP-A-0030759 and the secondary iterations mentioned therein.

Practical importance in the development of an exchange product for perborates, which is known in the form of tetrahydrate or of the monohydrate are only used today to the sodium percarbonate, which is known to be not a true peroxo compound, but an additive compound of the hydrogen peroxide with sodium carbonate with the formula Na2C03 ^• 1.5 H2O2 - compare, for example, the publisher F. Beer loc. cit., Chapter 2.2 Percarbonate. Sodium percarbonate is characterized by a considerably lower stability of the active oxygen, especially when used in detergents. In recent decades, extraordinarily intensive research and development work has been carried out with the aim of developing a bleaching agent and / or disinfectant that is really useful in practice and even superior to perborate based on percarbonate. For the relevant literature, reference is made, for example, to E. Rommel "sodium percarbonate, production, properties and use", soap-oil-fat waxes, 1977, 411-415 and the extensive secondary literature cited therein. From 1969 to 1976 alone, 60 patents were named for this task. In addition to the high content of active oxygen, sodium percarbonate also has a high dissolution rate in water. It develops bleaching effect even in the absence of bleach activators in the low temperature range. Numerous approaches in the state of the art deal with the sufficiently tight coating of the sodium percarbonate to exclude decomposition induced by moisture. Regarding the relevant patent literature, reference is made, for example, to DE-A 41 09953 and the extensive secondary literature cited therein. The coating of the percarbonate particle does not provide an answer to the following problem: The decomposition of the H2O2 once triggered provides water as the reaction product, which is now included in the coated particle. The decomposition itself is an exothermic reaction, so that the decomposition mechanism builds up quickly by increasing the temperature. It is known to add stabilizers against undesired decomposition to the sodium percarbonate. In particular, two triggering factors are taken into account in the relevant prior art: heavy metal compounds which can occur in several valence levels, in particular iron, act as decomposition catalysts in the ppm range. A maximum upper limit for the permissibility of such heavy metals is usually seen at about 5 ppm. To further reduce the catalytic activity, the use of complexing agents of inorganic and / or organic nature is recommended. However, water is also regarded as a "catalyst" for triggering the undesired percarbonate decomposition for the reasons given above.

The most important stabilizers in practice are silicates on the one hand and alkaline earth metals, in particular magnesium, on the other hand, wherein the silicates can be used as alkali silicates but also as alkaline earth silicate compounds. Magnesium is usually added in the form of water-soluble magnesium salts and, in particular, to the aqueous H2O2 solutions used for the reaction with soda. The concentration of these stabilizers is in the range up to about 1% by weight, based on the sodium percarbonate to be stabilized. For the relevant literature, reference is made, for example, to the cited publication E. Romrnel op. Cit., And to the following patent literature DE-C-21 33566 (preferred amounts of stabilizer from 0.2 to 0.5% by weight of MgSO4 and 1% by weight). % Sodium silicate, in each case based on the percarbonate obtained in the dry state), US Pat. No. 3,801,706 (MgCl2 0.2 to 1.0%, sodium silicate with the module 3.25 in amounts of 0.5 to 1.0%, in each case based on anhydrous sodium carbonate), and DE-A-2344017, where similar amounts of these and other stabilizers such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid or benzoic acid are described. The production of sodium percarbonate is possible by 2 basic processes, namely in the so-called dry process and in the wet process. In the dry process, caicinated soda is sprayed with concentrated hydrogen peroxide solution, the hydrogen peroxide being able to be added batchwise. In the meantime, drying is carried out using a hot or cold air stream.

In the wet process, the reaction between Na2CÜ3 and H2O2 takes place in the aqueous phase, the sodium percarbonate is precipitated - for the literature, see the publication E. Romme1 in soap-oil-fat waxes, and the secondary literature cited there. A modified drying process is described in DE-A 2344017 already mentioned. According to US Pat. No. 3,801,706, the percarbonate is to be prepared from its aqueous preparations containing small amounts of stabilizers by spray drying. DE-C-21 33 566 describes the application of hydrogen peroxide and in particular corresponding aqueous solutions, to which the stabilizers mentioned have been added in small amounts, to sodium carbonate in the fluidized bed.

Despite this extraordinarily intensive processing of the subject matter affected by the invention, there are still considerable difficulties to replace the perborate-based bleaching agent in other detergents and cleaning agents, for example, with other peroxo compounds, for example with percarbonate.

The teaching of the unpublished German patent application P4408359.9 is based on an approach which, to the knowledge of the applicant, has so far not appeared in the extensive literature. Bleaching agents and disinfectants of the type affected here are generally only one - albeit important - active ingredient component of a multi-component mixture. Especially in the field of In terms of quantity, detergents and cleaning agents can play an important role in alkali silicate compounds. Alkali silicates are not only known mixture components in agents of this type for adjusting and regulating the alkalinity of the wash liquor, in important technical configurations, alkali silicates can be used as builders or builder components. At least in this form, they make up a considerable percentage of the mixture of valuable substances, which can be, for example, in the range from 20 to 60% by weight, based on the total detergent. The concept according to the invention is based on this and at the same time on the fact that alkali silicates have crucial functional importance as stabilizers for easily decomposable peroxo compounds of the type of sodium percarbonate.

The teaching of the earlier application is shaped by the concept of mixing the unstable peroxo component so intensively with comparatively large amounts of the stabilizer and thus diluting it that microdisperse homogenized substance mixtures are present in which the smallest individual particles of the unstable per compound are surrounded by the stabilizing alkali silicate compound are. It immediately makes sense: this use of the stabilizer in a larger amount at the same time as a diluent for the unstable per-compound must lead to the inevitably triggered "catalytically" induced decomposition reactions no longer leading to the self-induced decomposition of the unstable material as a whole. In particular, the process of self-heating the decaying material by the exothermic reaction and the self-accelerating decomposition of substances are prevented.

It is also possible to use any known additional stabilizers. Solid multicomponent mixtures can be produced using widely known technologies. Details of this can be found in the earlier application mentioned, the disclosure of which is hereby expressly made the subject of the teaching of the invention described below. In a preferred embodiment, the teaching according to the invention uses a working principle of drying aqueous aqueous preparations, which is distinguished by the use of superheated steam as the drying gas stream. With this technology, the solid recyclables are produced in a form that is characterized by a multitude of advantages. As an example, reference is made here to the microporous structure with an increased BET surface area of the dry substance and the assurance of high water solubility when drying up aqueous alkali silicate solutions. Details of this are given below. Already here, however, reference is made to the applicant's parallel German patent applications according to P 4406591.4 and P 4406592.2, the content of which is hereby also made the subject of the disclosure of the invention.

Subject of the invention

In a first embodiment, the subject matter of the invention is a water-soluble multicomponent compound as a solid mixture, which can be used in particular as a bleaching and / or disinfectant, containing absorbed and / or bound hydrogen peroxide and, if appropriate, under its action in situ formed per compounds, taken up in a mixture of (K1) solid alkali silicates of the module range (molar ratio SiO 2: M2O where M = alkali metal) from 0.8 to 10 and

(K2) at least one further, preferably at least partially water-soluble, inorganic and / or organic solid component, which is in particular capable of binding H2O2 and optionally H2O. In this embodiment, the invention is characterized in that the proportions (K1) in the multi-component compound are at least 3-5% by weight and the amounts (K2) are at least 5-10% by weight - based on weight to the sum (Kl) + (K2) - that the multicomponent compound is further formed as an agglomerate of a large number of fine particles of component (K2) bonded to one another and, if appropriate, (Kl) whose fine particulate material is at least partially as a corresponding one Solid material has been introduced into the agglomeration, and that the introduction of H2O2 has been carried out during and / or preferably at least in part after the formation of the agglomerated multicompound compound.

In a particularly important embodiment, the invention relates to a multifunctional multi-substance compound in solid form for use in detergents and / or cleaning agents, containing at least 15% by weight of alkali silicates in the module range from 1 to 4, preferably from 1.2 to 3 , in a homogeneous mixture with at least 10% by weight of finely divided inorganic and / or organic water-soluble and / or water-dispersible salts, in particular from the field of builder or cobuilder components and / or builders for detergents and cleaning agents, by drying aqueous mixtures the components forming the multicompound compound have been produced to a preferably giant-capable product.

The teaching according to the invention is characterized here in that this multifunctional multicompound compound additionally contains H2O2 bound.

In a further embodiment, the invention relates to the process for the preparation of the multicomponent compounds described above, which process is characterized in that the finely divided component (s) to (K2) and, if appropriate, also components present as a solid to (K1) agglomerate and dry using a preferably aqueous liquid phase to give a pourable and free-flowing material and at the same time with / or after this drying Introduces H2O2 into the multi-substance material.

In this embodiment, a particularly important embodiment is that one works in at least one process step with superheated steam as the drying gas, the drying preferably being carried out in a spray and / or fluidized bed treatment.

Finally, the invention relates to detergents and cleaning agents in solid preparation form, in particular textile detergents based on a mixture of surfactants, builder components, bleaching agents and other customary valuable and / or auxiliary substances, which are characterized in that they are multifunctional builder and bleaching agent components Multi-component compounds according to the previous definition included.

Details of the teaching according to the invention

The principles of the trade according to the invention are based on the teaching of the earlier mentioned German patent application P4408359.9. However, the specific technical action is now modified in such a way that at least a portion of the components ^) (K2) as pre-formed fine particulate dry material is brought in intimate mixture with (K1) and from this mixture agglomeration and drying results in a bulk and / or free-flowing solid material is formed, which can be designed in particular as a coarse-grained powder and / or fine-grained material. During the agglomeration stage and / or preferably at least in part after the formation of the agglomerated multicomponent compound, H2O2 is introduced into this multicomponent agglomerate and bound therein.

The agglomeration stage using the components to (K1) and (K2) is preferably carried out with the intermediate participation of an aqueous phase which, in the preferred embodiments of the invention, has been discharged again at least in part from the solid material. The H2O2 is also introduced in a manner known per se in technically important embodiments in such a way that aqueous preparations of the H2O2 are introduced into the multicomponent compound. The following also applies here: in preferred embodiments, the water portion entered here is likewise at least partially discharged again by drying. In the following, the possible technologies for realizing this principle are discussed in detail. It can be seen from this that it can be particularly preferred to carry out the aqueous agglomeration of finely divided (K2) components in the presence of suitable preparation forms of the (Kl) component (s) in a preliminary stage and to pass the mixed product thus formed to a special drying stage subject, which enables or favors a subsequent penetrating impregnation of the dried multi-compound with the aqueous H2O2 preparation. This preferred drying stage for preparing the subsequent introduction of H2O2 is a treatment with superheated steam, for details see below.

An essential core of the action according to the invention lies in the previously described concept of giving the solid alkali silicate compounds known as effective H2O2 or peroxo stabilizers an even stronger and in particular multifunctional meaning that the proportion of the solid alkali silicates in the water-soluble compound -Compounds is raised substantially. The stabilizing alkali silicate simultaneously becomes "solid thinner" in the multi-substance mixture and thus leads to a spatial distancing of the solid components with peroxo structure, which are at risk of decay. This not only prevents the self-reinforcing further reaction in the case of initiated decomposition, for example in a percarbonate crystal, but the finely dispersed mixing of stabilizer and peroxocomponent preferred according to the invention also ensures that very small particles of the peroxocomponent are surrounded by the stabilizer.

However, the multifunctionality of this stabilizer component based on alkali silicates is not limited to this increased stabilizing effect. In practical use of the multicomponent compounds, the alkali silicate compounds now present in increased concentrations can have an independent function, which can be seen in the solid multicompound compound completely independently of their stabilizing effect. So this alkali silicate can function in particular in the field of detergents and cleaning agents Active ingredient component for setting the desired alkaline areas in the wash liquor. A very different option is more important: the alkali silicates can become active active components of the detergent and cleaning agent mixtures used, in particular by selecting suitable module ranges (molar ratio SiO 2: M 20, where M = alkali metal). In particular, the function of the alkali silicates as detergent builders and / or cobuilders for developing and strengthening the detergency in admixture with the surfactant compounds and the further components of a conventional detergent or cleaning agent formulation comes into consideration here.

An advantage that is important for the multifunctionality of the components used according to the invention and in particular the (KI) component is evident here: there is the possibility of free selection and optimized adaptation of the valuable component (KI) to the ultimately intended use of the multi-material compound. When the storage-stable dry form of this compound is obtained, which is provided as simple agglomeration and drying of the multicomponent mixture, there is no undesired change in the chemical nature of the component (K1) in particular, in the sense of a module shift. In this, the teaching according to the invention differs fundamentally from a proposal of the prior art for the production of a mixture of sodium silicate and sodium percarbonate. According to this proposal, sodium silicate is to be reacted with module 2 with aqueous carbonic acid in the presence of hydrogen peroxide. When the starting module is shifted from 2 to the end module from 4 in the sodium silicate portion of the end product, a mixture of the sodium percarbonate formed with the sodium silicate portion modified in the module is obtained. The teaching of the invention is free from such a constraint regarding the change in the chemical nature of component (K1). The selection of suitable alkali silicate compounds by type and amount in the multi-substance coumpounds according to the invention can be determined by technical considerations for the intended use, in particular for the use of the alkali silicates as detergent builders and / or co-builders. In this regard, reference is made to the general specialist knowledge, only a number of important aspects being particularly emphasized in the following.

Corresponding compounds of sodium and / or potassium are particularly suitable alkali silicates. Compounds of sodium can be of particular importance, especially in the field of detergents and cleaning agents which are commercially available today. The module - i.e. the molar ratio of SiO 2 to M2O, where M here denotes alkali metal, in particular therefore sodium and / or potassium, can be chosen within a very wide range from the point of view of stabilization. This fact is derived from the fact that not only alkali metal silicates have been described as stabilizers for, for example, percarbonate, the prior art also provides for the use of highly disperse silica as such for stabilizing sodium percarbonate, see, for example, DE-A 2748783. According to the information in this document, sodium silicate is formed on the surface of the percarbonate particles and thus has a stabilizing effect.

Alkali silicates suitable according to the invention thus correspond, for example, to the modulus range from about 0.8 to 10. If the stabilizing effect of the alkali silicate is not only taken into account, the technical teaching also places particular emphasis on the secondary effect of these stabilizers in the aqueous solution used Fleet, then additional considerations are appropriate here. It is known, for example, that alkali silicates with a module range of approximately 1 to 4 are of particular importance, so that these compounds become the preferred stabilizers if the multicomponent compounds are to be used in the specified field. Within this range, module values from approximately 1.2 to 3.8 and preferably from approximately 1.5 to 3.0 can be of particular importance, with module values in the range from 1.7 to 2.7 large in detergents and cleaning agents is of practical importance. It applies to the teaching according to the invention that these secondary requirements for the functionality of the alkali silicate can generally be met without hesitation in the ultimately required use without endangering the advantages of the improved stabilization of the peroxo compounds threatened by decomposition.

This first objective of the action according to the invention of stabilizing the multicomponent compounds against the undesired decomposition of the peroxo compounds influences the minimum amounts of alkali silicates in the multicomponent compound. The amount to be used is clearly above the maximum values of about 1% by weight recommended in the prior art and is preferably at lower limit values of at least 3-5% by weight and in particular at least about 10% by weight of alkali silicate on the sum of the proportions of (K1) - the alkali silicate compound (s) - and the components (K2) to be discussed in detail below - the other solid components used in a mixture with (K1). Further preferred lower limit values for the amount of (Kl) - again based on the sum (Kl) + (K2) - are at least about 15% by weight and in particular at least 25% by weight.

Together with the solid alkali silicate compounds (C1), the invention provides for the use of one or more further finely divided solid component (s) which are designated (K2) in the definition according to the invention. Representative of this (K2) components can be inorganic and / or organic compounds and in particular corresponding water-soluble salts. Particularly suitable compounds are those which are capable of binding H2O2 and, if appropriate, H2O. A decisive element here for the action according to the invention is that these (K2) representatives in turn do not have to be able to form H2O2 complex compounds of increased stability. The mere ability to add H2O2 even without special stability requirements determines the selection of preferred components of the class (K2). Here too, the facts can be understood from the Mode11 presentation on which the concept according to the invention is based: the components (K2) are present in a very fine distribution in the alkali silicate - the component (C1) - serving as stabilizer and diluent. If hydrogen peroxide is introduced into the mixed product in the manner to be described below, these (K2) components can to a certain extent serve as catchers for the H2O2 and, under normal conditions, fix them to the liquid component per se in situ and thus ensure the solid properties. It is known that numerous representatives of inorganic and / or organic salts are not only capable of such fixation, for example of water of crystallization, but can also fix the H2O2 molecule in a structural structure. In this respect, the definition of the (K2) components is very broad.

The carbonates, bicarbonates, sulfates, halides, borates, phosphates and / or polyphosphates may be mentioned from the range of inorganic salts without claiming to be complete. These salts are expediently also incorporated as alkali salts and in particular as sodium and / or potassium salts as component (K2) in the multi-compound compounds according to the invention. The prior art document cited at the beginning proves that all of these Components are also capable of attaching H2O2 molecules, so that this fixation of this compound, which is liquid at room temperature, is ensured in the solid compound. In this context, the following additional consideration applies: Even the alkali silicates for (K1) should - especially under the conditions for their condition described in detail below - be able to incorporate H2O2 components into their solid structure. In particular, this should apply to over-dried but nevertheless water-soluble forms of the alkali silicates in chain or band structure and / or surface structure, which are known in the technical field as so-called Q2 or Q3 forms. It is therefore entirely within the scope of the invention that at least portions of the hydrogen peroxide to be incorporated in the multi-component compound are also incorporated in the alkali silicate (C1) component. Nonetheless, the use of the (K2) mixture components is of essential importance to the invention. In preferred embodiments described below, they form the basis for a physical configuration of the dried material with a microporous structure and, accordingly, a comparatively large BET surface area and large cumulative volume.

In addition to or instead of the inorganic salts listed above in detail, organic (K2) components mixed with the alkali silicate can be used. As in the case of the inorganic salts mentioned above, the organic scavenger components should preferably be water-soluble and, in particular, should be able to incorporate the H2O2 molecule. Suitable representatives for such organic (K2) compounds are, in particular, alkali metal salts of lower carboxylic acids, with corresponding alkali metal salts of lower polyfunctional carboxylic acids being particularly preferred. Here too, the preferred alkali salts are corresponding compounds of sodium and / or potassium. Examples of preferred polyfunctional carboxylic acids are citric acid, succinic acid, adipic acid, glutaric acid, tartaric acid, sugar acids, amino carboxylic acids and / or nitrilotriacetic acid. In addition to or instead of such monomeric salts, corresponding oligomeric and / or polymeric polycarboxylates can also be present, as are used to a large extent as so-called cobuilder components in today's detergent formulations. Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid can be particularly suitable. Their relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. Also particularly preferred are biodegradable terpolymers, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers.

In an important embodiment, mixtures of several “scavenger substances” of the type specified are used as (K2) component (s). Here, general specialist knowledge of the conditions for the practical use of multi-component compounds, for example in detergents and cleaning agents, can again be decisive for the special selection of such (K2) mixtures. This is immediately understandable with an example: The (Kl) component based on alkali silicate can have the main builder function in the finished detergent, but this usually requires the co-use of a cobuilder component in order to achieve the desired detergency. Known cobuilders are organic polyfunctional carboxylate compounds, be it in the form of low molecular weight polyfunctional carboxylic acid salts, in particular citrates, or in the form of the previously described oligo- or polycarboxylates. For further application-technical reasons, however, the use of soda and / or sodium sulfate in the multi-component compound may also be desired. The invention enables any combination as ultimately required by experts without departing from the principle according to the invention. The inorganic and organic (K2) components present in a mixture then serve as “catcher substances” for at least a portion of the H2O2 in the multicomponent compound. The alkali silicate used as the (K1) component acts as a stabilizer and at the same time as a solid thinner for the (K2) carrier substances. In practice, each mixture component has the functionality intended for it, or is then filled out by it.

It also applies to the quantitative proportion of the (K2) components that there are preferred lower limits, these subsequent figures again refer to the sum of (Kl) + (K2). In particular, the following applies: The total of the (K2) components are preferably present in amounts of at least about 5% by weight and in particular of at least about 10% by weight. It may be expedient for the proportion of (K2) component (s) to be at least 15% by weight and preferably at least 20% by weight, in each case based on the sum of (Kl) + (K2) . For the blends of (K1) and (K2), the preferred upper limits for the amount of (K1) are approximately 95% by weight and preferably 90% by weight. Amounts of the (K1) component in the range from about 25 to 80% by weight can be particularly expedient. From this, the numerical value of about 75% by weight is derived for the preferred upper limit for the amount (K2). In general, amounts of (K2) component (s) in the range from about 15 to 60% by weight will be particularly expedient. It is further preferred that the (K2) components are at least largely dried in an anhydrous manner and are freed of water components which are bound, for example, as water of crystallization.

In this context, two embodiments can be distinguished according to the invention:

In a first embodiment, the amount (K1) in the multi-component compound is at most about 50% by weight and preferably not more than about 35-40% by weight, with a simultaneously increased amount of H2O2 binders (K2). This proportion (K2) can then be up to 75-80% by weight, for example. In this embodiment, comparatively large amounts of H2O2 can be stored in the multicompound compound and - due to the intimate mixing with the components - effectively stabilized. This component (s) (C1) is still present in a concentration which is significantly higher than in the prior art and can, for example, effectively correspond to its own function in the context of textile washing.

In the other of the embodiments addressed here, the amount (K1) is above 50% by weight. Here, in particular, there is the possibility of forming a multifunctional multi-substance compound in the sense of a builder / bleach for textile detergents. Multi-component components of the type according to the invention are capable of absorbing and fixing possibly considerable amounts of H2O2. It will be described in detail below that this peroxide can be introduced into the multicomponent compound either during the agglomeration and drying of the multicomponent mixture and / or subsequently. In the finished compound, the content of fixed H2O2 and / or its subsequent products, which arise in particular in situ, is at least about 0.2 to 0.3% by weight and preferably at least about 0.5% by weight. Higher H2O2 contents are important, which are then, for example, at least about 1% by weight and in particular at least about 3% by weight. Depending on the nature of the solid mixture of (K1) and (K2) components, considerable proportions of H2O2 can be stored in the goods in a storage-stable manner, so that preferred lower limits for the H2O2 content, for example at least 5% by weight, also remain at least 7 or 8% by weight, or at least 10% by weight, but possibly also significantly higher, for example 15 or 20% by weight. In this context, the following further considerations apply, which show a further considerable degree of freedom for the action according to the invention:

In the preferred embodiment according to the invention, the (K2) components used as “scavenger substances” are introduced into the mixture of substances free of H2O2 components. The hydrogen peroxide is added as a separate component in the course of drying and / or subsequently and incorporated into the multi-component compound. There is now practically freedom in the choice of the amount of hydrogen peroxide up to the maximum loadability or fixability of this component in the multi-component compound. So practically any percentage of the available capacity of the multi-compound with the hydrogen peroxide by fixing it in the compound be exploited. Another important advantage for the action according to the invention is immediately understandable from this:

The (K2) scavenger substances are not only capable of fixing H2O2, they are in particular able to bind water - be it in complex form, be it as water of crystallization or as a mere additive compound. In connection with the consideration given above, important advantages for the invention can be derived from this: The total free-standing capacity of the (K2) substances for fixing can be used for fixing H2O2 molecules in part, but also for fixing if necessary of water molecules are used. There is thus the possibility of these two components coexisting in the multicompound compound, with the ability of the alkali silicate - the (K1) component - to take water into its molecular structure and to take it into account fix. In the preferred embodiment described below in detail, to use this (K1) component in the form of an over-dried and accordingly greatly reduced residual water content, the possibility opens up in the practical entry of the hydrogen peroxide with commercially available aqueous per ¬ oxide solutions to work without thereby endangering the storage stability of the finished peroxide-containing multi-component compound. The amount of water introduced as part of this peroxide entry can, if desired, be at least largely discharged again by drying, but it may well be tolerable to leave not inconsiderable amounts of water in addition to the hydrogen peroxide in the material, without necessarily triggering instability with regard to the peroxide portion. Together with these new elements of the invention, use can be made of the specialist knowledge for optimizing the peroxide stabilization in the field concerned here. Without claiming completeness, a few important points are highlighted:

It also applies to the embodiment of the multi-component compounds according to the invention that catalytically active residues, in particular corresponding traces of heavy metal, are to be excluded as far as possible and / or are to be bound by additional complexing or masking in such a way that they lose their catalytic activity. Accordingly, it can also be preferred according to the invention to work with no more than a few ppm, generally no more than 2 to 5 ppm, in particular iron, in the material to be dried.

The use of additional stabilizing agents opens up the wide range of suitable components, which are listed in the literature cited at the beginning with individual representatives. Of particular importance here is the measure known per se of stabilizing the aqueous peroxide solution at least at the working stage of entry into the multicompound compound by using water-soluble stabilizers in small concentrations. In particular, the water-soluble magnesium salts such as magnesium sulfate, magnesium halide and comparable compounds come into consideration. Suitable organic stabilizers are, in particular, complexing agents, examples of which are only: salts of polyphoshonic acids, in particular l-hydroxyethane-l, l-diphosphonic acid (HEDP), diethylenetriaminepentamethylenephosphonic acid (DETPMP) or ethylenediaminetetramethylenephosphonic acid (EDTMP). Further examples are: ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA) or the stabilizers specified in detail in DE 2234135, DE 3125638 and EP 0442549. The amount of these known stabilizer components is in the usual range, ie with comparatively very small amounts based on the valuable substances of the multi-component compound according to the invention. In general, the stabilizers used in the prior art are at most about 1 to 3% by weight, based on the weight of the multi-component compound. Further information on complexing agents for heavy metals that are also suitable according to the invention can be found in the relevant specialist literature, for example Dr. L. Hartinger "Pocket Book of Wastewater Treatment for the Metalworking Industry", Vol. 1: Chemistry, Chapter 3.7.5 "Metal Precipitation" and Chapter 4.5 "Metal Complex Compounds", Carl Hanser Verlag Munich Vienna 1976 as well as "Teaching and Handbook of WASTEWATER TECHNOLOGY" , 3rd edition, vol.VII, chapter 8.2.2 "Neutralization and metal precipitation", Ernst & Sohn publishing house for architecture and technical sciences Berlin.

In a preferred embodiment, when the heavy metal masking agents are used, it may be expedient to incorporate these stabilizers into the components or multicomponent mixtures loaded with excessive levels of heavy metals before the multicomponent mixture is loaded with the aqueous H2O2. In this way it can be ensured that excessive levels of heavy metal residues are inactivated to such an extent that undesired catalysis of the H2O2 decomposition is prevented. In addition to or instead of such a pretreatment of the heavy metal-containing material with the stabilizers or masking agents, it may be desirable to also add small amounts of corresponding stabilizers or masking agents to the aqueous H 2 O 2 solutions which are incorporated into the multicomponent compound as part of its drying or as part of a separate subsequent loading ¬ step to be incorporated.

For a large-scale production of multi-component compounds in the sense of the invention, the mixture component is particularly important (Kl) to be seen as a problem component. The large-scale production of water glass generally leads to heavy metal contamination in areas which are significantly above the limit values previously given for reasons of stability. For example, it can be assumed that when working with industrially obtained aqueous alkali silicate solutions, in particular corresponding water glass solutions in the module area for detergents and cleaning agents, there are generally (C1) components with a considerable content of heavy metal impurities. For example, the content of undesired iron in the range above 50 ppm and in particular in the range from 100-250 ppm, based on solid alkali silicate, can already be present. In a particularly important embodiment of the teaching according to the invention, however, there is the possibility of using such starting materials which are comparatively heavily contaminated with heavy metal traces for the production of effectively stabilized multicomponent compounds in the sense of the invention. The following method of operation has proven to be useful here:

The alkali metal silicate component (C1) contaminated with heavy metal components is mixed in the form of an aqueous solution in a preliminary stage with the stabilizer or stabilizer mixture selected in each case, mixed intensively and at room temperature or else elevated temperatures for a period of at least about 10-15 minutes brought to abreaction. The reaction of the heavy metal impurities in the alkali metal silicate solution with the added stabilizers can be particularly suitable in the range of the room temperature with reaction times in the hour range. Particularly suitable stabilizers are the aforementioned compounds of the type of HEDP and the related substances mentioned in connection therewith which are capable of forming complexes with the heavy metal components. Only after this inertization of the (K1) component, carried out separately in a preliminary stage, is it mixed with the capture substances to (K2). In a particularly preferred embodiment according to the invention, the agglomeration of the capture components added in finely divided form to (K2) can take place using the pretreated and stabilized aqueous alkali silicate solution as the binding medium. The carrier compound, which can be loaded with H2O2 in a subsequent working step, is then formed from the agglomerate formed in this way by at least partial drying. Details will be given below.

The production of the preparation forms of the solid mixtures according to the invention and their loading with the hydrogen peroxide is controlled by the overarching idea of bringing the (K1) and (K2) components into the most intimate mixture possible. For this purpose, it can be particularly expedient to proceed in the previously described procedure: finely divided, but solid components for (K2) are agglomerated with aqueous preparations of component (s) for (K1) with simultaneous intensive mixing and dried in this form and thus leads into the solid phase. In particular, the free choice of the components for (Kl) and (K2) in terms of type and quantity allows the functions in the finished product to be optimally coordinated.

The agglomeration can take place in a manner known per se; reference is made, for example, to the relevant specialist literature.

The finely divided solid material - in particular the components of (K2) - can be used with average particle sizes in the range from, for example, 0.1 to 1.5 mm and in particular with average particle sizes in the range from 0.2 to 0.8 mm. A special one A suitable range for average particle sizes of these solid components can be 0.2 to 0.5 mm and in particular approximately 0.2 to 0.4 mm. Corresponding numerical ranges apply in the event that the components of (K1) are at least partly fed to the agglomeration process as solids.

As already indicated above, however, a preferred embodiment of the invention resides in the following embodiment: The multicompound compound is formed in a first process stage by wet agglomeration of the components used in finely divided solid form to (K2), with a particularly aqueous preparation as the liquid phase - Solution and optionally dispersion - of (Kl) components is used. In particular, the mixing ratios of (K2) to (Kl) also determine the respective offer forms. In particular in the production of multi-component compounds with high contents of (C1) components, their proportionate use as solid particles in the wet agglomeration process can be useful.

In preferred embodiments of the invention, the primary wet agglomerate is subjected to a drying process before the introduction of hydrogen peroxide. In principle, all drying techniques are suitable here, in particular corresponding processes using a hot gas phase as the drying medium. The use of hot air and / or hot inert gases can be particularly expedient here in order to exclude undesired reactions of the component ^) to (K1) with CO 2 portions of the drying gas.

The use of hot gas phases can be important, in particular in connection with the following embodiment of the teaching according to the invention: Preferred multi-component compounds of the invention lie the (Kl) component (alkali silicate) with a residual water content that is significantly lower than the equilibrium water content of the respective material. The water content of a typical water glass with module values in the range from about 2 to 3.7 is in the usual drying process in the range from about 18 to 20% by weight. According to the invention, it may be desirable to lower this water content below the limit of 18% by weight and in particular to a limit of at most 15% by weight. A further lowering of the residual water into the area of significantly over-dried water glasses may be desirable. In preferred embodiments, the residual water content of the (Kl) component is in the range from about 3 to 12% by weight and in particular in the range from about 5 to 10% by weight, based in each case on the (Kl )-Component. The alkali silicate is particularly X-ray amorphous. Methods for producing such over-dried sodium disilicate are described, for example, in EP-A-0444415. It describes the production of an amorphous sodium disilicate to be used as a builder in detergents and has a water content of 0.3 to 6% by weight. These highly dehydrated amorphous disilicates are produced in a multi-stage process which initially involves the production of a powdery amorphous material with a water content of 15 to 23% by weight. This material is subsequently treated with flue gas in countercurrent at temperatures of 250 to 500 ° C. The processed material is then shredded.

Such drying mechanisms can also be considered within the framework of the teaching according to the invention. It has been shown, however, that particularly useful results are obtained if a very specific working aid, namely superheated steam, is used as drying gas and / or protective gas in certain work steps described below. This very use of superheated steam as a drying and / or protective gas for drying up the multicomponent mixtures composed according to the invention has many advantages. First, only the most important elements are referred to:

Working with superheated steam is generally carried out by circulating the water vapor and thus excluding foreign gases, in particular excluding carbon dioxide. Considerable advantages are associated with this for the drying of alkali silicate compounds, in particular with regard to the setting of high solubilities. In her parallel German patent applications P 4406591.4 and P 4406592.2, the applicant describes the use of the known process method of superheated steam drying for drying aqueous solutions of alkali silicate compounds and mixtures of such alkali silicates with inorganic and / or organic salts, which are within the meaning of the invention Definition can be formed as (K2) components. The disclosure of these two parallel applications for industrial property rights is hereby expressly made part of the disclosure of the present application. To complete the disclosure of the invention, a brief summary can be summarized: A crucial core idea lies in the application of the principle of drying, in particular spray and / or fluidized bed drying, aqueous preparations of valuable materials and mixed materials with superheated steam as a hot gas stream for supplying the vaporization energy into the material to be dried and the simultaneous absorption of the evaporated water portion in the stream of superheated water vapor and removal of this evaporated water portion together with the superheated steam stream withdrawn from the drying zone. The discharged water is condensed and worked up, while the rest of the superheated steam in a closed circuit into the drying zone is returned after the amount of energy removed by the drying has been fed back to him.

The applicant describes this working principle of drying, in particular of valuable materials and mixed materials from the field of wetting agents, detergents and cleaning agents, in a number of published documents and older applications. The principle of hot steam drying disclosed therein is hereby expressly made the subject of the present disclosure of the invention. Reference is made here in particular to the following publications: DE-A 4030688 and the further publications according to DE-A 4204035; 4204090; 4206050; 4206 521; 4206495; 4208773; 4209432 and 4234376.

The closed circulation system of the superheated steam enables the CO 2 -free drying and thus avoids undesired secondary reactions in the material to be dried. The conditions of drying can be controlled as desired with regard to the residual water content. In particular, the removal of water is possible with simultaneous condensation of the silica residues to form oligomer and / or polymer compounds. Practically any degree of overdrying 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 the drying medium. The following also applies: the primary dry material is obtained in the form of a free-flowing granular material of considerable bulk weights, nevertheless this dry material has suitable BET surfaces for covering with other valuable and / or auxiliary substances 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. It is immediately understandable that a material of such a nature must be particularly well suited for subsequent implementation with aqueous peroxide solutions. This microporous inner structure is also of decisive importance for the dissolving behavior of the dry material according to the invention. Finally, it is also important for an embodiment to be described below, which provides for further covering of the grain structure with cladding layers.

One of the most important embodiments for the production of the multi-component compounds according to the invention is the application of this process principle of drying using superheated steam as the hot gas phase. Here, however, 2 alternative or alternatively usable methods can be distinguished:

The first embodiment provides for all components of the finished multicompound compound to be combined with one another and dried in the course of a material pass through agglomeration. The constituents can be fed to the drying zone in a mixture with one another, but also at least partly in separate streams and combined here in the course of the drying process.

In a second and particularly important embodiment, the hydrogen peroxide component is not fed to the drying stage at all or only in part. As the primary material of agglomeration and drying, a granular material falls out of the components (C1) and (K2) and any other components that may be used. As described in the aforementioned patent application by the applicant P 4406592.2, with such drying of alkali silicate in admixture with other solids, the process product obtained is a granular material with the desired microporous internal structure. The same applies correspondingly to the embodiment concerned here, to only use a portion of the amount of H2O2 to be entered in this drying stage. These embodiments then provide a downstream work stage in which the preferably microporous material to be dried is loaded with hydrogen peroxide. Reference can be made here to the previously discussed prior art, which describes the corresponding impregnation of a carrier with or without the use of the fluidized bed technology with aqueous H2O2 solutions. This loading stage can be combined with the simultaneous and / or subsequent discharge of the more volatile water fraction from the loading stage.

A further special feature of working with superheated water vapor in at least one of the process stages for obtaining the desired multicomponent compound is explicitly mentioned: As is known, the alkali silicates of the (Kl) component are used to discharge three-dimensional space - the so-called Q4 structure - enabled, which is characterized by limited water solubility. In the phase of superheated steam, no or practically no insoluble components are formed even if the (Kl) component is overdry. The alkali silicate portion of the dry material is characterized by high water solubility even at ambient temperature. Its proportion of insoluble material is usually <3% by weight and in particular <1% by weight. This high willingness to be water-soluble is precisely what the multi-functionality of the solid compounds aimed for according to the invention is the (Kl) component is also relevant to the decision, if, for example, the builder function is aimed at in practical use.

This effect, which regulates the solubility of the (K1) component, of the superheated steam can also be used, for example, as follows: A multicomponent mixture in the sense of the combinations according to the invention can initially be agglomerated and dried in any manner in the absence of superheated steam. In a subsequent work step, the water solubility of this multicomponent mixture and in particular the (K1) component is then regulated by treatment with superheated steam. The printed state of the art has corresponding information here, compare, for example, DE-A 2360502. For the use of such a modification of the process, it is understandable that the subsequent impregnation of a pre-formed dry multi-compound with the hydrogen peroxide is particularly useful.

The hydrogen peroxide can indeed be introduced during the agglomeration and drying of the aforementioned aqueous preparation of components (C1) and (K2), but the hydrogen peroxide is preferably introduced into a preformed dry material. For this embodiment which is preferred according to the invention, it is understandable that the dry material with the largest possible surface area should be offered for subsequent introduction of the hydrogen peroxide or its aqueous preparation forms. In this case, work can be carried out, for example, in the fluidized bed or in other forms; reference is made to this ¬ for example to DE-C 21 33566 and DE-A 2344017. In the last-mentioned document, the corresponding preparation of perhydrate compounds based on sodium carbonate, sodium phosphate or mixtures thereof is described. That extremely finely divided material (particle size of about 0.05 to 1.4 mm) is sprayed with an aqueous peroxide solution (concentration of 35 to 90% by weight) and for a period of, for example, 15 minutes in the range of moderately heated temperatures (20 to 60 ° C). In the first-mentioned publication, work is carried out under comparable conditions, but here in the fluidized bed using a fluidizing gas. Comparable method steps can be used in the embodiment of such a method which has now been modified according to the invention, but in particular the temperature can also be raised.

Particularly suitable for the production of the multi-component compounds according to the invention are processes, ^κ °; to which the drying of the aqueous peroxide solution added simultaneously or subsequently is carried out using and / or in the protection of a gas phase. This is immediately understandable in the following example: Gas phases can be used as carrier gas for the fluidized-bed drying and / or for the application of the hydrogen peroxide solution and the subsequent drying on a pre-formed, finely divided solid material. Basically, the use of flowing hot gas phases shortens the drying time and thus the period of temperature stress. The maximum desired temperature of the product can be set or controlled by suitable selection of the temperature of the hot gas phase. For example, the addition of H2O2 to selected (K2) components, for example sodium carbonate, is an exothermic reaction. When working with highly concentrated hydrogen peroxide solutions, it may be desirable to counteract overheating of the solid material by removing excess amounts of heat by means of the protective gas phase. Finally, a further modification of the bound multicompound compounds containing H2O2 falls within the scope of the teaching according to the invention. In particular, two treatment steps that can also be combined with one another must be taken into account here.

In the description of the prior art mentioned at the outset, reference is made to the numerous proposals for providing sodium percarbonate with a sufficiently dense coating in order to thereby rule out decomposition induced by moisture. This methodical approach is for

1

Sodium percarbonate crystals make only limited sense for the reasons given. This procedural measure can be expedient for the goods which are now stabilized in terms of storage according to the invention. Such a final coating with inorganic and / or organic coating substances can in particular prevent undesired interaction when used in solid detergents with other components of such active ingredient mixtures. The numerous materials from the proposals of the prior art come into consideration as Hü11 substances; reference is once again made to DE-A 41 09953 and the extensive secondary literature cited therein. A particularly simple example of an inorganic coating is the final covering of the outside surfaces of the manor with water glass, the alkali silicate used here being identical to or different from the (Kl) components. Organic coating materials can be applied as a melt, so that an additional post-drying step is not necessary here.

The second possibility of the aftertreatment of a multicompound compound, in particular with a microporous good structure, in the sense of the definition according to the invention makes use of the comparatively large BET surfaces and accordingly increased cumulative volumes, which are derived from the high microporosity of the goods. Here, the invention provides for additional valuable and / or auxiliary substances to be applied to the primary dry material in a form that is flowable at the application temperature and to fill the microporous internal structure of the material at least partially with it. Corresponding valuable substances and / or auxiliary substances from the field of wetting agents, detergents and cleaning agents are suitable as impregnating compounds. Particularly suitable here are surfactants or surfactant-containing liquid preparations which are preferably water-free, for example free-flowing nonionic surfactants, but also other builders or cobuilder components, anti-foaming agents, solubilizers and any other valuable substances.

Such loading of the exterior and interior structure with compounds which are flowable at the application temperature and which contain, in particular, oleophilic molecular components can lead to a substantial additional stabilization of the multi-component compounds containing peroxide when they are stored in a mixture with other mixture components, in particular from the field of detergents and cleaners. In this context, reference is again made to the publication E. Rornmel, soap-oil-fat-waxes, cited above, where storage tests are described in order to investigate the stability of the sodium percarbonate in detergents. It is shown here that a certain form of supply of the percarbonate, in which a coating of the percarbonate-containing multicomponent material is provided with selected detergent substances containing oleophilic molecular parts, stabilized the multicomponent mixture to such an extent that a long shelf life even in standard packaging with a water vapor permeability of approx. 100 g / m ^{2 •} day was found under normal conditions. This can also be done according to the invention Work result contribute to the multifunctional use of the components used. Components used as filler or shell material with oleophilic molecular components, for example nonionic surfactants and / or fatty alcohols, are given functional importance both in terms of the increased storage stability and the desired and / or required valuable components in practical use.

The bulk densities of the multicomponent material, in particular in the agglomeration and drying with superheated steam as drying gas, are usually at least about 150 g / 1 and preferably at least 200 g / 1. These lower numerical values already apply to the multi-component compound consisting of (K1) and (K2) components. The bulk densities of the material are significantly increased by the loading with peroxide and the possibly additional final covering and / or loading of the microporous grain interior with further valuable and / or auxiliary substances. In particular, they are at least 350 g / l. The bulk densities of the combined material can be varied very largely freely by suitable measures. The values aimed for in modern detergents with bulk densities of at least about 700 g / l can thus be set at any time.

We expressly refer to a possible variation in the formation and composition of the multi-component compounds: In the definition of the (K2) components, it is stated at the beginning that those carrier compounds which form comparatively stable complexes with H2O2 are also suitable here. In particular, alkali borate can be used as carrier or catcher component. In important embodiments, however, such a (K2) component will only be present in part and in particular in a mixture with other H2O2-binding (K2) components. That is also possible The use of further auxiliary and / or valuable materials in the primary structure of the multi-component compound, insofar as the implementation of the principles of the inventive action is not prevented by these components used.

The following elements have proven to be particularly helpful for optimizing the work result and setting optimal stabilities in the finished multifunctional compound:

It may furthermore be expedient to use very mild temperature conditions when loading a preformed carrier compound composed of the (K1) and (K2) components with an aqueous hydrogen peroxide solution. For example, the use of loading temperatures below 35 ° C. and in particular up to a maximum of about 30 ° C. may be expedient, preferably at the same time preferably applying aqueous H2 O 2 solutions which are as highly concentrated as possible. The application in the fluidized bed has proven particularly successful here. Corresponding commercially available hydrogen peroxide solutions with a content of about 70% H2O2 are suitable, for example. This loading stage is generally carried out in the presence of a protective gas phase. Here, air can be used as a protective gas, in particular when working at the low temperatures mentioned. It may also be expedient not to keep the temperature of this protective gas phase above 35 ° C. at the lower temperature values mentioned. The information in the following examples shows that a technically acceptable post-drying period - which is usually not more than about 1 hour - enables the metered-in water to be sufficiently discharged.

Additional stabilizers can be added to the multifunctional compound together with the aqueous hydrogen peroxide solution. As a rule, however, this is in the previous one The embodiment described is not necessary, even if the relatively large traces of heavy metal, which are entered on an industrial scale, are present, but have previously been masked by separate inactivation.

B e i s p i e l e

example 1

In a spray tower, a slurry of 99% by weight sodium water glass with the module 2.0 and 1% by weight complexing agent for iron with the trade name "Turpinal SL ^R " was steam-dried. The complex-forming component is hydroxyethane-l, l-diphosphonic acid (HEDP). The water glass / complexing agent compound dried in this way had a bulk density of 100 g / l. In a compaction step (roller press) the bulk density was raised to 550 g / 1.

A solid mixture of 30% by weight of the sodium water glass described above (module 2.0) and 70% soda was sprayed with a liquid mixture in a Lödige mixer. The liquid mixture consisted of 70% aqueous H2O2 solution, which is necessary for the stoichiometric conversion of the soda used above to sodium percarbonate (Na2CÜ3, 1.5 H2O2), 5% by weight of an aqueous water glass solution N 2.0 and 0.03% by weight .-% HEDP. The data in% by weight relate to the amount of solids mixture used.

The liquid mixture was sprayed on quickly and the amount of water entered evaporated to a large extent and was withdrawn from the mixer via a vacuum connection. The aqueous water glass solution acted as a binder for the solids used. The finished agglomerate of water glass N and sodium percarbonate had a bulk density of 600 g / 1.

99% of the H2O2 could be converted with the soda to sodium percarbonate. The agglomerated finished product was then dried in a fluidized bed for a further 20 min. Example 2

The procedure was as in Example 1. After completion, the granules were coated with a moisture-protecting layer of a Ciβ fatty alcohol ("Lorol C 18 ^R ) and a nonionic surfactant with 40 EO units (" Dehydol TA 40 "), mixing ratio 80:20. The end product contained 20% of the organic components.

Example 3

The procedure was as in Examples 1 and 2. The granules of Example 2 were mixed in a die press after intersective mixing with the organic components, in this case 80% Dehydol TA 40 and 20% Dehypon LT 104 ^R (fatty alcohol C12-Cis + 10 E0, n-butyl) shaped about 1 mm granules. The final spherical shape was given to them in a Marumerizer.

Example 4

The procedure was as in Examples 1 to 3. The 1 mm granules (average grain diameter) were covered with a final protective layer. The coating layer (15% by weight with respect to the amount of granules) consisted of 80% by weight of fatty alcohol Lorol C18 and 20% by weight of nonionic surfactant Dehydol TA 40.

Example 5

The procedure was as in Examples 2 to 4. In this case, the solid mixture consisted of 30% sodium water glass 2.0 including complexing agent, 20% tri-Na citrate and 50% soda. The solid mixture was dried in a spray tower with superheated steam. While spraying with a 70% H2θ2 solution the slightly soluble tri-Na citrate was partially dissolved and served as a binder for the build-up granulation. The H2O2 was added stoichiometrically to the soda and tri-sodium citrate in order to produce the corresponding addition compounds. The yield of H2θ2 addition compounds was 94% after drying to remove residual water. The granules were then coated in a Lödige mixer with a 30% layer of 55% by weight Dehydol TA 40, 30% by weight Lorol C18 and 15% by weight Dehypon LT 104.

Example 6

The procedure was as in Examples 1 to 5. The granules from Example 5, consisting of water glass N 2.0 with HEDP, percitrate (C6Hsθ7Na3 ^• 2 H2O2), percarbonate (Na2Cθ3 ^• 1.5 H2O2), were mixed with a nonionic surfactant mixture of 70% by weight Dehydol TA 40 and 30% by weight Dehypon KT 104 mixed and pressed to approx. 1 mm granules. 15% by weight of nonionic surfactant was added with respect to the starting material. The coating layer which closes on the outside has been applied to the granules in a fluidized bed. A mixture of antifoam ("paraffin SIK", mixture of different paraffin C chain lengths with an average melting point of 58 ° C.) and nonionic surfactant dehydol TA 40 has been used. The mixing ratio was 94: 6. The finished granules contained 15% coating material.

The compounds produced in this way from builder, alkali and bleach or with an additional integrated cobuilder and the z. B. Moisture-protective coating layer showed good to very good stabilities when stored in open containers without and with admixture of other detergent components. The content of active oxygen decreased by an average of 1.5% within 6 weeks.

Claims

Patent claims 1. At least partially water-soluble solid multi-component compound, in particular for use in detergents and cleaning agents, bleaching agents and / or disinfectants, containing absorbed and / or bound hydrogen peroxide (H2O2) and, if appropriate, per compounds formed under its influence, taken up in a mix of - (K1) solid alkali silicates of the module range (molar ratio SiO 2: M2O, where M = alkali metal) from 0.8 to 10 and - (K2) at least one further, preferably at least partially water-soluble, inorganic and / or organic solid component which is capable of absorbing H2O2 and, if appropriate, H2O, characterized in that - in the multi-component compound, the proportions (Kl) are at least 3 to 5% by weight and the proportions (K2) are at least 5 to 10% by weight - weight percent based in each case on the sum (Kl) + (K2), the multicomponent compound is designed as an agglomerate of a large number of fine particles of component (K2) and optionally (K1), which are firmly bonded to one another and whose fine particulate material has been introduced into the agglomeration at least partially as a corresponding solid material, - And that the entry of H2O2 was carried out during and / or preferably at least partially after the formation of the agglomerated multicompound compound. 2. Multi-component compound according to claim 1, characterized in that the formation of the multi-component compound is carried out as an agglomerate with the intermediate participation of an aqueous phase has been, preferably at least a portion of this aqueous auxiliary liquid having been withdrawn from the multi-compound. 3. Multi-component compound according to claims 1 and 2, characterized gekenn¬ characterized in that it is designed as a pourable and / or free-flowing solid material and in particular as a coarse-grained powder and / or granular material. 4. Multi-component compound according to claims 1 to 3, characterized gekenn¬ characterized in that at least a portion of the component (Kl) is water-soluble and has been distributed during the agglomeration in dissolved form over the granular material and dried thereon. 5. Multi-component compound according to claims 1 to 4, characterized gekenn¬ characterized in that the components (Kl) are at least partially present as a binder in the agglomerate. 6. Multi-component compound according to claims 1 to 5, characterized gekenn¬ characterized in that the loading of the multi-component compound with H2O2 has been carried out at least predominantly after the agglomeration of the finely divided mixture, but also mixing components containing H2O2 and / or per compounds in the agglomeration stage may have been used. 7. Multi-component compound according to claims 1 to 6, characterized gekenn¬ characterized in that at least the solid particles of the Kompen¬ te ^) to (Kl) H2θ2 stabilizers, in particular organic and / or inorganic masking agents and / or complexing agents for the inactivation of Schwermeta11spuren , contain. 8. Multi-component compound according to claims 1 to 7, characterized gekenn¬ characterized in that the stabilizers in a particularly aqueous solution of component (s) to (Kl) have been incorporated and brought here for reaction with the heavy metal traces therein. 9. Multi-compound according to claims 1 to 8, characterized gekenn¬ characterized in that organic complexing agents of the type HEDP, EDTA, NTA, DETPMP and / or EDTMP are at least partially incorporated into the component (Kl) as stabilizers. 10. Multi-component compound according to claims 1 to 9, characterized in that selected components or a plurality of compounds capable of binding H2O2, in particular corresponding inorganic and / or organic salts, are present as component (K2). 11. Multi-component compound according to claims 1 to 10, characterized gekenn¬ characterized in that at least partially as component (K2) water-soluble inorganic salts, in particular carbonates, bicarbonates, sulfates, halides, borates, phosphates and / or polyphosphates are present. 12. Multi-component compound according to claims 1 to 11, characterized gekenn¬ characterized in that at least partially as component (K2) alkali salts of lower and preferably polyfunctional carboxylic acids, such as citric acid, succinic acid, adipic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids and / or nitrilotriacetic acid and / or polymeric polycarboxylates are present. 13. Multi-component compound according to claims 1 to 12, characterized gekenn¬ characterized in that as component (K2) mixtures of inorganic and organic alkali salts, in particular corresponding carbonates, sulfates and / or borates, together with salts of citric acid, adipic acid, succinic acid, glutaric acid , Tartaric acid and / or sugar acids. 14. Multi-component compound according to claims 1 to 13, characterized gekenn¬ characterized in that its proportion (Kl) at most about 50 wt .-%, preferably not more than 35 to 40 wt .-%, while increasing the proportion of H2O2 binders (K2), or that - in particular for the formation of a multifunctional multi-component compound, for example as a builder / bleach for textile detergents - the proportion (Kl) is above 50% by weight. 15. Multi-component compound according to claims 1 to 14, characterized gekenn¬ characterized in that its proportion (K2) at least 15 wt .-%, preferably at least 20 wt .-%, but in particular not more than 75 to 80 wt .-% %. 16. Multi-component compound according to claims 1 to 15, characterized gekenn¬ characterized in that its content of H2O2 and / or its secondary products at least 0.5 wt .-%, preferably at least 1 wt .-% and in particular at least 3 wt. -%, e.g. at least 5 to 10 wt .-% - here also percent by weight based on the sum of (Kl) + (K2) - is. 17. Multi-component compound according to claims 1 to 16, characterized gekenn¬ characterized in that it contains as component (Kl) water-soluble alkali metal silicates, in particular sodium and / or potassium water glasses, whose module preferably in the range of 1 to 4 lies. 18. Multi-component compound according to claims 1 to 17, characterized gekenn¬ characterized in that the adherent agglomerates of the finely divided contents to (Kl) and (K2) have been dried by means of and / or in the protection of a hot gas phase. 19. Multi-component compound according to claims 1 to 18, characterized gekenn¬ characterized in that the drying has been carried out in particular still H2Ü2-free agglomerates in superheated steam as a hot gas and / or protective gas phase. 20. Multi-component compound according to claims 1 to 19, characterized gekenn¬ characterized in that it has been dried in a multi-stage process, preferably in at least one process stage - in particular at least in the last drying stage of the multi-component compound not yet loaded with H2O2 - with over ¬ heated steam has been worked as a drying and protective gas phase. 21. Multi-component compound according to claims 1 to 20, characterized gekenn¬ characterized in that its (Kl) portion is over-dried and its water content is in particular at most about 15 wt .-%, but is preferably below and for example in the range of about 5 to 12 wt .-% is. 22. Multi-component compound according to claims 1 to 21, characterized gekenn¬ characterized in that the (K2) -Aπteile dried at least largely free of water and are at least partially free of water, for example, as water bound to Kristall¬. 23. Multi-component compound according to claims 1 to 22, characterized gekenn¬ characterized in that there are additional stabilizers for H2O2, in particular magnesium ions and / or other known stabilizers, and in particular masking agents for polyvalent metal ions. 24. Multi-component compound according to claims 1 to 23, characterized in that it is provided with inorganic and / or organic coating layers which are preferably solid at room temperature and is sealed in particular. 25. Multi-component compound according to claims 1 to 24, characterized gekenn¬ characterized in that as coating and / or as the microporous Gutinnenstruktur at least partially filling loading dried water glasses and / or organic solid or flowable compounds with oleophilic molecular components, e.g. Fatty alcohols and / or nonionic surfactants. 26. Multifunctional multicomponent compound in solid form for use in detergents and / or cleaning agents, containing at least 15% by weight of alkali silicates in the module range from 1 to 4, preferably from 1.2 to 3, in a mixture with at least 10% by weight .-% of finely divided inorganic and / or organic water-soluble and / or water-dispersible salts, in particular from the field of builder or cobuilder components and / or builders for detergents and cleaning agents, which is caused by agglomeration and drying of mixtures of the multicomponent -Compound-forming components to a preferably free-flowing material has been produced, characterized in that it additionally contains H2O2 bound. 27. Multifunctional compound according to claim 26, characterized geken¬ characterized in that the H2O2 has been incorporated in the context of drying and / or by subsequent application in the multi-compound. 28. Multifunctional compound according to claims 26 and 27, characterized in that the H2O2 has been introduced in the form of an aqueous solution into the agglomerated multi-component compound, the water content preferably being removed at least partly by drying. 29. Multifunctional compound according to claims 26 to 28, characterized in that the multi-compound has been dried by exposure and / or in the protection of a hot gas phase. 30. Multifunctional compound according to claims 26 to 29, characterized in that the multicomponent compound has been prepared by drying water-containing agglomerates of the components forming the multicomponent compound with a hot gas phase. 31. Multifunctional compound according to claims 26 to 30, characterized in that superheated steam has been used as the hot gas phase for drying the carrier not loaded with H2O2. 32. Multifunctional compound according to claims 26 to 31, characterized in that the drying of the multi-component compound has been carried out under conditions that its water glass portion is present as an over-dried material - preferably with residual water content below 15% by weight. 33. Multifunctional compound according to claims 26 to 32, characterized in that its alkali silicate content - preferably as sodium and / or potassium silicate - at least 15 wt .-% and preferably 25 to 80 wt .-% and in particular 45 to 65 wt .-% is - percent by weight based on the sum of anhydrous inorganic and optionally organic components of the multi-component compound. 34. Multifunctional compound according to claims 26 to 33, characterized in that its content of inorganic and / or organic salts is 15 to 75% by weight, in particular 20 to 60% by weight. 35. Multifunctional compound according to claims 26 to 34, characterized in that its H2O2 content is at least 0.5% by weight, preferably at least 2% by weight and in particular at least 5 to 10% by weight. 36. Multifunctional compound according to claims 26 to 35, characterized in that it is provided with inorganic and / or organic coating and protective layers. 37. Multifunctional compound according to claims 26 to 36, characterized in that as a covering, but in particular also as an impregnating compound in the microporous gut structure, valuable and / or auxiliary substances from the area of wetting agents, detergents and cleaning agents - for example further builders or Cobuilder components, surfactants, in particular nonionic surfactants, anti-foaming agents and / or solubilizers - are present. 38. Multifunctional compound according to claims 26 to 37, characterized in that it has bulk densities of at least 150 g / 1, preferably of at least 200 g / 1 and in particular of at least 350 to 400 g / 1. 39. Multifunctional compound according to claims 26 to 38, characterized in that there is at least the alkali silicate portion characterized by high solubility in water even at ambient temperature, with its proportion of insoluble material preferably being <3% by weight and in particular <1% by weight. 40. Multifunctional compound according to claims 26 to 39, characterized in that at least 50% by weight, preferably at least 80% by weight, of the alkali metal silicate component is present as an over-dried material with an oligomer or polymer structure of the silica residues, where preferably the at least predominant proportion of these oligosilicones or polysilicic acids has Q2 and / or Q3 structure. 41. Multifunctional compound according to claims 26 to 40, characterized in that the silicate portion of the dry material is X-ray amorphous. 42. Multifunctional compound according to claims 26 to 41, characterized in that the module of the incorporated X-ray-amorphous alkali silicates, in particular corresponding sodium silicates, in the range from about 1.5 to 3.0, preferably in the range from 1.7 to 2.7. 43. Multifunctional compound according to claims 26 to 42, characterized in that it contains further stabilizers against undesired H2θ2 decomposition, e.g. Contains magnesium salts and / or masking agents for polyvalent metal ions. 44. A process for the preparation of the multicomponent compounds according to claims 1 to 43, characterized in that the finely divided component (s) are converted into (K2) and, if appropriate, also components present as a solid with (K1) a preferably aqueous liquid phase to a bulk and free-flowing material agglomerates and dries and simultaneously introduces H2O2 into the multi-material material with and / or after this drying. 45. The method according to claim 44, characterized in that for the agglomeration the component (s) (K1) is used at least in part as an aqueous preparation. 46. Process according to claims 44 and 45, characterized in that aqueous water glass solutions are used as agglomeration aids, which have been passivated prior to their entry by reaction with complexing agents for heavy metals. 47. Process according to claims 44 to 46, characterized in that the preferably dried agglomerate of (Kl) and (K2), which is particularly over-dried with respect to component (K1), is acted upon with aqueous H2O2 and optionally after-dried, it being further preferred can be that one works with 30 to 80 wt .-%, preferably 50 to 75 wt .-% aqueous H2O2 solutions, to which known stabilizers, in particular magnesium salts, can be added in a low concentration for additional stabilization. 48. Process according to claims 44 to 47, characterized in that the drying and preferably also the overdrying is carried out as part of a spray and / or fluidized bed treatment with a hot gas phase as the drying medium. 49. The method according to claims 44 to 48, characterized in that one works before the application of the H2O2 in at least one drying stage with superheated steam as the drying gas. 50. The method according to claims 44 to 49, characterized in that the preferably over-dried multi-compound with an aqueous and optionally containing additional stabilizers containing H2O2 solution, preferably working in a fluidized bed and preferably at least a portion of the water introduced again discharges. 51. Detergent and cleaning agent in solid preparation form, in particular textile detergent based on a mixture of surfactants, builder components, bleaching agents and other usual valuable and / or auxiliary substances, characterized in that they are used as a bleaching agent component and optionally as multifunctional builder and bleach component contain multi-component compounds according to claims 1 to 43.