ES2224224T3 - PROCEDURE FOR THE MANUFACTURE OF A WASHING OR CLEANING AGENT IN THE FORM OF PARTICLES. - Google Patents

Abstract

The invention relates to washing and detergent particulates and to several substances or starting materials treated for the preparation of these particulates. The invention provides for the manufacturing of washing and detergent agents of the type undergoing improved disintegration when they dissolve in an aqueous bath, even when they have a reduced surface area, especially a spherical form (e.g. pearls). The invention also provides an economical production method requiring no costly drying steps. According to the invention, these washing and detergent particulates and the substances or starting materials treated for their preparation must have an apparent density greater than 600 g/l. Moreover, these washing and detergent compounds must be produced by combination of washing and detergent mixtures and/or starting materials and must be formed simultaneously or in consecutive steps. For this purpose, the method involves preparing first a pre-mixture containing the individual starting materials and/or mixtures of several substances which are solid at ambient temperature and at a pressure of 1 bar, turning then this mixture into a granule with applied compression forces, before further possible processing or treatment. This pre-mixture is essentially anhydrous and a liquid forming additive, in the form of a polymer which has inflated in an essentially non aqueous solution, is used in the forming conditions, especially at ambient temperature and at a pressure of 1 bar.

Description

Procedure for the manufacture of an agent washing or cleaning in the form of particles.

The invention relates to a method for Quickly cleaning or cleaning agents manufacturing soluble, compacted in the form of particles, or components with various products, which they provide, in admixture with others components, tale agents, with the help of a procedure granulation specially adapted as well as the agents of cleaning and washing manufactured in this way.

Washing or cleaning agents in the form of particles, with bulk weights above 600 g / l, belong to the state of the art for quite some time now. In the last years, the weight gain in bulk was also accompanied by a concentration of components with washing and cleaning activity, of so that the consumer had to dose not only less volume, but also less dough per washing or cleaning process. Increasing of bulk weight, and especially again the concentration more high agents in substances with washing activity or cleaning, was obtained by subjectively worse solubility from the point of view of the consumer, due to speeds of slower dissolution of the applied agent. This delay of undesirable dissolution is triggered, among other things, due to that a series of anionic and non-ionic surfactants, and especially corresponding mixtures of surfactants, tend to form gel phases in the solution in water. Such gels can be presented already in the case of contents in  10% surfactants by weight, based on the total agent, that is, in the case of quantities of surfactants common in washing or cleaning agents under any point of view. According to experience, the tendency to gel formation also increases with the granulated structure of particles, each time more compact

The specification of the European patent EP 0486 592 B1 describes granulated washing or cleaning agents, or well extruded, with apparent densities above 600 g / l, which contain anionic and / or non-ionic surfactants in amounts of at least 15% by weight, and up to about 35% by weight. These are obtained according to a procedure in which press a solid premix, susceptible to spreading, containing a plasticizing and / or sliding agent, bar-shaped at high pressures, between 25 and 200 bar, are cut and the bar to the default granulation dimension by means of a device of cut after the exit of the perforated mold, and it is rounded. The premix consists, at least partially, of components solids, to which components are added, if any liquids, as liquid nonionic surfactants at temperature ambient. As stated above, in embodiments Preference is given to using aqueous preparations as agents. plasticizers and / or sliders. However, they also enter boiling point organic liquids relatively high, if necessary again mixed with water. However, the patent does not disclose procedural conditions. to comply in the case of an anhydrous extrusion. The products of obtained extrusion can already be used as a washing agent or cleaning, or elaborate additionally with other granules or powdery components to give washing or cleaning agents finishes Through high grain compactness, and the contents in relatively high surfactants, but also due to the ball or pearl shape desired by the consumer, which they present a significantly smaller surface area compared to granules conventional, you can reach the difficulties mentioned formerly depending on the combination of agents selected surfactants.

By international patent application WO-A-93/15180 is known to be improve the dissolution rate of extruded agents using in the premix short chain alkyl sulfates, especially alkyl sulfates with 8 to a maximum of 16 carbon atoms, that are introduced into the premix in a certain way. Without However, this measure is not enough in all cases to raise the dissolution rates of the total agent in the desired magnitude

German patent application DE 195 19 139 A1 proposes, for the solution of the conflict between high degree of compacted individual grain, especially extruded body, on the one hand, and the rapid redisolution of washing agents or cleaning finishes in aqueous baths also required, especially free of gelling, set up washing agents or cleaning in the form of particles with a higher bulk density than 600 g / l, which contain anionic and / or non-surfactant agents ionic in amounts of at least 15% by weight, such that at least two different granulated components of the which at least one is extruded, and at least one is not extruded, the content of surfactants of the Extruded component, including soaps, to a maximum of 15% by weight, referred to the respective extruded component. They are introduced other surfactant components of the washing or cleaning agent, finished, in the agent by one or more components not extruded While this procedure solves the problem of highly gelled cleaning or cleaning agents compacted, and with high content of surfactants, in the application in an aqueous bath, this also involves a series of new problems Disintegration processes may occur, and correspondingly fluctuations in the reproducibility of desired result of washing or cleaning. Also, not only the Extruded fraction of agents is of high density, the products Dried extrusion are, at the same time, relatively hard. Under the conditions of transport, storage and employment, you can expose the relatively softer granulate fraction to mechanical forces that partially lead to its crumbling, and with this to the formation of dust fractions and fine fractions by abrasion

Conventional procedures generally work with components of both solid and liquid washing or cleaning agents at room temperature; aqueous solutions and / or dispersions are also widely used as auxiliary granulating agents, or, as in the case of EP 0 486 592 B1, as plasticizing and / or sliding agents. Such procedures have the risk that gel-like structures that contribute to delayed dissolution in the redisolution in the aqueous bath will be produced, even when obtaining the washing or cleaning agents. In addition, especially the processes in which water, aqueous solutions or aqueous dispersions are used as auxiliary granulating agents, have the disadvantage of having to connect, downstream, drying, energy inconvenience in most cases, to obtain a final product susceptible to spreading, or stable to storage, and also shredding and / or sieving the obtained agglomerates, often quite coarse (see also " Size Enlargement by Agglomeration ", W. Pietsch, John Wiley & Sons, 1990, page 180) . Another drawback of this process is that, due to the dissolution of solid and water-soluble components, especially under the influence of pressure during extrusion, particle increases, as well as crystallizations, can be achieved, which, in general, exert again one had a negative influence on the dissolution behavior of the finished agents.

One method for obtaining heavy granules with the aid of an aqueous granulating auxiliary agent is the granulation in two stages, first generating still plastic agglomerates in a usual mixer / granulator, which is then treated in installations, such as a spheronizer. , rotocublator, Marumerizer, etc., is treated with auxiliary agent for liquid and / or powder molding, and is usually dried next. The granulate and subsequent rounding can be carried out, for example, in fluidized bed granulators, which contain a rotating disk. In this case, solid starting materials are first fluidized in the fluidized bed, and then agglomerated with auxiliary agent for liquid molding, which is introduced into the fluidized bed through tangentially oriented nozzles ( "Size Enlargement by Agglomeration", W. Pietsch, John Wiley & Sons, 1990, pages 450 to 451 ). In principle, this method can also be applied for non-aqueous procedures (melting coating procedures), but it is not possible to take advantage of the installation, a subsequent drying.

In the technical literature ( "Size Enlargement by Agglomeration", W. Pietsch, John Wiley & Sons, 1990, pages 450 to 441 ) only two methods for granulating under high pressure are known, which can be carried out completely without water. In this case, they are tableted in presses for tablets, and compacted by rolling, generating, in the last mentioned procedure, usually scabs that are subsequently broken to give granulated products, but irregularly. For this reason, in some systems the so-called pre-breakers are used to configure the starting product in a more homogeneous way from the point of view of its shape for the true granulation step, or ground. Then, undesirable fine and / or coarse grain fractions of the granules obtained in this way can be screened, and if appropriate recycled.

The international patent application WO-A-93/02176 describes a procedure for obtaining washing agents or solid cleaning with high bulk weights by meeting raw materials of solid washing or cleaning agents and liquids, under simultaneous or subsequent shaping, using as solid components, for example, agents anionic surfactants and adjuvants, and agents nonionic surfactants as liquid components, being put to disposal of the latter in an intimate mix with a breaker of structure such as polyethylene glycol or polypropylene glycol, or alcohols ethoxylated fatty acids with 8 to 18 carbon atoms with 20 to 45 groups of ethylene oxide (EO). As liquid surfactants not ionic are preferred linear ethoxylated alcohols, or branched with methyl in position 2, which have 8 to 20 atoms of carbon in the carbon chain, and on average 1 to 15 moles of ethylene oxide per mole of alcohol. In addition to the breakers of structure mentioned above, water is also described as adequate structural breaker in principle, whose use, without However, it is less preferred, since the agents can be impoverish in water during storage due to internal drying of the agents, and with it would no longer be effective, or not in its entirety, the desired dissolution solubility effect enhanced by use of a structure breaker. According to the teaching of this International patent application, agent mixtures non-ionic surfactants and structure breakers, which presented as a solution, or as a dispersion, can be use in all known granulation procedures, in that mixtures and / or manufactured raw materials are used individually. It is also possible, and even preferred, the use in an extrusion procedure according to the request of International Patent WO-A-91/02047 (or from European patent application EP 0 486 592 B1). By consequently, the use of aqueous solutions is also suggested, pastes or aqueous dispersions, not using water as structure breaker, as stated above, and it is usually removed by drying after the extrusion. Extrusion without addition is not explicitly suggested of water; even in the part of examples it is carried out, additionally, and separately from the mixture of surfactant not ionic-breaker structure, adding aqueous solutions; However, above all, this document is not indicate procedural conditions under which it can be carried carry out an extrusion free of water.

European patent application EP 0 337 330 describes a procedure for increasing the bulk weight of a spray dried washing agent by granulation in a mixer, with the addition of non-ionic compounds. To these ethoxylated and / or nonionic surfactants belong propoxylates, such as primary or secondary alcohols with 8 to 20 carbon atoms, and 2 to 20 moles of alkylene oxide per mole of alcohol, especially agents being added to the mixer nonionic surfactants with 2 to 6 EO, and HLB values of 11 or less. Ethylene glycols and propylene glycols can also be used. as non-ionic compounds.

In European patent application EP 0 711 828 a procedure for obtaining tablets is described, pressing a product wrapped in the form of particles. The enveloping substance is an auxiliary agent for molding or water-soluble disintegrant, with melting temperatures between 35 and 90 ° C However, in this case it is indicated as a characteristic essential that compacting / tabletting should be carried out at temperatures that are at least 28ºC, but at any case below the melting temperature of the auxiliary agent for the molding

It is known, by patent application International WO-A-96/10071, a procedure for obtaining granules with bulk weights of at least 650 g / l, and contained in surfactants of at least 40% by weight, the granulate being carried out in one step in a mixer with high shear speed, at temperatures between room temperature and 60ºC. As solid raw materials they serve particles with a particle size between 0.1 and 500 µm, must have at least 15% by weight of particles a size of particle above 50 µm, but being present fine particles sufficiently reduced, so that a especially high surface area of solid material. How auxiliary agent for molding serve agent mixtures surfactants consisting of anionic surfactants and nonionic surfactants in weight ratios of 2: 8 a 8: 2, which can have up to 20% by weight of water. As agents nonionic surfactants are indicated primary alcohols with 12 to 15 carbon atoms, with 3 to 7 EO. In the scope of the procedure mixtures of agents are especially advantageous surfactants containing up to 20% by weight of water, since This mode increases the viscosity of the mixture, and you can Better control the process. Additionally, the agent mixture Surfactants may also contain polyethylene glycols.

In the patent specification US 5 108 646 describes the obtaining of agglomerates adjuvants, agglomerating 50 to 75 parts by weight of aluminosilicates, or crystalline layered silicates, with 20 to 35 parts by weight of a binding agent. The agents Suitable binders are, above all, agent pastes highly viscous anionic surfactants, which may contain between 0 and 90% by weight of water. But they also enter consideration of polymers, such as polyethylene glycols, with weights molecular between 1000 and 20000, as well as mixtures of these and agents usual non-ionic surfactants, such as alcohols with 9 to 16 carbon atoms, with 4 to 8 EO, as long as the melting range does not start below 35 ° C, or below 45 ° C. The operation agglomeration takes place in a so-called intensive mixer, with a very determined power supply, relatively high. In the case of power supplies above indicated values an over agglomeration to a mass occurs pasty, in the case of smaller power supplies they obtain only finely divided powders, or very light agglomerates with an untimely wide grain spectrum.

Faced with this, the task of the invention consisted of in obtaining washing or cleaning agents in the form of particles, or components with several products, which they provide in mixture with other components said agents, which will present a improved disintegration at the time of dissolution in the bath aqueous, even in the case of reduced surface area, especially in the case of a spherical shape (pearl shape). In addition, the procedure should be convenient from the point of view economic, and be able to do without complicated stages for the dried In addition, the procedure should be economically favorable and can eliminate complicated drying stages.

Therefore, the object of the invention is a procedure for obtaining washing agents or cleaning in the form of particles, or components of several treated products or raw materials, which they provide in mixture with other components such agents, with bulk weights above 600 g / liter by combining the mixtures and / or the Raw materials for washing or cleaning agents with molding simultaneous or subsequent, first preparing a premix, which contains the individual raw materials and / or the mixtures, which are presented as solid products at temperature ambient and at a pressure of 1 bar, and then transformed this premix in a grain by applying forces of compaction and, if necessary, the continuation of the transformation or processing, characterized in that the premix it is substantially free of water and an auxiliary agent is used for liquid molding under the conditions for molding, especially even at room temperature and at a pressure of 1 bar, in the form of a non-aqueous solution of a swollen polymer, choosing the non-aqueous liquid component of the auxiliary agent for molding between monovalent, divalent or trivalent, liquid at room temperature, with points of boil (at 1 bar) above 80ºC among the following: n-propanol, iso-propanol, n-butanol, s-butanol, iso-butanol, ethylene glycol, 1,2- or 1,3-propylene glycol, glycerin, di- or triethylene- or propylene glycol or mixtures thereof.

In this case, it will be understood in the field of invention by "substantially anhydrous" a state in which the liquid water content, that is, not present in the form of water of  hydration and / or constitution water, is below a 2% by weight, preferably below 1% by weight, and especially even below 0.5% by weight, referred respectively to the premix. Therefore, you can introduce water into the procedure to obtain the premix sensitively only in chemical bound form and / or physical, or as a component of raw materials, or of the mixtures, which are presented as solid product at temperatures below 45 ° C, at a pressure of 1 bar, but not as a liquid, dissolution or dispersion Advantageously the premix has a total water content of not more than 15% by weight, presenting this water not in free liquid form, but linked from chemical and / or physical form, and being especially preferred that the water content, not bound with zeolite and / or with silicates, in the premix, it does not exceed 10% by weight, preferably less than 7% by weight, and especially preferably 2 at 5% by weight maximum.

In the scope of the invention it is understood as particulate washing or cleaning agents preferably those that do not have fractions in the form of powder, and especially particle sizes below 200 \ mum. Especially preferred are such distributions of particle size that have at least particles with a diameter of at least 400 µm at least 90% by weight. In a Especially preferred embodiment of the invention, the obtained washing or cleaning agents, compounds or materials treated premiums are composed, at least 70% by weight, advantageously at least 80% by weight, and especially preferably up to 100% by weight, by spherical particles (in pearl shape) with a particle size distribution that It has at least 80% by weight of particles between 0.8 and 2.0 mm. The washing or cleaning agents, in the form of particles, in the meaning of the present invention, may be constituted by tablets with usual dimensions for tablets of agents washing or cleaning for domestic applications, for example with weights from 15 to 40 g, especially from 20 to 30 g, with a  diameter from about 35 mm to 40 mm.

Swollen polymers, anhydrous, which used in the sense of the present invention as agents auxiliary for the molding, are those that lead to states gelatinous in non-aqueous liquids. They are especially suitable those systems consisting of non-aqueous liquid and polymer, presenting at room temperature, in the presence of the polymer, a 20 times higher viscosity, especially 300 times up to 500 times greater at least than the non-aqueous liquid alone. Viscosity of auxiliary agent for molding, that is, of the combination formed by the non-aqueous liquid and by the polymer, it is found, at room temperature, preferably in the range from 200 mPas up to 10,000 mPas, especially from 400 mPas to 6,000 mPas, measured for example with the help of a rotation viscometer Brookfield At a higher temperature, for example at 60 ° C, the viscosity preferably deviates only relatively little from the values corresponding to the ambient temperature and it is found, preferably, in the range from 250 mPas to 2,500 mPas. TO liquids belong monovalent, divalent or trivalent, liquid at room temperature, with melting points (at 1 bar) above 80 ° C, especially above 120 ° C, following: n-propanol, iso-propanol, n-butanol, s-butanol, iso-butanol, ethylene glycol, 1,2- or 1,3-propylene glycol, glycerin, di- and triethylene- or -propylene glycol or mixtures thereof. Especially glycerin and / or ethylene glycol. As polymers that lead to systems swollen in such water-free liquids, the polyvinylpyrrolidone, polyacrylic acid, copolymers constituted by acrylic acid and maleic acid, the polyvinyl alcohol, xanthan, starches partially hydrolyzed, alginates, amylopectin, starches carriers of methyl ether, hydroxyethyl ether, hydroxypropyl ether and / or hydroxybutyl ether or celluloses, phosphated starches such as starch diphosphate, as well as polymers inorganic such stratified silicates as well as their mixtures Polyvinylpyrrolidones will preferably be understood as those with relative molecular weights of up to 30,000 as maximum. In this case, intervals are especially preferred. of relative molecular weights between 3,000 and 30,000, for example close to 10,000. To the polymers used preferably hydroxypropyl starches and the starch diphosphate. The concentration of polymers in the anhydrous liquid preferably represents from 5% by weight to a 20% by weight, especially from about 6% by weight Up to 12% by weight.

The content in auxiliary agents for molding supposed, preferably in relation to the premix to be compacted, preferably at least 2% by weight, but without However less than 20% by weight, especially less than 15% in weight and especially preferably in amounts comprised in the range from 3% by weight to 10% by weight. At The description of this invention will be discussed in order to simplify, only one of the auxiliary agent for molding. However, in this case it should be indicated that it is possible, in itself, the use of several different auxiliary agents for molding and mixtures formed by various auxiliary agents for molding

It is understood by washing or cleaning agents those compositions that can be used for washing or cleaning, without having to add other components. On the contrary, a mixture of several products or a mixture is consisting of at least 2 components commonly used in washing or cleaning agents; however, the mixtures are they will normally use only in admixture with other components of preferred mode together with other mixtures. In the scope of this invention, a treated raw material is a raw material, in state divided in a relatively fine way, which became a coarser particle through the procedure according to invention. Strictly speaking, a treated raw material is, in the scope of the invention, a mixture when the treatment agent is a component commonly used in washing agents or cleaning.

The components used in the procedure according to the invention - with the exception of non-surfactants ionic, if present, liquids at temperatures below of 45 ° C and a pressure of 1 bar- can be mixtures obtained by separate, as well as raw materials, presented in powdery or particle form (finely divided up to rude), but that, in any case, are presented in solid form at room temperature, and at a pressure of 1 bar. By way of For example, they can be used as corpuscular particles beads, obtained by spray drying, or granules of an agglomeration procedure, etc. The composition of the mixtures itself is not essential for the invention, with the exception of water content, which must be sized in such a way that the premix is substantially free of water, as defined above, and not preferably containing more than 10% in weight of hydration water and / or constitution water. In this case, in a preferred embodiment mixtures are used over-dried in the premix. Such mixtures can be obtained, from Example way, by spray drying, regulating the temperature control so that the temperatures tower outlet are located above 100 ° C, so Example at 110 ° C, or above. Similarly, it is possible use solid mixtures in the premix, which serve as support for liquids, for example surfactants nonionic, liquid, or silicone oil and / or paraffins. These mixtures may contain water in the indicated range previously, the mixtures being scattered, and remaining spreadable, or at least transportable, preferably also at elevated temperatures of at least 45 ° C. However it is preferably used in the premix, mixtures with a maximum 12% by weight, and especially preferably, with a maximum of 9% by weight of water, referred to the premix. Preferably, the premix does not contain water at all free, that is, water that is not linked in any way with a solid substance, and present, therefore, "in form liquid ", since already very small quantities, so Example about 0.2 or 0.5% by weight, based on the premix, are sufficient to dissolve the molding agent, which It is, in itself, water soluble. This would result in the melting point reduction, or softening point of the final product and therefore would lose so much in its aptitude to scattered, as well as in bulk weight.

Surprisingly, it has been observed that indifferent in any way in what solid raw material, or in what solid mixture the water is bound to. In this way, it is due consider less critical the water that is linked to the adjuvant substances, described below in greater detail, such as zeolite or silicates, especially if the water is linked with zeolite A, with zeolite P, or MAP and / or with the zeolite X. On the contrary, it is preferred that water, which is linked with other solid components, other than those mentioned adjuvant substances, preferably contained in amounts less than 3% by weight in the premix. Thus, In an embodiment of the invention it is preferred that the water content bound in the premix is not more than 10% by weight, and / or that the water content not bound to the zeolite and / or with silicates is less than 7% by weight, and, preferably, from a maximum of 2 to 5% by weight as maximum. In this case, it is especially advantageous that the premix does not contain water at all, which is not linked to the adjuvant substances However, this can only be done. technically with difficulty, since, as a rule, they are always dragged at least traces of water with the materials raw and with mixtures.

The content of solid mixtures, used in the premix, in liquid, non-aqueous components, to temperatures below 45 ° C, excluding agents molding auxiliaries, liquids at room temperature, ascends preferably, up to 10% by weight, advantageously up to 6% by weight, referred respectively to the premix. In the premix it they will especially use solid mixtures, which contain agents nonionic surfactants, liquids at temperatures below 45 ° C and at a pressure of 1 bar, which were obtained separately according to all types of procurement known - by way of example by spray drying, granulation or spraying by means of support pearl nozzles. This way you can obtain premixes, which admit, by way of example, up to approximately 10% by weight, preferably below, especially up to a maximum of 8% by weight, and, so Example, between 1 and 5% by weight of agents nonionic surfactants, referred to the finished agent.

Mixtures containing water in the form indicated above and / or serving as a support for liquids, especially for non-ionic surfactants, liquids a ambient temperature, that is, they contain said components liquid at room temperature, and can be used according to invention, preferably do not have a point of softening below 45 ° C. Similarly, the subjects individual premiums, used separately, have a point of melting of at least 45 ° C. The melting point, or the point of softening of all individual raw materials and of mixtures, used in the premix, are preferably found above 45 ° C, and advantageously at least 50 ° C.

In a preferred embodiment of the invention, at least 80% by weight, especially at least 85% by weight, and especially preferably at least 90% by weight of all individual mixtures and raw materials, used in the premix, have a softening point, or point melting significantly higher than temperatures, which are reached under the procedural conditions, with the exception of the agent auxiliary for molding, which is liquid at room temperature. In practice, only for economic reasons, the temperatures for molding will not be above 150 ° C, preferably not above 120 ° C. Thus, at least one 80% by weight of the mixtures used and raw materials individual, has a softening point, or point melting, above 150 ° C. at normal pressure (1 bar).

In addition to solid components and auxiliary agents for molding, liquids at room temperature, the premix may contain up to 10% by weight of agents nonionic surfactants, liquids at temperatures below 45 ° C, and at a pressure of 1 bar, especially alcohols alkoxylated, commonly used in washing agents or cleaning, such as fatty alcohols or oxoalcohols with a carbon chain length between 8 and 20, and especially on average 3 to 7 units of ethylene oxide per mole of alcohol (see more exact description below). The addition of liquid nonionic surfactants, can be carried out in amounts that still ensure that the premix is presented in the form spreadable When such surfactants are not incorporated ionic, liquid, in the premix, it will be preferred to incorporate in the  procedure, separately from each other, the agents nonionic surfactants, liquids, and auxiliary agent for the molding, disintegrating action. In a preferred form of embodiment of the invention the agents are applied superficially liquid surfactants, in a continuous production process, especially by means of nozzles, on the dust stream, and They are absorbed by the latter.

However, the premix also contains the less a raw material, or at least a mixture, which serve as auxiliary agents for molding, as described previously. The auxiliary agent for molding can be mixed with the usual components of the premix in the form of a polymer swollen, anhydrous, as a previous step to the molding stage. This is especially preferred when molding is carried out by of an extrusion stage or with the help of a entablet process or according to any other pressing process. I could also apply over the premix by means of nozzles during molding or can be added, drop by drop, to the premix, which is preferred, in in particular, in the case of molding by granulation in formation. The temperature during the molding stage is preferably at room temperature or at temperature which is generated by the incorporation of energy from the device molding, however, it is also possible to heat the premix and, if necessary, the auxiliary agent for molding, added separately during molding, at higher temperatures, by example from 35 ° C to 80 ° C, the temperatures in the range from 45 ° C to 65 ° C.

It has been found advantageous that the auxiliary agent for the molding it is distributed as homogeneously as possible in the product to be compacted during the procedure stage of the compacting molding, not intended to be limited to this theory, the applicant considers that, through a homogeneous distribution of auxiliary agent for molding, in the sense of a binder, within the premix under the procedural conditions of compacted, solid mixtures, and raw materials individual present, if any, are wrapped by the agent binder, and then they are glued together so that the finished final products are constituted almost exactly by this large number of small individual particles, which held together by the binding agent, which adopts the function of a separation wall, preferably thin, between These individual particles. In this case, in the idealized way it can be started from a honeycomb structure, being loaded these honeycombs with solid products (mixtures or raw materials individual). In the case of contact with water, even with water cold, that is, in an exemplary way at the beginning of a process Machine wash, these thin separation walls are they dissolve, or they decompose almost instantaneously; so surprising, this is also the case of the auxiliary agent for the molding does not dissolve, in itself, quickly in water at temperature ambient. However, preferably, those auxiliary agents for molding that can dissolve almost by complete in a test procedure, as indicated more forward, at a concentration of 8 g of auxiliary agent for molding on 1 liter of water at 30 ° C in the 90 second interval. In some cases it is advantageous, however, to adjust so controlled, ie retard, solubility by means of a additive.

The auxiliary agent for molding should be of such so that the adhesive properties of the temperatures for molding. Moreover, it is also essential for the selection of type and quantity of auxiliary agent for the molding used, that the properties are certainly not lost binders after the molding stage inside the product final, which ensures the cohesion of the final product, but that the final product itself is not sticky under the conditions usual storage or transport. Surprisingly, in this However, a final product that does not have tendency to stickiness, when auxiliary agents are used for molding liquids at room temperature or temperature ambient or at slightly elevated temperatures of approximately 30ºC, that is to say at summer temperatures and under the conditions of Storage and transport.

The meeting of mixtures and / or raw materials of washing or cleaning agents, with simultaneous molding or Subsequently, it can be done by usual procedures, in which compaction forces are applied, such as granulation, compacted, for example compacted by lamination or extrusion, or entabletting, if necessary under the addition of agents usual disintegrants, and pelletized. In this case, it also can be used in the premix granules dried by spraying, by way of prefabricated mixtures, but the invention does not It is limited to it in any way. On the contrary, in the method according to the invention it is possible not to use granules spray dried, as they can also be made without Raw materials problems very finely divided, with fractions powdery, without having to carry out a previous mixture, of For example, spray drying.

Conducting the procedure noticeably in absence of water allows not only the one that can be made peroxy bleaching agents without loss of activity, it is also possible to produce bleaching agents peroxy type and bleach activators together in a particle, without fear of serious loss of activity.

In a preferred embodiment of the invention the compacting molding of the process will be carried out with the help of an agglomeration stage, granulating, so binder, premix in a suitable device for it and exerting the auxiliary agent for molding, previously described, the role of a binding agent. The procedure of granulation can be carried out continuously or discontinuous In this case, it is preferably derived from such way, that the solid components of the premix, to be compacted, it is arranged in a granulator, being able to be used as such also a mixer, if necessary the powder is bound optionally present by adding a non-surfactant ionic liquid and the auxiliary agent is incorporated into the granulator for molding. The desired average particle size of the granulate can be adjusted through the type and amount of auxiliary agent for molding and through the parameters of the machine and work, such as for example the number of revolutions and residence time as well as temperature. How  suitable granulators can be used, for example, pelletizers, rotating drums, mixers with plow arm with Lödige® signature shredder, high mixers performance with rotating mixing bowl and fluidized by example of the firm Laeis Bucher® or Eirich®, intensive mixers with cutting heads for example from LIPP Mischtechnik® or Imcatec®, Drais®, Fukae® or Forberg® mixers as well as the called Rotorcoater® of the firm Glatt® with rotating disk horizontal as well as with rotating disk inclined at 50º. Less suitable are the Lödige® CB mixers, the mixers PK-Niro® zigzag, a Ballestra® kneader mixer as well as Hosokawa® mixers or Schugi®. Similarly, a moving bed is less suitable or a horizontal mixer, for example a Nautamixer®. In the field of this embodiment of the process according to the invention it is preferred to work at room temperature or at temperature that is set due to the energy input of the mixer or granulator, i.e. no heating stage  individual, as for example described in the request for international patent WO 94/13779 and in the state of the art there described In this case it should be considered as an advantage of method according to the invention which is necessary a two-stage granulation procedure, described for example in European patent application EP 0 367 339, in which the granulate it is compressed first of all in a high speed mixer and at then compressed in a mixer and granulator with low rotation speed, but granulation can be carried out compactor only in one stage by using the polymer swollen anhydrous

The agents according to the invention in the form of tablets can be manufactured by entantering presses traditional, for example eccentric presses or rotary presses, with compression forces in the range from, for example 200. 10 5 Pa up to 1,500. 10 5 Pa.

In another preferred embodiment of the process according to the invention the products are mixed together solids in a usual mixing and / or granulator device for solid and spreadable premix manufacturing, first of all to room temperature at slightly elevated temperatures, which preferably in the range from temperature ambient up to 35 ° C. The precompaction stage of the procedure according to the invention is then carried out by means of a extrusion of the premix obtained in this way, as described for example in European patent EP 0 486 592 B1 or in the international patent applications WO-A-93/02176 and WO-A-94/09111. In this case it press the premix under pressure in the form of bars and the bar will chop, after the exit of the perforated mold, by means of a cutting device up to a predetermined dimension for the granulated. The homogeneous and solid premix contains, as a rule In general, a plasticizing and / or lubricating agent that has as action the plastic softening of the premix under pressure or under the contribution of specific work and be extrudable. According European patent EP 0 486 592 B1 belong in this regard especially anionic surfactants such as alkylbenzenesulfonates and / or alkyl sulfates (fatty), as well as also polymers such as polycarboxylates. With the help of  method according to the invention it is possible, however, to give up completely of such plasticizers and / or lubricants solids, known since the function of a lubricating agent It can be exercised by the auxiliary agent for molding, previously defined. The auxiliary agent for molding prevents or reduces at least the formation of scabs on the walls of the apparatus and on the tools for compaction. This is valid not only for processing in the extruder, but also for the work for example in mixers / granulators or rollers that Work continuously.

For the explanation of the procedure itself extrusion, in this case expressly refers to patents and requests cited above. In a preferred form of embodiment of the invention, the premix is fed preferably continuously to a laminating extruder planetary, or to a 2-tree extruder, or 2-extruder spindles, with spindle driving with rotation in it direction or with turning in opposite directions, whose housing and head of granulation-extruder may be heated to the previously determined extrusion temperature. Under the action of Shearing the spindles of the extruder compacts the premix under pressure, which preferably amounts to at least 25 bar, but that can also be placed below this value, in the case of extremely high flows depending on the installation used, compacted, plasticized, extruded in shape of thin bars through perforated nozzle plates in the head of the extruder and finally the product crumbles extruded by means of a rotating detachment blade, preferably to give granules grains approximately spherical to cylindrical. The hole diameter of the plates of perforated nozzles and the length of cut of bar adjust in this case to the dimension selected for the granulate. In this embodiment, obtaining granules of a predetermined particle size, substantially uniform, the absolute particle sizes may be adapted, in particular, for the intended purpose of employment. In general they are preferred particle diameters up to a maximum of 0.8 cm. The important embodiments provide in this case the obtaining homogeneous granules on a millimeter scale, so Example in the range of 0.5 to 5 mm, and especially in the range of 0.8 to 3 mm. The length / diameter ratio of the detached primary granules are found, in this case, in the range from about 1: 1 to about 3: 1 in a important embodiment. Alternatively they can be carried carry out extrusions / presses also in low extruders pressure, in the Kahl press or the Bextruder®.

In addition, it is preferred to feed granules primary still plastic to an additional processing stage molding in this case, the present edges are rounded eventually after the compaction stage, so that you can obtain, ultimately, spherical grains up to approximately spherical, in case these are no longer formed in the first stage of molding by compacting. If desired, at this stage you can concomitantly use reduced amounts of dry powder, of Example zeolite powder, such as NaA zeolite powder. This forming can be done in devices for spheronization, commercial. In this case, it should be ensured that they occur only reduced amounts of fine grain fraction at this stage. Without However, in the scope of the present invention there is more than one drying, which is described as a preferred embodiment in the prior art documents cited above, since the process according to the invention is carried out substantially in absence of water, that is, without the addition of free water, no linked.

The essence of a preferred embodiment of the invention is that the distribution of grain sizes of the premix is substantially wider than that of the product final obtained according to the invention and that of the final product according to the invention. In this case, the premix may contain fractions. noticeably larger fine grains, even fractions of powder, if necessary also fractions of coarser grain, but being preferred to transform a premix with distribution of relatively wide particle sizes, and relatively fractions raised in fine grain, in a final product with distribution of relatively narrow particle sizes, and fractions relatively small fine grain.

Since the process according to the invention is carried out in substantially anhydrous medium - that is, with exception of water contents ("impurities") of the materials solid premiums used, not only minimized and even excluded the danger of gelling of the surfactant raw materials already in the process of obtaining, but additionally is set to provision also a valuable procedure from the point of ecological view, because in this way, by suppressing a subsequent drying step, not only energy is saved, but emissions can also be avoided, as they occur predominantly in conventional drying types.

It has been observed that the behavior of redisolution of the washing or cleaning agents manufactured according to the invention, in return to the agents manufactured from traditional way, now it depends substantially only on dissolution behavior of the isolated components; how much the greater the number of components contained, which dissolve from a relatively fast way, the faster it gets they will also solubilize the finished agents; the higher the number of components of relatively slow solubility content, the more slowly the agents will also be solubilized. Obviously, interactions no longer play any role. undesirable during redisolution, such as gels, etc., in the process according to the invention, even in the case of agents washing or cleaning with very high densities, so Example above 750 and 800 g / l. In this way, the agents, mixtures and treated raw materials, obtained from In this way, they have an improved dissolution rate compared to those agents, mixtures, and treated raw materials, which they certainly have the same final composition, but they haven't manufactured according to the method according to the invention, it is say, they have not been manufactured under anhydrous conditions, such as use of a swollen polymer as an auxiliary agent for molding

The dissolution behavior of the agent washing or cleaning, in the form of particles, which has been manufactured according to the method of the invention, it now depends only on the dissolution behavior of individual raw materials and of the mixtures used. Without pretending to limit this theory, the applicant assumes that this special behavior to the dissolution is caused by a particle structure similar to a honeycomb, these honeycombs being loaded with product solid.

Another object of the invention are mixtures and treated raw materials, obtained with the help of the procedure according to the invention, by way of example granules adjuvants, bleach activating granules, or granules enzymatic Especially the subjects treated show a surprisingly high dissolution rate in water, about all if the raw material was used very finely distributed, if necessary in milled form.

Especially preferably they are set to disposal of granulated base, mixtures and treated raw materials, that have a spherical shape, or a pearl shape.

The bulk weight of the products of the procedure, manufactured according to the invention, is found preferably above 700 g / l, especially between 750 and 1000 g / l. Even if the granules with other components, which present bulk weights more reduced, the bulk weight of the final product is not reduced in the extension that would be expected normally. It is assumed that approximately spherical agents, and especially the products extrudates, which have been manufactured according to the procedures of the invention, more closely resemble the ideal configuration of a sphere with a smooth, "lubricated" surface, that agents and extruded products, manufactured according to the procedures conventional, and especially aqueous. In this way you get a better spatial padding, which leads to a higher bulk weight, even when components that have no structure or structure are added spherical, nor a bulk weight so high.

The products of the procedure, in the form of particles obtained can be used directly as an agent of washing or cleaning, or they can be treated further and / or They can be prepared previously according to usual methods. Between usual subsequent treatments count, so Example, sprinkled with finely divided components of washing or cleaning agents, for example with zeolites, whereby the bulk weight is further increased in general. However, it also constitutes a further preferred treatment. the procedure according to German patent applications DE 195 24 287 and DE 195 47 457, being able to glue components powdery or at least finely divided (so-called fine fractions) on the products of the procedure in the form of particles, obtained according to the invention, which serve as a core, and producing, therefore, agents presenting these called fine fractions as an outer shell. This is advantageously carried out by means of an agglomeration stage, The auxiliary agents can be used as binding agents for molding the process according to the invention. In relation to the possible fusion agglomeration of the fine fractions on the basic granules according to the invention and manufactured according to the invention will expressly refer to the disclosure given in the German patent applications DE195 24 287 A1 and DE 195 47 457 A1.

In general, elaboration means the particulate process products, manufactured according to the invention, they serve as mixtures, with which they can be mix other components, if necessary also other mixtures. In This case will refer to the descriptions of the requests of patent and cited patent documents, that is, especially to European patent EP 0 486 592 B1, as well as applications for German patent DE 195 19 139, DE 195 24 287, and DE 195 47 457. In addition to enzymes, bleach activators and foam inhibitors, especially salts, such as silicates (crystalline or amorphous), including metasilicate, carbonate, bicarbonate, sulfate, bisulfate, citrate, or others polycarboxylates, as well as organic acids, such as acid Citrus in the preparation. In this case it is especially preferred use the mixing components in granulated form, and with a particle size distribution, which is adjusted to the distribution of agent particle sizes and mixtures obtained according to the invention.

In a preferred embodiment of the invention a washing agent in the form of particles, which is constituted at least 80% by weight per mixtures and / or treated raw materials, obtained according to the invention. Especially it is constituted by at least 80% in weight per base granulate, manufactured according to the invention. The Remaining components may have been obtained and mixed according to Any known procedure. However, in this case it is preferably obtain these remaining components, which may be mixtures and / or raw materials treated, according to the procedure according to the invention. In this way, the obtaining base granules and the remaining components with an aptitude for spreading, with a bulk weight, with a size and with a particle size distribution approximately same. It is also possible to manufacture from the mixture of mixtures, manufactured according to the invention, and / or raw materials treated with the aforementioned remaining components, molded bodies older, for example tablets. However, it should be considered as especially advantageous as possible, with the help of method according to the invention, really use all components of a washing or full cleaning agent by way of premix and effect granulation to give splinters anhydrous

Now follow a detailed description of the possible additional components of the agents according to the invention, and of the components used in the procedure according to the invention.

The important components of the agents according to the invention and the components, which are used in the process according to the invention, they are surfactants, especially anionic surfactants, which may be contained, by less, in amounts of 0.5% by weight in the agents according to the invention, or in the agents manufactured according to the invention. Among these are, especially, sulphonates and sulfates, as well as soaps.

As sulphonate surfactants preferably alkylbenzenesulfonates are considered with 9 to 13 carbon atoms, olefinsulfonates, that is, mixtures constituted by alkene and hydroxyalkanesulfonates, as well as disulfonates, such as those obtained, for example, from monoolefins with 12 to 18 carbon atoms with double bond located at the end or inside the chain, by sulfonation with gaseous sulfur trioxide, and subsequent alkaline hydrolysis or Acid sulfonation products. Also suitable are alkanesulfonates, which are obtained from alkanes with 12 to 18 carbon atoms, for example by sulfocloration or sulfoxidation, with subsequent hydrolysis, or neutralization. Similarly, acid esters are also suitable α-sulfograms (estersulfonates), for example the α-sulphonated methyl esters of the coconut, palm kernel or tallow hydrogenated fatty acids, which are obtained by α-sulfonation of the methyl esters of fatty acids of plant and / or animal origin with 8 to 20 carbon atoms in the fatty acid molecule, and subsequent neutralization to give mono-salts water soluble. In this case it is preferably the esters α-sulfonated fatty acids hydrogenated coconut, palm, palm kernel or tallow seeds, acid sulfonation products may also be present unsaturated fatty acids, by way of example oleic acid, in amounts reduced, preferably in amounts not exceeding approximately 2 to 3% by weight. They are especially preferred alkyl esters of acids α-sulfograms, which have a chain of alkyl with no more than 4 carbon atoms in the ester group, for example, methyl, ethyl, propyl and butyl esters. From especially advantageous, the methyl esters of the α-sulfograms (MES) as well as his saponified disals. Other anionic surfactants, suitable are sulfated fatty acid glycerin esters, representing mono-di- and tri-esters, as well as mixtures thereof, such as they are obtained in obtaining by esterification by means of a monoglycerin with 1 to 3 moles of fatty acids, or in the transesterification of triglycerides with 0.3 to 2 moles of glycerin. As alkyl (en) yl sulfates, preference is given to alkaline salts, and especially sodium salts, of semisters of sulfuric acid with fatty alcohols with 12 to 18 carbon atoms, for example from alcohols coconut fatty, tallow fatty alcohols, lauric alcohol, myristic alcohol, cetyl alcohol or stearic alcohol, or oxoalcohols with 10 to 20 carbon atoms, and those half esters of secondary alcohols with these chain lengths. In addition, they are preferred alkylated sulfates with those mentioned chain lengths, containing a chain alkyl moiety Linear synthetic, obtained on petrochemical basis, presented degradation behavior such as mixtures suitable, based on fat chemistry raw materials. They are especially preferred, in the interest of washing technology, alkyl sulfates with 12 to 16 carbon atoms and sulfates of alkyl with 12 to 15 carbon atoms, as well as sulfates of alkyl with 14 to 15 carbon atoms. They are also agents suitable anionic surfactants sulfates of 2,3-alkyl, which are obtained, so Example, according to US patent applications US 3,234,258 or 5,075,041, and which can be purchased as commercial products of the Shell Oil Company under the name DAN®. Also suitable are alcohol monosulfates with 7 to 21 straight chain or branched chain carbon atoms, ethoxylated with 1 to 6 moles of ethylene oxide, such as alcohols with 9 to 11 carbon atoms, branched with 2-methyl with an average of 3.5 moles of oxide ethylene (OE) or fatty alcohols with 12 to 18 carbon atoms with 1 to 4 OE. Normally, these are used in washing agents only in relatively small quantities, for example in quantities from 1 to 5% by weight, due to its high performance to the foam Also, other anionic surfactants Preferred are the salts of alkylsulfosuccinic acid, which they also call sulfosuccinates or esters of sulfosuccinic acid and the monoesters and / or diesters of sulfosuccinic acids with alcohols, preferably fatty alcohols and, especially, with ethoxylated fatty alcohols. Preferred Sulfosuccinates contain fatty alcohol residues with 8 to 18 carbon atoms, or mixtures thereof. Especially preferred sulphosuccinates they contain a fatty alcohol residue, which is derived from alcohols ethoxylated fatty acids, which represent non-surfactants Ionic considered by themselves. In this case they are especially preferred in turn sulphosuccinates, whose alcohol residues fatty are derived from ethoxylated fatty alcohols with a distribution of the close counterparts. Similarly, it is also possible use alkylsuccinic acid preferably with 8 to 18 carbon atoms in the alkyl (en) yl chain, or its salts. They come into consideration, as surfactants additional anionic, fatty acid derivatives of amino acids, for example N-methyltaurine (taurides) and / or N-methylglycine (sarcosides). In In this case, sarcosides are especially preferred, or sarcosinates, and, in this case, especially acid sarcosinates  higher fat and, if appropriate, unsaturated once or several times, like oleyl sarcosinate. They come into consideration, by way of other anionic surfactants, especially soaps, preferably in amounts from 0.2 to 5% by weight. Especially suitable are soaps of saturated fatty acids, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and of behenic acid, as well as, especially, soaps mixtures derived from natural fatty acids, for example from acids Coconut, palm kernel or tallow fatty. Along with these soaps, or as substitutes for soaps, can be used, also, the known salts of alkenyl succinic acid.

Anionic surfactants (with inclusion of soaps) can be presented in the form of their salts sodium, potassium or ammonium, as well as salts soluble organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in form of their sodium or potassium salts, especially in the form of sodium salts Surfactants are contained in the agents according to the invention, or are used in the process according to the invention, preferably, in amounts from 1 to 30% by weight, and especially in quantities from 5 to 25% by weight.

In addition to anionic surfactants and of cationic, zwitterionic and surface-active agents amphoteric, non-surfactants are especially preferred ionic

They are preferably used as agents non-ionic alkoxylated alcohols surfactants, advantageously ethoxylates, especially primary, preferably with 8 to 18 carbon atoms, and an average of 1 to 12 moles of oxide of ethylene (OE) per mole of alcohol, in which the alcoholic remainder it can be linear, or be branched with methyl preferably in position 2, or it may contain linear and branched remains with methyl in mixture, as they usually occur in residues oxoalcoholics However, they are especially preferred alcoholic ethoxylates with linear residues constituted by alcohols of native origin with 12 to 18 carbon atoms, per example from coconut fatty alcohols, palm kernels, of tallow, or oleic alcohol, and on average from 2 to 8 moles of OE  per mole of alcohol. To the preferred ethoxylated alcohols they belong, for example, alcohols with 12 to 14 atoms carbon with 3 OE or 4 OE, alcohols with 9 to 11 carbon atoms with 7 OE, alcohols with 13 to 15 carbon atoms with 3 OE, 5 OE, 7 OE or 8 OE, alcohols with 12 to 18 carbon atoms with 3 OE, 5 OE or 7 OE, and mixtures thereof, as mixtures consisting of alcohol with 12 to 14 carbon atoms with 3 OE, and alcohol with 12 to 18 carbon atoms carbon with 7 OE. The degrees of ethoxylation indicated represent statistical mean values, which can be an integer or Fractional for a special product. Alcoholic ethoxylates Preferred have a narrow counterpart distribution (narrow range ethoxylates, NRE). Additionally to these agents nonionic surfactants, alcohols can also be used fatty with more than 12 OE. In this respect, the alcohols are examples fatty (tallow) with 14 OE, 16EO, 20 EO, 25 OE, 30 OE or 40 OE.

To non-ionic surfactants belong, also, the alkyl glycosides of the general formula RO (G) x, in which R means a remainder aliphatic, primary, straight chain or branched chain with methyl, especially branched with methyl in position 2, with 8 up to 22, preferably with 12 to 18 carbon atoms, and G is the symbol of a glucose unit with 5 or 6 carbon atoms, preferably glucose. The x degree of oligomerization, which indicates the distribution of monoglycosides and oligoglycosides, is a arbitrary number between 1 and 10; preferably x takes values from 1.2 to 1.4. Similarly, the amides of the polyhydroxy fatty acids of the formula (I), in which R 2 CO represents an aliphatic acyl moiety, with 6 to 22 atoms of carbon, R 3 represents hydrogen, an alkyl moiety or hydroxyalkyl with 1 to 4 carbon atoms, and [Z] represents a linear or branched polyhydroxyalkyl moiety with 3 to 10 atoms of carbon, and 3 to 10 hydroxyl groups.

\uelm{N}{\uelm{\para}{R ^{3} }}

---[Z](I) R2 --- CO ---

 \ uelm {N} {\ uelm {\ para} {R3}} 

--- [Z]

The amides of polyhydroxy fatty acids are preferably derived from reducing sugars with 5 or 6 atoms of carbon, especially glucose. To the group of amides of polyhydroxy fatty acids also belong to the compounds of the formula (II)

\uelm{N}{\uelm{\para}{R ^{5} ---O---R ^{6} }}

---[Z](II) R 4 --- CO ---

 \ uelm {N} {\ uelm {\ para} {R 5} --- O --- R 6}} 

--- [Z]

in which R 4 represents a linear or branched alkyl or alkenyl moiety with 7 to 12 atoms of carbon, R 5 represents a linear, branched or branched alkyl moiety cyclic, or an aryl moiety with 2 to 8 carbon atoms, and R 6 represents a linear, branched or cyclic alkyl moiety, or a aryl moiety, or an oxy-alkyl moiety with 1 to 8 atoms carbon, with alkyl moieties having 1 to 4 atoms of preference being preferred carbon or the phenyl moiety, and [Z] represents a moiety linear polyhydroxyalkyl, whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated derivatives, preferably ethoxylated or propoxylated of these residues. Too in this case [Z] is preferably obtained by amination by reduction of a sugar, such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The compounds N-alkoxy N-aryloxy-substituted can be transform then, as an example according to teaching of the international patent application WO-A-95/07331, in the amides of desired polyhydroxy fatty acids, by reaction with esters of methyl fatty acids in the presence of an alkoxide by way of  catalyst. Other class of non-ionic surfactants used, preferably, which are used in the process according to the invention either as sole non-ionic surfactants or in combination with other non-ionic surfactants, especially with alcohols alkoxylated fatty acids and / or with alkyl glycosides, are alkyl esters of alkoxylated fatty acids, preferably ethoxylated or ethoxylated and propoxylated, preferably with 1 to 4 atoms of carbon in the alkyl chains, especially methyl esters of fatty acids, such as those described, so For example, in Japanese patent application JP 58/217598, or which are preferably obtained according to the procedure described in WO-A- international patent application 90/13533. As nonionic surfactants, preference is given to methyl esters of fatty acids with 12 to 18 atoms of carbon with an average of 3 to 15 EO, especially with an average from 5 to 12 EO. Non-surfactants may also be suitable. ionic type of amine oxides, by way of example oxide of N-coco-alkyl-N, N-dimethylamine and oxide of N-tallow-alkyl-N, N-dihydroxyethylamine,  and fatty acid alkanolamides. The amount of these agents nonionic surfactants is preferably not greater than that of ethoxylated fatty alcohols, especially does not amount to more than half of the same.

As other surfactants enter consideration of the so-called geminal surfactants. In general it is understood by these those compounds that have two hydrophilic groups per molecule. Generally, these groups are separated from each other by a so-called "spacer". As a rule In general, this spacer is a carbon chain, which should be long enough for hydrophilic groups to have a enough distance for them to react independently of each other. Such surfactants are generally distinguished by a critical micellar concentration unusually reduced, and by the ability to greatly reduce The surface tension of the water. In exceptional cases, under the expression geminal surfactants are understood not only such dimer surfactants, but also correspondingly trimer surfactants. The agents Suitable geminal surfactants are, for example, mixed sulfated hydroxyethers according to the patent application German DE 43 21 022 A1, or alcohol bis-sulfates dimer and tris-sulfates of alcohol ether sulfates trimer according to German patent application DE 195 03 061 A1. The mixed dimer and trimer ethers blocked in their terminal groups according to German patent application DE 195 13 391 distinguishes especially for its bi- and multifunctionality. In this way, the said surfactants blocked in their terminal groups they have good moisturizing properties, and in this case they are poor in foam, so that they are especially suitable for use in washing or machine cleaning procedures. But nevertheless, polyhydroxy fatty acid amides can also be used polyhydroxygrasic geminals or polyamides, as described in international patent applications WO-A-95/19953, WO-A-95/19954 and WO-A-95/19955.

To the most important components of the agents washing or cleaning belong in addition to the agents surfactants, first of all inorganic adjuvant substances and organic.

The zeolite used, finely crystalline, synthetic, and that contains bound water, is preferably the zeolite A and / or zeolite P. As zeolite P is used, so Example, zeolite MAP® (commercial product of the firm Crosfield). However, zeolite X is also appropriate, as well as mixtures of zeolites A, X and / or P. Zeolite can be used as spray dried powder, or as suspension not dried, still wet from obtaining, stabilized. In the case of use the zeolite as a suspension, it may contain additions reduced non-ionic surfactants as stabilizers, for example, from 1 to 3% by weight, based on the zeolite, of ethoxylated fatty alcohols with 12 to 18 atoms of carbon, with 2 to 5 ethylene oxide groups, fatty alcohols with 12 to 14 carbon atoms with 4 to 5 ethylene oxide groups, or ethoxylated isotridecanoles. The appropriate zeolites have a average particle size of less than 10 µm (distribution of volume; measurement method: Coulter Counter), and contain preferably 18 to 22% by weight, especially 20 to a 22% by weight of bound water.

The substitutes, or partial substitutes Suitable for phosphates and zeolites are alkali silicates crystalline, stratified, of the general formula NaMSi x O 2 x + 1 and H 2 O, meaning M sodium or hydrogen, being x a number from 1.9 to 4, e and a number from 0 to 20, and being preferred values for x 2, 3 or 4. Such silicates are described stratified, by way of example, in the request for European patent EP-A-0 164 514. The preferred crystalline layered silicates of the formula indicated are those in which M represents sodium, and x adopts values 2 or 3. Especially preferred are disilicates of β-, as well as δ-sodium Na_ {2} Si_ {2} O_ {5}. and H2O. To adjuvant substances Preferred also belong sodium silicates with a module Na 2 O: SiO 2 from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8, and especially from 1: 2 to 1: 2.6, which are delayed in dissolution, and have secondary washing properties. The delay of dissolution against conventional amorphous sodium silicates se can cause in this case in various ways, so Example by surface treatment, mixed, compacted / pressed, or by overdrying. In the scope of this invention is understood under the concept "amorphous" also "amorphous according to x-rays". That is, silicates do not provide crisp reflections of sharp x-rays, such as which are typical for crystalline substances, but in any case one or more maximums of diffracted X radiation, which have a width of several units of degree of diffraction angle in X-ray diffraction experiments. However, it can be reached easily even to especially good adjuvant properties if silicate particles provide maximum diffraction diffuse, or even sharp, in lightning diffraction experiments X. This should be interpreted so that the products present microcrystalline intervals of magnitude 10 up to a few hundred nm, with values up to a maximum of 50 nm being preferred, and especially up to a maximum of 20 nm. Such silicates called X-ray amorphous, which also have a delay of dissolution against conventional soluble glasses, it described, for example, in the patent application German DE 44 00 024 A1. Silicates are especially preferred pressed / compacted, compound amorphous silicates and silicates X-ray amorphous, over-dried.

Naturally, it is also possible to use the phosphates generally known as adjuvant substances, in so much such employment should not be avoided for ecological reasons. Especially appropriate are the sodium salts of orthophosphates, of pyrophosphates, and especially of tripolyphosphates. its content does not generally amount to more than 25% by weight, preferably not more than 20% by weight, referred respectively to the finished agent. In some cases it has been observed that, especially, tripolyphosphates lead to synergistic improvement of the secondary washing power already in small quantities, up to maximum 10% by weight, based on the finished agent, in combination  with other adjuvant substances.

The substitutes, or partial substitutes suitable for zeolite, they are stratified silicates of origin natural or synthetic Such stratified silicates are known, by way of example, by patent applications DE 23 34 899, EP 0 026 529 and DE 35 26 405. Their aptitude for employment is not limited to one composition, or special structural formula. Without However, smectites are preferred in this case, especially Bentonites Suitable stratified silicates, which belong to the group of smellates swellable with water, they are, so Example, Montmorillonite, Hectorite or Saponite. Additionally, in the crystalline lattice of silicates stratified according to the above formulas may be Small amounts of iron incorporated. In addition, silicates Stratified can contain hydrogen ions, alkaline, alkaline earths, especially Na + and Ca 2+, due to their ion exchange properties. The amount of water of hydration is almost always in the range of 8 to a 20% by weight, and is dependent on the swelling state, or on the type of elaboration Useful stratified silicates are known, for example, by US 3 966 publications 629, EP 0 026 529 and EP 0 028 432. Preferably used stratified silicates, which are substantially free of ions calcium due to an alkaline treatment, and which are iron ions strongly dyes.

Useful organic structuring substances they are, for example, polycarboxylic acids Usable in the form of its sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, acid tartaric acid, saccharic acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as it is not necessary to repair such use for ecological reasons, as well as mixtures thereof. Preferred salts are the salts of polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, saccharic acids and mixtures thereof. The acids themselves can also be used. Acids possess, in addition to their adjuvant action, typically also the property of an acidified component, and, by consequently, they also serve to adjust a more pH value Reduced and softer of washing or cleaning agents. In This case should be mentioned especially citric acid, acid succinic, glutaric acid, adipic acid, gluconic acid, and any mixture of these. These acids are preferably used if they are used in the premix according to the invention, and are not added subsequently. Other organic adjuvant substances Appropriate are dextrins, for example oligomers, or well carbohydrate polymers, which can be obtained by partial hydrolysis of starches. You can carry out the hydrolysis according to usual procedures, so Example by acidic or enzymatic catalysis. Preferably they are hydrolysis products with weights molecular molecules in the range of 400 to 500000. In this case it is preferably a polysaccharide with an equivalent of dextrose (DE) in the range of 0.5 to 40, especially 2 to 30, with DE being a usual measure for the reducing action of a polysaccharide in comparison with dextrose, which has a DE of 100. They are employable both maltodextrins with a DE between 3 and 20 and glucose syrups dry with a DE between 20 and 37, as well as the so-called yellow dextrins and white dextrins with molecular weights plus elevated, in the range of 2000 to 30000. A dextrin is described preferred in European patent application PE 0 703 292 A1. At  case of the oxidized derivatives of such dextrins is about their reaction products with oxidizing agents, which are suitable for oxidize at least one alcohol function of the saccharide ring to give the carboxylic acid function. Such oxidized dextrins are known, and procedures for obtaining it, for example by European patent applications EP 0 232 202, EP 0 427 349, EP 0 472 042 and EP 0 542 496, as well as patent applications WO 92/18542, WO 93/08251, WO 94/28030, WO 95/07303, WO  95/12619 and WO 95/20608. It can be especially advantageous a C6 oxidized product of saccharide ring. They are also suitable oxidized oligosaccharides according to the patent application German DE 196 00 018. Other suitable adjuvants are the oxidisuccinates and other succinate derivatives, preferably ethylenediamine disuccinate. In this context Glycerin disuccinates are also particularly preferred. and glycerin trisuccinates, as described, so For example, in US 4 US patent applications 524 009, US 4 639 325, in European patent application EP 0 150 930 and Japanese patent application JP 93/339896. The amounts appropriate employment are found in formulations containing zeolite and / or silicate, in 3 to 15% by weight. Other adjuvants Useful organics are, for example, acids acetylated hydroxycarboxylic acids, or their salts, which can be present, if necessary, also in the form of lactone, and that they contain at least 4 carbon atoms and at least one hydroxy group, as well as a maximum of two acid groups. Such are described adjuvants, for example, in the patent application International WO-A-95/20029. The Suitable polymeric polycarboxylates are exemplary, the sodium salts of polyacrylic acid or acid polymetacrylic, for example those with a weight molecular molecular from 800 to 150000 (referred to acid). The Suitable copolymer polycarboxylates are especially those Acrylic acid with methacrylic acid and acrylic acid or acid methacrylic with maleic acid. They have been shown especially suitable 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. Its relative molecular weight, referred to free acid, generally amounts to 5000 to 200000, preferably 10,000 to 120000, and especially 50,000 to 100,000. The content of the agents in polycarboxylates (co) polymers is in the usual range, and preferably amounts to 1 to 10% by weight. They are especially preferred too biodegradable polymers consisting of more than two units of different monomer, for example those that, according to DE 43 00 772, contain as monomers salts of acrylic acid and of methacrylic acid, as well as vinyl alcohol, or derivatives of vinyl alcohol, or, according to DE 42 21 381, contain as monomers salts of acrylic acid and acid 2-alkylsulfonic acid, as well as derivatives of sugars Other preferred copolymers are those that are described in German patent applications DE 43 03 320 and DE 44 17 734, and which preferably have acrolein monomers and acrylic acid / acrylic acid salts, or acrolein and acetate Vinyl Similarly, they should be cited as other substances preferred adjuvants polymeric aminodicarboxylic acids, its salts or its precursor substances. Are especially polyasparaginic acids, or their salts and derivatives, of which it is disclosed, in the patent application German DE 195 40 086, which also have an action bleaching stabilizer, in addition to adjuvant properties. Other suitable adjuvant substances are polyacetals, which are can be obtained by reacting dialdehydes with acids polyolcarboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP 0 280 223. Polyacetals Preferred are obtained from dialdehydes, such as glyoxal, glutaric aldehyde, terephthalic aldehyde, as well as mixtures thereof, and from polyolcarboxylic acids, such as acid gluconic and / or glucoheptonic acid.

Agents may additionally contain also components that positively influence elimination by washing oils and fats from textile materials. This effect is especially evident if a material gets dirty textile that was previously washed several times with an agent washing according to the invention, which contains these components oil and grease solvents. To the solvent components of Preferred oils and fats belong, by way of example, nonionic cellulose ethers, such as methylcellulose and methylhydroxypropylcellulose, with a fraction in methoxyl groups of 15 to 30% by weight, and in hydroxypropoxy groups of 1 to 1 15% by weight, referred respectively to non-cellulose ethers ionic as well as polymers of phthalic acid and / or acid Terephthalic known for the state of the art, or its derivatives, especially polymers of ethylene terephthalates and / or of polyethylene glycol terephthalates, or derivatives thereof modified by anionic and / or non-ionic route. Of these are Especially preferred are sulfonated derivatives of polymers of phthalic acid and terephthalic acid.

Other appropriate components of the agents are water-soluble inorganic salts, such as bicarbonates, carbonates, amorphous silicates, such as delayed dissolution silicates mentioned above, or mixtures thereof; especially it uses alkali carbonate and amorphous alkali silicate, especially sodium silicate with a Na 2 O: SiO 2 molar ratio of 1: 1 at 1: 4.5, preferably from 1: 2 to 1: 3.5. In this case, the content of the agents in sodium carbonate preferably amounts to 20% by weight, advantageously between 5 and 15% in weight. The content of the agents in sodium silicate is -if should not be used as an adjuvant substance - in general up to 10% by weight, and preferably is between 2 and 8% in weight, otherwise above. According to the teaching of the International patent application WO 94/01222 can be substituted alkaline carbonates also for sulfur-free amino acids, which they have 2 to 11 carbon atoms, and, if appropriate, another group carboxyl and / or amino, and / or its salts. In this case, in the field of this invention it is possible to make a partial substitution to complete with alkaline carbonates by glycine, or glycinate.

To the other components of the washing agents belong grating inhibitors, foam inhibitors, bleaching agents and bleaching activators, brighteners optics, enzymes, fabric softeners, colorants and odorizing products, as well as neutral salts, such as sulfates and chlorides, in the form of their sodium salts or potassium.

For the reduction of the pH value of the agents acid or salt salts can also be used for washing or cleaning slightly alkaline salts. In this case they are preferred as components of acidified bisulfates and / or bicarbonates, or acids organic polycarboxyls mentioned above, which can be simultaneously use also as adjuvant substances. Especially preferred is the use of citric acid, which is mixing well later (usual procedure mode), or It is well used in the solid pre-mix - in anhydrous form.

Among the compounds that serve as agents of bleaching, which provide H2O2 in water, has especially meaning sodium perborate tetrahydrate, and the sodium perborate monohydrate. Other useful bleaching agents are, by way of example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates, as well as peracid salts that provide H 2 O 2 or peracids, such as perbenzoates, peroxophthalates, diperacelaic acid, phthaloiminoperacid, or diperdodecanoic diacid. The content of the agents in bleaching agents amounts preferably at 5 to 25% by weight, and especially at 10 to 20% by weight, advantageously using perborate monohydrate or percarbonate.

Whitening activators can be used compounds that form aliphatic peroxocarboxylic acids under the perhydrolysis conditions with preferably 1 to 10 carbon atoms, especially with 2 to 4 carbon atoms and / or substituted perbenzoic acids. Are suitable substances bearing O- and / or N-acyl groups, with the number of carbon atoms cited and / or benzoyl groups if appropriate replaced. Polyacylated alkylenediamines are preferred, especially tetraacetylethylenediamine (TAED), derivatives triazine acylates, especially the 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially the tetraacetylglycoluryl (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), the acylated phenolsulfonates, especially the n-nonanoyl- or isononanoylbenzenesulfonate (n- o well iso-NOBS), the acid anhydrides carboxylic acids, especially phthalic acid anhydride, acylated polyvalent alcohols, especially triacetin, the ethylene glycol diacetate, the 2,5-diacetoxy-2,5-dihydrofuran and the enolésteres, known by the German requests DE 196 16 693 and DE 196 16 767 as well as acetylated sorbitol and mannitol or either their mixtures described in European patent application EP 0 525 239 (SORMAN), acylated saccharic derivatives, especially the pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetylactose as well as glucamine acetylated, if necessary N-rented and the gluconolactone, and / or N-acylated lactams, by example N-benzoylcaprolactam, which are known for international patent applications WO-A-94/27970, WO-A-94/28102, WO-A-94/28103, WO-A-95/00626, WO-A-95/14759 and WO-A-95/17498. Acylacetals hydrophilic substitutes, known by the patent application German DE 196 16 769 and acillactams, described in the application German patent DE 196 16 770 as well as in the patent application International WO 95/14075, will also be used in a manner preferential. You can also use the combinations of conventional bleach activators, known by the application German patent DE 44 43 177. Such bleaching activators they are contained in the usual quantitative range, preferably in amounts from 1% by weight to 10% by weight, especially from 2% by weight to 8% by weight, based on agent set.

In the case of employment in washing procedures by machine, it may be advantageous to add inhibitors of The usual foam. As foam inhibitors are suitable, by way of example, soaps of natural or synthetic origin, that have a high fraction of fatty acids with 18 to 24 carbon atoms Foam inhibitors type no suitable surfactants are, for example, organopolysiloxanes and their mixtures with microfine silicic acid, in given case silanized, as well as paraffins, waxes, waxes microcrystallines, and mixtures with silanized silicic acid or bisestearylethylene diamide. Mixtures are also advantageously used. consisting of various foam inhibitors, for example those made from silicones, paraffins, or waxes. Inhibitors of foam, especially foam inhibitors that contain silicone and / or paraffin, are preferably bound with a granulated, soluble, or dispersible support substance in water In this case, mixtures are especially preferred. constituted by paraffins and bisesteariletilendiamides.

As salts of polyphosphonic acids are used preferably the sodium salts, of neutral reactivity, of Example way of 1,1-diphosphonate 1-hydroxyethane, pentamethylene phosphonate diethylenetriamine or ethylenediamine tetramethylene phosphonate in amounts of 0.1 to 1.5% by weight.

Enzymes, preferably, are those of the classes of hydrolases, such as proteases, cutinases, cellulases or mixtures thereof. Oxirreductases are also suitable. Enzyme active products obtained from bacterial or fungal strains, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens, are particularly suitable. Preferably, subtilisin type proteases will be used, and especially proteases that are obtained from Bacillus lentus . In this case, enzymatic mixtures, for example constituted by proteases and amylases or by proteases and lipases or by proteases and cellulases or by cellulases and lipases, have a particular interest. Peroxidases or oxidases have also been found suitable in some cases. Suitable amylases belong, especially α-amylases, iso-amylases, polyulanases and pectinases. As cellulases, preferably, cellobiohydrolases, endoglucanases and β-glucoxidases, which are also called cellobiases, or mixtures thereof, will be used. Since cellulase types are differentiated by their CMCase and avicelase activities, the desired activities can be established by specific mixtures of cellulases. Enzymes may be absorbed onto support materials and / or embedded in coating substances for protection against premature decomposition. The proportion of enzymes, enzymatic mixtures or enzymatic granules may be, for example, from about 0.1 to 5% by weight, preferably from about 0.1 to 2% by weight.

In addition to the aforementioned phosphonates, the agents may also contain other stabilizers of enzymes For example, 0.5 to 1% can be used by weight of sodium formate. It is also possible to use proteases, which are stabilized with soluble calcium salts, and they have a calcium content, preferably, of approximately 1.2% by weight, based on the enzyme. In addition to Calcium salts, magnesium salts also serve as stabilizers However, employment is especially advantageous. of boron compounds, by way of boric acid, boron oxide, borax, and other alkali metal borates, such as salts of orthoboric acid (H 3 BO 3), of metabolic acid (HBO2), and pyroboric acid (tetraboric acid H 2 B 4 O 7).

Grating inhibitors are intended keep suspended dirt in the bathroom fibers and thus prevent the deposition of the dirt. In this case, water soluble colloids are suitable, the most of the time of an organic nature, for example salts Water soluble polymeric carboxylic acids, glues, jellies, salts of ether carboxylic acids or ethersulfonic acids of starches or cellulose or salts of acidic acid esters sulfuric acid from cellulose or starches. Are also suitable for this purpose polyamides containing soluble, acidic groups in water In addition, soluble starch preparations and other starch products different from those above indicated, for example degraded starches, aldehyde starches etc. Polyvinylpyrrolidone can also be used. However it they will preferably employ cellulose ethers such as the carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkylcellulose and mixed ethers, such as the methylhydroxyethylcellulose, methylhydroxypropylcellulose, methyl carboxymethyl cellulose and mixtures thereof, as well as the polyvinylpyrrolidone for example in amounts from 0.1 to 5% by weight, referred to the agent.

Agents may contain, such as brighteners optical, acid derivatives diamino-stilbendisulfonic acid or its salts with alkali metals. Suitable, for example, acid salts 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilben-2,2'-disulfonic  or similarly constituted compounds, bearing, instead from the morpholino group, a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. In addition, brighteners of the type of substituted diphenylstyrene, for example the alkaline salts of 4,4'-bis (2-sulfoestyryl) -diphenyl, of the 4,4'-bis (4-chloro-3-sulfoestyryl) -diphenyl, or of 4- (4-Chlorostyryl) -4 '- (2-sulfo-styryl) -diphenyl. Mixtures of the brighteners can also be used previously cited.

Examples Example 1

Agents E1 to E5 were manufactured as well as also the agents, which do not correspond to the invention, V1 and V2 (in relation to the composition see table 1) in the manner next:

It was prepared in a load mixer (mixer Lödige® 20 liter plow arm), which was equipped with a knife holder head shredder (crusher), a premix, constituted by the components indicated in table 1, taking carried out the addition of the nonionic surfactant in the stream of powder by spraying through nozzles. Then you homogenize the mixture for another 2 minutes, and then fed a twin screw extruder, whose granulator head it was preheated to temperatures between 50 and 65 ° C, preferably at 62 ° C. The premix was plasticized under the action shear spindles of the extruder and then the premix was plasticized and extruded, respectively, to the pressure indicated in table 1, through the perforated plate of the extruder head, to give fine bars with a diameter of 1.4 mm, which crumbled after the nozzle exit, by means of a detachment blade, to give granules approximately spherical (length / diameter ratio approximately 1, hot release). The granulate obtained, hot, spheronized for one minute in an apparatus for the commercial spheronized Marumerizer® type, and coated, if necessary, with a finely divided powder.

The bulk weight of extruded products, obtained, as well as their corresponding values in the solubility test (test L) described below, have been indicated in table 1.

It is seen that, when they are used of polymers swollen, anhydrous, according to the invention, WQP1 to WQP4, including when used in smaller quantities than a usual agent, plasticizing aid, high products are obtained quality with extrusion pressure clearly lower (at least one 30%)

For the determination of the behavior of residue, or the solubility behavior (test L) is dispersed in a 2 liter beaker, 8 g of agent a be analyzed under stirring (800 rpm with stirrer of laboratory / propeller head, centered at 1.5 cm distance from the bottom of the beaker), and stirred for 1.5 minutes at 30 ° C. The test was carried out with water from a hardness of 16º d. The washing bleach was then poured into through a sieve (80 µm). The beaker was washed with Very little cold water through the sieve. The sieves were dried in the dryer cabinet at 40 ° C ± 2 ° C until proof of weight, and weighed the washing agent residue. A double was carried out determination; the residue is given as a percentage as an average value of Both individual determinations. When they showed up deviations from individual results by more than 20% between yes, additional tests were usually carried out; without However, this was not necessary in the case of these trials.

For comparison purposes another V3 agent was prepared, which contained the same components, in the final product, as E2, but in which the copolymer had not been introduced in form swollen, anhydrous, but it was introduced into the procedure as aqueous solution approximately 30% by weight. Then you drying off excess water in a fluidized bed. He Bulk weight of extruded product V3 was 770 g / l, test L It resulted in a value of 28%.

Compositions of the spray-dried powders SP1 and SP2

Spray dried powder 1: 26.00% by weight of alkylbenzenesulfonates with 9 to 13 atoms of carbon, 8.50% by weight of carbonate sodium, 41.33% by weight of zeolite A, referred to the active substance anhydrous, 9.50% by weight of sodium salt acrylic acid copolymer and acid maleic, 1.00% by weight of phosphonate, 12.00% by weight of Water, 0.42% by weight of brightener optical, rest salts from solutions.

Spray dried powder 2: 26.00% by weight of alkylbenzenesulfonates with 9 to 13 atoms of carbon, 42.83% by weight of zeolite A, referred to the active substance anhydrate, 5.50% by weight of sodium salt of copolymer of acrylic acid and acid maleic, 1.00% by weight of phosphonate, 5.00% by weight carbonate of sodium, 6.00% by weight of sulfate sodium, 12.00% by weight of Water, 0.42% by weight of brightener optical, salt residues from solutions.

TABLE 1

one

to)

92% by weight of active substance, 3.70% sodium sulfate, 2.80% in weight of other salts from raw materials and parts not sulfated, 1.50% by weight of water.

b)

Composition 42.5% by weight of carbonate sodium, 2.5% by weight of sodium silicate modulus 3.3, 45% in weight of sodium sulfate, 10% by weight of water.

C)

Mix formed by 10% by weight of polyvinylpyrrolidone (Luviskol® K30, BASF manufacturer) and 90% by weight of glycerin.

d)

Mix formed by 10% by weight of acrylic acid / maleic acid copolymer, Na salt (Sokalan® CP5, manufacturer BASF) and 90% by weight of glycerin.

and)

Mix formed by 10% by weight of starch diphosphate and 90% by weight glycerin.

F)

Mix formed by 6% by weight of hydroxypolyalmidones and 94% by weight of ethylene glycol.

Example 2

They were arranged in a mixer with plow arm with shredder (manufacturer signature Lödige) the components indicated in table 2 (with the exception of swollen polymer anhydrous, WQP) with the temperature indicated in table 2 (temperature "rest") and mixed together, joining as the last component the non-ionic liquid surfactant for agglutination of powder. The swollen polymer, anhydrous, was then added, corresponding that presented the temperature indicated also in Table 2 (WQP temperature), after which the binder granulation of the material approximately after 2 minutes After another 8 minutes up to 10 minutes of mixture were obtained granules G1 to G11, indicated in the table 2, with bulk weights and solubilities equally there indicated (determination as in example 1) as well as with the grain size distribution indicated in table 3. It is especially worth considering all the components of the usual recipes for the agents of washing, including enzymatic granules, of the polymers for the release of dirt from regulators of foam and bleach activators (TAED) (G10 and G11).

TABLE 2

3

to)

Composition as in the example one.

b)

Mixture consisting of 4% by weight of hydroxypropyl starches and 96% by weight of ethylene glycol.

C)

Mix formed by 6% by weight of hydroxypropyl starches and 94% ethylene glycol as in the example one.

d)

Mix formed by 8% by weight of hydroxypropyl starches and 92% by weight of ethylene glycol.

and)

Mix formed by 10% by weight of hydroxypropyl starches and 90% ethylene glycol.

TABLE 3 Screening analysis and determination of grain size distribution

5

Example 3

For the manufacture of other washing agents granules G12 to G14 were worked as in example 2, using, however, instead of the mixer with plow arm,  an intensive mixer with inclined plate and a fluidizer (manufacturer Eirich signature) as a device for granulation.

TABLE 4

6

to)

Composition as in the example one.

b)

Addition in the elaboration.

C)

Composition as in the example 2.

TABLE 5 Screening analysis for termination of grain size distribution

8

Claims (15)

1. Procedure for the manufacture of washing or cleaning agents in the form of particles or components with various treated products or raw materials, which provide such agents in admixture with other components, with bulk weights above 600 g / liter, by combining mixtures and / or raw materials for washing or cleaning agents with simultaneous or subsequent molding, first a premix is manufactured, containing the individual raw materials and / or mixtures, which are presented as solid products to the ambient temperature and at a pressure of 1 bar, and then this premix is transformed into a grain under the action of compaction forces as well as, if necessary, the processing is continued or elaborated, characterized in that the premix is essentially free of water and an auxiliary agent is used for liquid molding under the conditions for molding, especially even at room temperature. at a pressure of 1 bar, in the form of a non-aqueous solution of a swollen polymer, the non-aqueous liquid components being chosen as the auxiliary agent for molding between monovalent, divalent or trivalent alcohols, liquid at room temperature, with a dot melting (at 1 bar) above 80 ° C among the following: n-propanol, iso-propanol, n-butanol, s-butanol, iso-butanol, ethylene glycol, 1,2- or 1,3-propylene glycol, glycerin, di- or triethylene- or -propylene glycol or mixtures thereof. 2. Method according to claim 1, characterized in that the swollen polymer, anhydrous, is a system consisting of a non-aqueous liquid and the polymer, which has at least 20 times higher viscosity at room temperature, in the presence of the polymer, especially 300 to 500 times greater than that of non-aqueous liquid alone. Method according to claims 1 or 2, characterized in that the viscosity of the auxiliary agent for molding at room temperature is in the range from 200 mPas to 10,000 mPas, especially from 400 mPas to 6,000 mPas. 4. Method according to claim 3, wherein the viscosity at 60 the auxiliary agent for molding is in the range from 250 mPas to 2,500 mPas. 5. Process according to one of claims 1 to 4, characterized in that the nonaqueous liquid component of the auxiliary agent for molding is selected from monovalentess, divalent or trivalent alcohols, liquid at room temperature with melting points (at 1 bar) above 120 ° C. 6. Method according to one of claims 1 to 5, characterized in that the polymer, which leads the swollen system into an swollen liquid, is chosen from polyvinylpyrrolidone, polyacrylic acid, copolymers formed by acrylic acid and maleic acid, polyvinyl alcohol, xanthan, partially hydrolyzed starches, alginates, mylopectin, starches bearing methyl ether, hydroxyethyl ether, hydroxypropyl ether and / or hydroxybutyl ether or cellulose groups, phosphate starches, such as starch diphosphate and inorganic polymers such as stratified silicates as well as mixtures thereof. Method according to one of claims 1 to 6, characterized in that in the auxiliary agent for molding the concentration of the polymer in the anhydrous liquid amounts from 5% by weight to 20% by weight, especially from 6% by weight. Up to 12% by weight. Method according to one of the claims 1 to 7, characterized in that the content in the auxiliary agent for molding, referring to the compacted premix, is from 2% by weight to less than 20% by weight, especially from 3 % by weight up to 10% by weight. Method according to one of claims 1 to 8, characterized in that an auxiliary agent is used for molding that dissolves at least almost completely at a concentration of 8 g in 1 liter of water at 30 ° C, within 90 seconds. . Method according to one of claims 1 to 9, characterized in that the premix has, in total, a water content of not more than 15% by weight, this water being presented in a non-free form and preferably the water content not bound with the zeolite and / or with the silicates does not represent more than 10% by weight and, especially, it supposes less than 7% by weight. Method according to one of claims 1 to 10, characterized in that the compacting molding is carried out with the aid of an agglomeration stage, the premix being granulated by agglomeration in a suitable device for this purpose and the auxiliary agent for molding, in form of the swollen, anhydrous polymer, plays the role of a binding agent. 12. Method according to claim 11, characterized in that the solid components of the premix are arranged, to be compacted, in a granulator, and a mixer can also be used as such, if necessary the powder presently binds by adding a surfactant Non-ionic liquid and the auxiliary agent for molding is incorporated into the granulator. 13. Method according to claims 11 or 12, characterized in that the agglomeration process is carried out with machine and working parameters as well as with a type and quantity of the auxiliary agent for molding in the form of the anhydrous swollen polymer of such so that granulate grains with at least approximately spherical geometric shape (pearl shape) are produced. 14. Method according to one of claims 1 to 10, characterized in that the molding is carried out by extrusion, the premix being compacted under pressure, plasticized, extruded in the form of a thin bar through the perforated nozzle plates in the extruder head and, finally, crumbles by means of a rotating detachment blade, preferably to give approximately spherical grains (pearl shape) to cylindrical. 15. Method according to one of claims 1 to 14, characterized in that a premix with a relatively wide grain size distribution and relatively high proportions of fine grain is transformed into a final product with a distribution.