DE19638599A1 - Process for producing a particulate detergent or cleaning agent - Google Patents

Abstract

The invention aims at providing particulate washing or cleaning agents, compounds or raw materials with apparent densities above 600 g/l for the latter which even with a reduced surface, in particular with a spherical shape disintegrate better when they are dissolved in an aqueous bath. Moreover, the particulate washing or cleaning agents, compounds or treated raw materials should be produced by joining washing or cleaning agent compounds and/or raw materials, at the same time as or after they are shaped. For that purpose, at first an essentially anhydrous premixture is produced, containing individual raw materials and/or compounds which are solid under standard conditions and have a melting or softening point not below 45 DEG C, as well as up to 10 wt % optional non-ionic surfactants which are liquid at temperatures below 45 DEG C and under 1 bar pressure. The mixture is granulated by applying compacting forces at temperatures of at least 45 DEG C, then further processed or conditioned; the premixture contains at least one raw material or compound which is solid under 1 bar pressure and at temperatures below 45 DEG C, but which melts under processing conditions, forming a molten mass which acts as a polyfunctional, water-soluble binder which serves as a lubricant during the production of the washing and cleaning agent and as an adhésive for the solid washing or cleaning agent compounds or raw materials, but which has a disintegrating effect when the washing or cleaning agent is dissolved again in an aqueous bath.

Description

The invention relates to a method for producing quick-soluble, compressed part Chen-shaped washing or cleaning agents or compounds or treated raw material fen for this as well as detergents or compounds or compounds produced in this way or treated raw materials for this, which from the point of view of the consumer a significantly better have quality.

Particulate detergents or cleaning agents with bulk weights above 600 g / l have been state of the art for quite some time. In the past few years went with the Increasing the bulk density also increases the concentration of active washing and cleaning Ingredients, so that the consumer not only less volume, but also we had to dose less mass per washing or cleaning process. The increase in Bulk density and in particular the higher concentration of the agents washing or cleaning-active substances was generally bought out by a from the point of view of the consumer subjectively poorer solubility, since slower solving speed of the agent used. This unwanted release delay is under other triggered by the fact that a number of practical anionic and nonionic Surfactants and above all corresponding surfactant mixtures when dissolved in water Formation of gel phases tend. Such gelling can already be done with tenside ten of 10 wt .-%, based on the total agent, that is in washing or Detergent usual amounts of surfactants occur. The tendency to form gels Experience has shown that the part also takes part with the increasingly compact grain structure go to.

EP-B-0 486 592 describes granular or extruded washing or cleaning agents detergent with bulk weights above 600 g / l, the anionic and / or nonionic Contain surfactants in amounts of at least 15 wt .-% and up to about 35 wt .-%. she are produced using a process in which a solid, free-flowing premix, which is a plasticizer and / or lubricant from preferably aqueous surfactant pastes and / or aqueous polymer solutions at high pressures between 25 and 200 bar strand-pressed and the strand after exiting the hole shape by means of a cutting device is cut to the predetermined granule size and rounded.  

The premix consists at least in part of solid ingredients which are added if necessary, liquid ingredients such as nonionic surfactants that are liquid at room temperature are mixed. As said above, plasticizers and / or lubricants are preferred in Embodiments of aqueous preparations used. However, there are also ver equally high-boiling organic liquids, if necessary again in Ab mix with water, in question. However, the patent does not disclose any procedures to be followed conditions for the case of an anhydrous extrusion. The extrudates produced can either already be used as a detergent or cleaning agent or subsequently Lich with other granules or powder components to finished washing or cleaning be prepared. Due to the high compactness of the grain and the relative high surfactant content, but also through the ball or per desired by the consumer lenform, which has a significantly smaller surface area than conventional granules may have, depending on the surfactant combinations selected difficulties mentioned above.

From international patent application WO-A-93/15180 it is known that the Lösege speed of such extruded means can be improved in that in the solid premix short-chain alkyl sulfates, especially C₈ to a maximum of C₁₆ alkyl sulfates are used, which are introduced into the premix in a certain way will. However, this measure is not sufficient in all cases to speed up the release of the entire agent to the desired extent.

The German patent application DE 195 19 139.0 proposes to solve the conflict between The high degree of compaction of the individual grain, in particular the extrudate, on the on the one hand and the rapid and in particular non-retaliation required The detergents or detergents can be redissolved in aqueous liquors, particulate detergents or cleaning agents with a bulk density above 600 g / l, which anionic and / or nonionic surfactants in amounts of at least 15% by weight included to design such that at least two different granular components are used, of which at least one is extruded and at least one is not ex is trudged, the surfactant content of the extruded component including the soaps a maximum of 15 wt .-%, based on the respective extruded component. Wei tere surfactant components of the finished detergent or cleaning agent are by or several non-extruded component (s) introduced into the agent. This procedure solves although the problem of gelling highly compressed and high-surfactant washing or Detergent when used in an aqueous liquor, but also includes a number of new problems. There can be segregation processes and accordingly  Fluctuations in the reproducibility of the desired washer or cleaner result. In addition, the extruded portion of the funds is not only of a high level Density, the dried extrudates are also comparatively hard. Among the Conditions of transportation, storage and use can be the comparatively softer Granulate portion thus be exposed to mechanical forces that are proportional to its Reduction and thus the formation of dust and fine particles through abrasion.

Conventional methods generally work with both fixed and room systems temperature liquid ingredients of washing or cleaning agents; also aqueous solutions gene and / or dispersions are used as granulation aids or as in the case of EP-B 0 486 592 widely used as plasticizers and / or lubricants. Such ver Driving styles have the risk that during the manufacture of the washing or Detergent gel-like structures are created, which lead to a loosening of the detachment dissolve in the aqueous liquor. In addition, the processes in which water, aqueous solutions or aqueous dispersions as a granulating aid be set, the disadvantage that in most cases an energetically unfavorable Drying must be added to a free-flowing or storage-stable end product to get, and also crushed the often very rough agglomerates obtained and / or must be sieved (see also "Size Enlargement by Agglomeration", W. Pietsch, John Wiley & Sons, 1990, page 180). Another disadvantage of these methods is in that it dissolves solid and water-soluble constituents, especially un ter the pressure influence during the extrusion to particle enlargement and to crystallization tion can come, which in turn adversely affects the dissolution behavior impact on finished funds.

A method for the production of heavy granules with the help of an aqueous Granulation aid is the two-stage granulation, whereby initially in a übli Chen mixer / granulator still plastic primary agglomerates are generated, which closing in apparatus such as a rounder, rotocoater, marumerizer etc. with liquid Binder and / or dust subsequently treated and usually then ge be dried. The granulation and simultaneous rounding can, for example, in Wir Fluid bed granulators, which contain a rotating disk, are carried out. Solid starting materials are first fluidized in the fluidized bed and then with liquid binder, which is inserted into the fluidized bed via tangentially aligned nozzles is given, agglomerated ("Size Enlargement by Agglomeration", W. Pietsch, John Wiley & Sons, 1990, pages 450 to 451). In principle, this method can also be used for non-aqueous  Other processes are used (melt coating process), but then the advantage the apparatus to be able to effect simultaneous drying is not used.

In the specialist literature ("Size Enlargement by Agglomeration", W. Pietsch, John Wiley & Sons, 1990, pages 440 to 441) are only two methods for granulation under high pressure known which can be carried out completely water-free. These are for tableting in tablet presses and for roller compaction, the last mentioned methods are usually generated Schülpen, which subsequently to granules broken, but irregularly shaped products. For this reason, who the so-called Prebreaker used in some systems to already the initial pro is more uniform in shape for the actual granulation or grinding step shape. Subsequently, undesirable fine and / or coarse-grained fractions can be obtained provided granules are sieved and optionally recycled.

International patent application WO-A-93/02176 describes a process for the production solid detergents or cleaning agents with high bulk densities by combining add solid and liquid detergent or cleaning agent raw materials at the same time or subsequent shaping, with anionic surfactants, for example, as solid constituents and builder substances and nonionic surfactants are used as liquid constituents, wherein the latter in an intimate mixture with a structure breaker such as polyethylene glycol or Polypropylene glycol or ethoxylated C₈-C₁₈ fatty alcohols with 20 to 45 EO provided were. The liquid nonionic surfactants are ethoxylated linear or in the 2-position methyl branched alcohols preferred which have 8 to 20 carbon atoms in the carbon chain and have an average of 1 to 15 moles of ethylene oxide per mole of alcohol. Besides the above Structural breakers mentioned is also water in principle as a suitable structure breaker described, but its use is less preferred because the funds during the situation depletion of water due to the internal drying of the agents and thus the desired effect of the improved dissolving speed by using a structure br would no longer or no longer be fully effective. According to the teaching In this international patent application, the mixtures of nonionic surfactants and structure turbrechern, which are available either as a solution or as a dispersion, in all known Granulation processes are used in which separately produced compounds and / or Raw materials are used. Use in an extrusion process according to the international patent application WO-A-91/02047 (or European patent EP-B-0 486 592) is possible and even preferred. Accordingly, the use of aqueous solutions, pastes or aqueous dispersions suggested, the water as mentioned above is not used as a structure breaker and usually after  the extrusion is dried away. An extrusion without the addition of water will not be ex explicitly suggested; even in the example section, in addition to and separately from the nonionic surfactant Structure breaker mixture the addition of aqueous solutions; but above all calls this Document also no process conditions under which an anhydrous extrusion can be carried out.

European patent application EP-A-0 337 330 describes a method for increasing the bulk density of a spray-dried detergent by granulation in one Mixer with the addition of non-ionic compounds. These include ethoxylated and / or propoxylated nonionic surfactants such as primary or secondary alcohols with 8 to 20 carbon atoms and 2 to 20 moles of alkylene oxide per mole of alcohol, in particular non-ionic surfactants with 2 to 6 EO and HLB values of 11 or less in the mixer be set. Ethylene glycols and propylene glycols can also be used as non-ionic compounds applications are used.

European patent application EP-A-0 711 828 describes a method for the production described by tablets, wherein a coated particulate product is pressed. The Enveloping substance is a water-soluble binder or disintegrant with enamel temperatures between 35 and 90 ° C. However, an essential feature is given here ben that the compacting / tableting should be carried out at temperatures that at least at 28 ° C, but in any case below the melting temperature of the bindemite lying.

From the international patent application WO-A-96/10071 is a process for the production of granules with bulk densities of at least 650 g / l and surfactant contents of min at least 40 wt .-% known, the granulation process in one step in a Mi with a high shear rate at temperatures between room temperature and 60 ° C to be led. Particles with a particle size between 0.1 serve as solid feedstocks and 500 µm, with at least 15% by weight of the particles having a particle size above Should have 50 microns, but there are enough small, fine particles so that a particularly high surface area of the solid feed material results. Serve as a binder Surfactant mixtures of anionic surfactants and nonionic surfactants in weight ratios from 2: 8 to 8: 2, which can have up to 20% by weight of water. As non-ionic surfactants primary C₁₂-C₁₅ alcohols are given with 3 to 7 EO. Are particularly advantageous in Within the specified process, surfactant mixtures which contain up to 20% by weight Water included, as this increases the viscosity of the mixture and the process better becomes trollable. In addition, the surfactant mixture can also contain polyethylene glycols.  

The production of Builderag is described in US Pat. No. 5,108,646 described glomerates, 50 to 75 parts by weight of aluminosilicates or crystalline Layer silicates are agglomerated with 20 to 35 parts by weight of a binder. Appropriate Most of the binders are highly viscous anionic surfactant pastes, which are between 0 and 90 Wt .-% water can contain. But also polymers like polyethylene glycols with molecules Lar weights between 1000 and 20000 come into consideration, as well as mixtures this and usual nonionic surfactants such as C₉-C₁₆ alcohols with 4 to 8 EO, as long as the melting range does not begin below 35 ° C or below 45 ° C. The agglomeration takes place in a so-called intensive mixer with a very specific, relatively high energy entry instead. An over-agglomeration occurs at energy inputs above the specified values ration to a dough-like mass, with lower energy inputs only finely divided powders or very light agglomerates with an undesirably wide grain spectrum received.

In contrast, the object of the invention was particulate washing or To produce cleaning agents or compounds or treated raw materials for this, which even with a reduced surface, especially with a spherical shape (pearl shape) a ver have better disintegration in the dissolution in the aqueous liquor. Furthermore the process should be economically favorable and costly drying steps ver can do without.

The invention is therefore a Ver in a first embodiment of the invention drive to the production of particulate detergents or cleaning agents or Com pounds or treated raw materials for this with bulk weights above 600 g / l Joining detergent or cleaning agent compounds and / or raw materials together simultaneous or subsequent shaping, initially with a premix represents which individual raw materials and / or compounds that are at room temperature and one Pressure of 1 bar as a solid and a melting point or softening point not below 45 ° C, and optionally up to 10 wt .-% at temperatures contains liquid nonionic surfactants below 45 ° C and a pressure of 1 bar, and under Use of compaction forces at temperatures of at least 45 ° C in a grain leads and, if necessary, subsequently processed or prepared. Here apply the stipulations that

• - The premix is essentially anhydrous and
• - In the premix, at least one raw material or compound that or a pressure of 1 bar and temperatures below 45 ° C in solid form  is present, but is present as a melt under the processing conditions, whereby this melt serves as a polyfunctional, water-soluble binder, which in the preparation of the agents both the function of a lubricant and an adhesive function for the solid detergent or cleaning agent compounds exercises or raw materials when redissolving the agent in an aqueous liquor however, has a disintegrating effect.

In the context of this invention, a condition is "substantially water-free" understand where the content of liquid, i.e. H. not in the form of water of hydration and / or Constitutional water below 2% by weight, preferably below 1% by weight and in particular even less than 0.5% by weight, based in each case on the premix. Accordingly, water can essentially only be chemically and / or physically bound form or as part of the at temperatures below 45 ° C at a Pressure of 1 bar as raw materials or compounds, but not as rivers liquid, solution or dispersion in the process for the preparation of the premix be brought. The premix advantageously has a total water content of not more than 15% by weight, so this water is not in liquid form but chemically and / or physically bound, i.e. not in free form, and it it is particularly preferred that the content of not zeolite and / or silicates bound water in the solid premix not more than 10% by weight, preferably is less than 7% by weight and, with particular preference, a maximum of 2 to 5% by weight.

Particulate detergents or cleaning agents are used in the context of the invention preferably understood those that have no dust-like components and in particular none Have particle sizes below 200 microns. Such particles are in particular size distributions preferred, which at least 90 wt .-% of particles with a Have a diameter of at least 400 µm. In a particularly preferred embodiment Form of the invention, the detergents or cleaning agents, Com pounds or treated raw materials to at least 70 wt .-%, advantageously to min at least 80% by weight and, with particular preference, up to 100% by weight spherical (pearl-shaped) particles with a particle size distribution which min at least 80 wt .-% particles between 0.8 and 2.0 mm.

Detergents or cleaning agents are understood to mean compositions of this type which Washing or cleaning can be used without usually further In Ingredients must be added. A compound, however, consists of at least 2 Components usually used in washing or cleaning agents; Compounds  but are usually only mixed with other ingredients, preferably used together with other compounds. A treated raw material is the This invention is a relatively finely divided raw material, which by the inventive method in a coarser particle has been transferred. Strictly speaking, a treated raw material is in the Within the scope of the invention, a compound if the treatment agent is usually in Detergent or cleaning agent used ingredient.

The ingredients used in the process according to the invention can - with Aus took the possibly existing at temperatures below 45 ° C and a Pressure of 1 bar liquid non-ionic surfactants - separately manufactured compounds, however also be raw materials, which are powdery or particulate (fine to coarse), in any case but in solid form at room temperature and a pressure of 1 bar. As partiku Lary particles can, for example, be beads produced by spray drying (Fluidized bed) granules etc. are used. The composition of the compounds in itself is immaterial to the invention with the exception of the water content, which is so must be such that the premix is essentially anhydrous as defined above and preferably not more than 10% by weight of water of hydration and / or constitution it contains. It is also possible that solid compounds are used in the premix those that are used as carriers of liquids, for example liquid nonionic surfactants or Silicone oil and / or paraffins. These compounds can add water to the above given framework, the compounds are free-flowing and even at higher Temperatures of at least 45 ° C remain free-flowing or at least conveyable. In particular but it is particularly preferred that compounds with a maximum of 10% by weight and with particular preference with a maximum of 7 wt .-% water, based on the pre mixed, can be used. Free water, that is water that is not in any form a solid is bound and is therefore "in liquid form" is preferably done not included in the premix, since very small amounts, e.g. around 0.2 or 0.5% by weight, based on the premix, is sufficient to obtain the water-soluble bin to be resolved. This would have the consequence that the melting point or softening point reduced and the end product ver both in terms of flowability and bulk density would corrode.

Surprisingly, it has been shown that it is by no means indifferent on which solid raw material or in which solid compound the water is bound. That's how it is Water attached to builder substances such as zeolite or silicates (description of the substances see below), especially if the water on zeolite A, zeolite P or MAP and / or Zeolite X is considered less critical. On the other hand, it is preferred that  Water, which has other solid components than the builder substances mentioned is bound, preferably contained in amounts of less than 3% by weight in the premix is. In one embodiment of the invention, it is therefore preferred that the content of ge bound water in the premix is not more than 10% by weight and / or the content less than 7% by weight of water not bound to zeolite and / or silicates and is in particular a maximum of 2 to 5% by weight. It is particularly advantageous if that Premix contains no water at all, which is not bound to the builder substances. This is technically difficult to realize, however, because of the raw materials and Compounds at least always traces of water are brought in.

The content of the solid compounds used in the premix at at temperatures below half-45 ° C non-aqueous liquids is preferably also or additionally to 10% by weight, advantageously up to 6% by weight, again based on the premix. In particular, solid compounds are used in the premix, which are customary for Temperatures below 45 ° C and a pressure of 1 bar liquid non-ionic ten contain side, according to all known types of production - for example by spray Drying, granulation or spraying of carrier beads - were made separately. On in this way, premixes can be prepared, for example up to about 10 % By weight, preferably below, in particular up to a maximum of 8% by weight and for example between 1 and 5% by weight of nonionic surfactants, based on the finished agent to let.

Compounds that contain water in the form specified above and / or as a carrier for liquids, especially for nonionic surfactants that are liquid at room temperature NEN, ie they contain liquid ingredients at room temperature and according to the invention can in any case have a softening point below 45 ° C on. The separately used raw materials also have a melting point of we at least 45 ° C. The melting point or the softening point of all is preferably Individual raw materials and compounds used in the premix above 45 ° C and above partially at at least 50 ° C.

In a preferred embodiment of the invention, at least 80% by weight, in particular in particular at least 85% by weight and with particular preference at least 90% by weight of the compounds and individual raw materials used in the premix is much higher Softening point or melting point than reached under the process conditions will. In practice, the process temperatures become economical Reasons not above 150 ° C, preferably not above 120 ° C. Consequently  at least 80% by weight of the compounds and individual raw materials used Have softening point or melting point above 150 ° C. Usually lies the softening point or melting point even far above this temperature. If Ingredients are used that decompose under the influence of temperature, for example Peroxy bleaching agents such as perborate or percarbonate, the decomposition temperature is Ingredients at a pressure of 1 bar and especially at higher pressures, which in the extrusion processes according to the invention and preferred are also available edge above 45 ° C.

In addition to the solid constituents, the premix can add up to 10% by weight Temperatures below 45 ° C and a pressure of 1 bar liquid non-ionic, ten side, especially the alk. commonly used in washing or cleaning agents oxylated alcohols, such as fatty alcohols or oxo alcohols with a carbon chain length between 8 and 20 and especially an average of 3 to 7 ethylene oxide units per mole of alcohol (see below for a more detailed description). The addition of the liquid non-ionic surfactants can be done in amounts that still ensure that the premix is pourable Form is present. If such liquid nonionic surfactants are introduced into the premix, then so it is preferred that liquid nonionic surfactants and the disintegrating binder can be introduced separately into the process. In a preferred embodiment Rungsform the invention, the liquid nonionic surfactants in a continuous product tion process applied in particular by means of nozzles to the powder stream and from last rem sucked up.

However, the premix also contains at least one raw material or at least one com pound, which or which serves as a binder, is solid at room temperature, while rend compression under the process conditions but liquid in the form of a Melt is present. The binder itself can be melted onto the premix once be sprayed on or added dropwise to the premix, but on the other hand it also has proven to be advantageous to incorporate the binder in solid form as a powder in the premix bring. The melting point or softening point is at a pressure of 1 bar at least 45 ° C and (especially for economic reasons) preferably below of 200 ° C, especially below 150 ° C. If the binder is in the form of a melt introduced the premix, the temperature in the melting vessel is also more than 45 ° C to a maximum of about 200 ° C, the temperature in the melting vessel Melting temperature or the temperature of the softening point of the binder or Binder mixture can exceed significantly.  

The type of suitable binder and the temperature in the compression step tion are interdependent. Since it has proven to be advantageous if the bandage medium in the process step of compression as homogeneous as possible in that the well distributed, temperatures must be in the compression step conditions in which the binder at least softens, but preferably completely and not is only partially in molten form. So becomes a binder with high Melting point or high softening point must be selected in the process step the compression a temperature can be set, which the melting of the bin ensures. In addition, depending on the desired combination of the end product, temperature-sensitive raw materials should also be processed can. Here the upper temperature limit is determined by the decomposition temperature of the sensi tive raw material given, it is preferred to be significantly below the decomposition working temperature of this raw material. However, the lower limit is for the Melting point or softening point is of such great importance, because at Melting points or softening points below 45 ° C usually an end pro product is obtained, even at room temperature and slightly elevated temperatures by 30 ° C, i.e. at summer temperatures and under storage or transport conditions to Sticking tends. It has proven to be particularly advantageous if a few degrees, for example 2 to 20 ° C, above the melting point or above the softening point point is being worked on.

Without wishing to be limited to this theory, the applicant is of the opinion that due to the homogeneous distribution of the binder within the premix Process conditions of compression of the solid compounds and, if necessary existing individual raw materials are thus enclosed by the binder and then are glued together that the finished end products almost exactly from the many small individual particles that are built up by the binder that the Task of a preferably thin partition between these individual particles takes, are held together. In the idealized form it can be of a honeycomb Similar structure can be assumed, these honeycombs with solids (compounds or individual raw materials) are filled. In contact with water, also with cold water, so for example at the beginning of a machine wash, loosen or disintegrate these thin partitions almost instantaneously; Surprisingly, this is also the case the case when the binder itself at room temperature, for example due to a Crystal structure, is not quickly soluble in water. However, such are preferred Binder used, which is in a test procedure as described below in a  Concentration of 8 g binder in 1 l water at 30 ° C within 90 seconds na have it completely detached.

The binder or binders must therefore be of the type that the adhesive properties even at temperatures significantly above the melting point or the exp point, are still preserved. On the other hand, it is also essential for that Choice of the type and amount of the binder (s) used, that the bin the properties after re-cooling within the end product cohesion, the cohesion of the end product is assured, but that the end pro product itself not glued under normal storage and transport conditions.

In the further course of the description of this invention, for the sake of simplicity, only of one or the binder. However, it should be made clear that at there is always the use of several different binders and mixtures from different binders is possible.

In a preferred embodiment of the invention, a binder is used that at temperatures up to a maximum of 130 ° C, preferably up to a maximum of 100 ° C and in particular up to 90 ° C is already completely in the form of a melt. The binder must therefore, depending on Ver drive and process conditions are selected or the process conditions, in particular the process temperature, if a certain binder is required is desired - to be adapted to the binder.

Preferred binders used alone or in a mixture with other binders can be, are polyethylene glycols, 1,2-polypropylene glycols and modified poly ethylene glycols and polypropylene glycols. The modified polyalkylene glycols include in particular the sulfates and / or the disulfates of polyethylene glycols or polypropy lenglycols with a molecular weight between 600 and 12000 and in particular between 1000 and 4000. Another group consists of mono- and / or disuccinates the polyalkylene glycols, which in turn have molecular weights between 600 and 6000, preferably have between 1000 and 4000. For a more detailed description of the modified polyalkylene glycol ether is based on the disclosure of the international Pa tent registration WO-A-93/02176 referenced. For the purposes of this invention, poly ethylene glycols such polymers, in the production of which, in addition to ethylene glycol, also C₃-C₅- Glycols and glycerin and mixtures of these can be used as starting molecules. Also included are ethoxylated derivatives such as trimethylol propane with 5 to 30 EO.  

The preferred polyethylene glycols can be linear or branched Have structure, with linear polyethylene glycols being preferred in particular.

The particularly preferred polyethylene glycols include those with relative moles cooling masses between 2000 and 12000, advantageously around 4000, polyethylene-gly kole with relative molecular weights below 3500 and above 5000 especially in Combination with polyethylene glycols with a relative molecular mass around 4000 used and such combinations advantageously to more than 50 wt .-%, based on the total amount of polyethylene glycols, polyethylene glycols with a rela tive molecular weight between 3500 and 5000. However, as a binder also polyethylene glycols are used, which per se at room temperature and a Pressure of 1 bar in liquid state; here is mainly from polyethylene glycol a relative molecular mass of 200, 400 and 600. However, these should be on liquid polyethylene glycols only in a mixture with at least one other Binders are used, this mixture again the inventive requirements must meet, i.e. a melting point or softening point of at least must be above 45 ° C.

Low molecular weight polyvinylpyrrolidones and derivatives of are also suitable as binders these with relative molecular masses up to a maximum of 30,000. Relative Mo are preferred here ranges between 3000 and 30,000, for example around 10,000. Polyvinylpyrroli are preferably not done as sole binders, but in combination with others ren, especially in combination with polyethylene glycols.

Raw materials have proven to be suitable further binders, which raw materials are washable. or have cleaning-active properties, for example nonionic surfactants with melting points of at least 45 ° C or mixtures of non-ionic surfactants and other binders. Preferred nonionic surfactants include alkoxy gelled fatty or oxo alcohols, especially C₁₂-C₁₈ alcohols. Alkoxylie degrees, in particular degrees of ethoxylation of on average 18 to 80 AO, in particular special EO per mole of alcohol and mixtures of these proved to be particularly advantageous sen. Especially fatty alcohols with an average of 18 to 35 EO, especially with through on average 20 to 25 EO, show advantageous binder properties in the sense of the present Invention. Optionally, ethoxylated alcohols can also be used in binder mixtures less EO units per mole of alcohol, for example Tallow fatty alcohol with 14 EO. However, it is preferred to use this relatively low ethoxylated Al only use alcohols in a mixture with higher ethoxylated alcohols. Advantageously  the content of these relatively low ethoxylated alcohols in the binders is less than 50% by weight, in particular less than 40% by weight, based on the total amount binder used. Mainly usually used in washing or cleaning agents set nonionic surfactants such as C₁₂-C₁₈ alcohols with an average of 3 to 7 EO, which are liquid per se at room temperature, are preferably in the binder only available in the amounts that less than 2% by weight of this does not ionic surfactants, based on the process end product, are provided. How be Already described above, however, it is less preferred in the binder mixtures use liquid non-ionic surfactants at room temperature. In a particularly advantageous way In this embodiment, such nonionic surfactants are not part of the bin detergent mixture, as these not only lower the softening point of the mixture, but can also contribute to the stickiness of the end product and also by their Tendency to gelation on contact with water, also the requirement of rapid dissolution of the binder / partition in the end product is not as desired Scope is sufficient. Likewise, it is not preferred that the usual in washing or cleaning anionic surfactants or their precursors, the anionic surfactant acids, used in the bin are included.

Other non-ionic surfactants that are suitable as binders do not pose a problem pulmonary fatty acid methyl ester ethoxylates, especially those with average 10 to 25 EO (see below for a more detailed description of this group of substances). Especially be preferred representatives of this group of substances are predominantly based on C₁₆-C₁₈ fatty acids Methyl ester, for example hardened beef tallow methyl ester with an average of 12 EO or with an average of 20 EO.

In a preferred embodiment of the invention, a mixture is used as the binder used which C₁₂-C₁₈ fatty alcohol based on coconut or tallow with an average of 20 EO and polyethylene glycol with a relative molecular weight of 400 to 4000 are used.

In a further preferred embodiment of the invention, a Mi Schung used, which is based predominantly on C₁₆-C₁ Fetts fatty acids with methyl esters on average 10 to 25 EO, especially hardened beef tallow methyl ester with through an average of 12 EO or an average of 20 EO, and a C₁₂-C₁₈ fatty alcohol based Coconut or tallow with an average of 20 EO and / or polyethylene glycol with a relative Contains molecular mass from 400 to 4000.  

Binders have proven to be particularly advantageous embodiments of the invention sen, either alone on polyethylene glycols with a molecular weight around 4000 or with a mixture of C₁₂-C₁₈ fatty alcohol based on coconut or tallow on average 20 EO and one of the fatty acid methyl ester ethoxylates described above or on a mixture of C₁₂-C₁₈ fatty alcohol based on coconut or tallow with average 20 EO, one of the fatty acid methyl ester ethoxylates described above and a polyethylene lenglycol, in particular with a molecular weight of around 4000.

Other raw materials such as trimethylolpropylene etc. (commercial products from BASF, Federal republic of Germany) can be used in binder mixtures, especially in mixtures with polyethylene glycols; however, they cannot act as the sole binder can be used because they fulfill a binding / adhesive function, but none disintegrating effect.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further binders, alone or in combination with other binders, in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4. Particularly suitable are those alkyl glycosides which have a degree of softening above 80 ° C and a melting point above 140 ° C. Highly concentrated compounds with contents of at least 70% by weight alkyl glycosides, preferably at least 80% by weight alkyl glycosides, are also suitable. Using high shear forces, the melt agglomeration and in particular the melt extrusion with such highly concentrated compounds can already be carried out at temperatures which are above the softening point but still below the melting temperature. Although alkyl glycosides can also be used as the sole binder, it is preferred to use mixtures from alkyl glycosides and other binders. In particular, here are mixtures of polyethylene glycols and alkyl glycosides, advantageously in weight ratios of 25: 1 to 1: 5, with particular preference from 10: 1 to 2: 1.

Also as a binder, especially in combination with polyethylene glycols and / or Alkyl glycosides, polyhydroxy fatty acid amides of the formula (I) are suitable, in which R²CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R³ for hydrogen, one Alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] for a linear or  branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 Hydroxyl groups.

The polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, especially from glucose.

The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

in the R³ for a linear or branched alkyl or alkenyl radical with 7 to 12 carbons atoms, R⁴ for a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R⁵ for a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, where C₁-C₄ alkyl or phenyl radicals are preferred, and [Z] for a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxy lated, preferably ethoxylated or propoxylated derivatives of this radical. [Z] will also here preferably by reductive amination of a sugar such as glucose, fructose, Get maltose, lactose, galactose, mannose or xylose. The N-alkoxy or N-aryloxy Substituted compounds can then, for example, according to the teaching of international Patent application WO-A-95/07331 by reaction with fatty acid methyl esters in counter were an alkoxide as a catalyst in the desired polyhydroxy fatty acid amides leads. Particularly preferred glucamides already melt at 95 to 105 ° C. But here too - as with the alkyl glycosides - norma is sufficient in the process according to the invention Working temperatures, which are above the softening temperature, but un are below the melting temperature.

The content of binder or binders in the premix is preferably at least at least 2% by weight, but less than 15% by weight, in particular less than 10% by weight particular preference of 3 to 6 wt .-%, each based on the premix.  

In a preferred embodiment of the method according to the invention, the Solids for the production of the solid and free-flowing premix initially at room temperature to slightly elevated temperatures, preferably below the melting point temperature or the softening point of the binder and especially at Tempe veratures up to 35 ° C in a conventional mixing and / or granulating device mixes. These solids also include those which, according to the European Pa tent EP-B-0 486 592 can serve as a plasticizer and / or lubricant. These include ins special anionic surfactants such as alkylbenzenesulfonates and / or (fatty) alkyl sulfates, but also Polymers such as polymeric polycarboxylates. A more detailed description of the possible Anionic surfactants and polymers appear later in the list of possible ingredients. The The function of a lubricant can also depend on the binder or binders or the binder mixtures are perceived.

The binders are preferably added as the last component. Your encore can as already stated above, as a solid, i.e. at a processing temperature that is below is half of its melting point or its softening point, or take place as a melt. However, the admixture is advantageously carried out under such conditions that that the most uniform, homogeneous distribution of the binder in the solid mixture is reached. With very finely divided binders, this can occur at temperatures below half 40 ° C, for example at temperatures of the binder between 15 and 30 ° C be be made. However, the binder advantageously has temperatures at which are already in the form of a melt, i.e. above the softening point, in particular which is in the form of a complete melt. Preferred temperatures of Melt are at 60 to 150 ° C with particular preference for the temperature range from 80 to 120 ° C. During the mixing process, which is from room temperature to light elevated temperature occurs, the melt solidifies almost immediately, and the Vorge According to the invention, mix is in solid, free-flowing form.

The assembly of the detergent or cleaning agent compounds and / or raw materials with simultaneous or subsequent shaping can be done by conventional methods in de compression forces such as granulating, compacting, for example Roll compacting or extruding, or tableting and pelleting.

The actual granulation, compacting, tableting, pelleting or Ex trusion process takes place according to the invention at processing temperatures that at least in Compression step at least if not the temperature of the softening point correspond to the temperature of the melting point. In a preferred embodiment  the process temperature is significantly above the melting point or above half the temperature at which the binder is in the form of a melt. In particular it is but preferred that the process temperature in the compression step be no more than 20 ° C above the melting temperature or the upper limit of the melting range of the binder tels lies. It is technically possible to use even higher temperatures put; however, it has been shown that a temperature difference to the melting temperature or sufficient for the softening temperature of the binder of 20 ° C. in general is appropriate and even higher temperatures have no additional advantages. Therefore it - particularly also for energy reasons - is particularly preferred, above however as close as possible to the melting point or the upper temperature limit of the Melting range of the binder to work. Such a temperature control has the further advantage that thermally sensitive raw materials, such as peroxy bleaching agents such as perborate and / or percarbonate, but also enzymes, increasingly without gra four loss of active substance can be processed. The possibility of exact Temperature control of the binder, especially in the crucial step of compacting tion, i.e. between the mixing / homogenization of the premix and the form giving, allows an energetically very favorable and for the temperature sensitive Be components of the premix extremely gentle process management, since the premix only is exposed to the higher temperatures for a short time. Preferably the duration is Exposure to temperature between 10 seconds and a maximum of 5 minutes, especially be she wears a maximum of 3 minutes.

In a preferred embodiment of the invention, the method according to the invention carried out by means of an extrusion, as described, for example, in the European patent EP B-0 486 592 or international patent applications WO-A-93/02176 and WO-A- 94/09111. A solid premix becomes strand-like under pressure pressed and the strand after exiting the hole shape by means of a cutting device can be cut to the predeterminable size of the granulate. The homogeneous and solid premix contains a plasticizer and / or lubricant, which causes the Premix plastically softened under the pressure or under the entry of specific work and becomes extrudable. Preferred plasticizers and / or lubricants are surfactants and / or Polymers which, with the exception of the above, are within the scope of the present invention non-ionic surfactants, however, not in liquid and in particular not in aqueous, but be introduced into the premix in solid form.

To explain the actual extrusion process, we hereby expressly refer to the referenced above patents and patent applications. In a preferred embodiment  form of the invention, the premix is preferably continuously a 2- Screw extruder fed with co-rotating or counter-rotating screw guidance, its housing and its extruder pelletizing head to the predetermined extrusion temperature can be heated. Under the shear of the extruder screw the premix under pressure, which is preferably at least 25 bar, at extreme high throughputs depending on the apparatus used but also below can lie, compressed, plasticized, in the form of fine strands through the perforated nozzle plate in the Extruder head extruded and finally the extrudate using a rotating tee knife preferably reduced to approximately spherical to cylindrical granules. The hole diameter of the perforated nozzle plate and the length of the strand cut are determined the selected granule size is coordinated. In this embodiment, Her provision of granules of a substantially uniformly predeterminable particle size, with the absolute particle sizes being the intended use can be adapted. In general, particle diameters up to a maximum of 0.8 cm prefers. Important embodiments see the production of uniform Granules in the millimeter range, for example in the range from 0.5 to 5 mm and ins especially in the range of about 0.8 to 3 mm. The length / diameter ratio of the In an important embodiment, chipped primary granules lie in the Range from about 1: 1 to about 3: 1. It is further preferred that the still plastic primary to supply granulate to a further shaping processing step; thereby on Raw extrudate edges rounded off, so that ultimately spherical to approximately spherical extrudate grains can be obtained. If desired you can use this Stage small amounts of dry powder, for example zeolite powder such as zeolite NaA Powder to be used. This shape can be found in standard rounding machines respectively. It should be ensured that only small amounts of fine are used in this stage grain proportion arise. A drying process which is described in the above-mentioned documents of the The prior art is described as a preferred embodiment, but is unnecessary in the context of the present invention, since the method according to the invention essentially Chen water-free, i.e. without the addition of free, unbound water.

In a particularly preferred embodiment, the invention now provides that the Temperature control in the transition area of the screw, the pre-distributor and the nozzles plate is designed such that the melting temperature of the binder or the upper Limit of the melting range of the binder at least reached, but preferably over is taken. The duration of the temperature influence is in the compression range Extrusion preferably less than 2 minutes and in particular in a range between 30 seconds and 1 minute.  

In a particularly advantageous embodiment of the invention, the bin used demittel a melting temperature or a melting range up to 75 ° C; Procedural temperatures which are a maximum of 10 ° C and in particular a maximum of 5 ° C above the enamel temperature or the upper temperature limit of the melting range of the binder, have then proven to be particularly cheap.

Under these process conditions, the binder exercises in addition to those previously mentioned effects also function as a lubricant and prevent or prevent it at least reduces sticking to apparatus walls and compaction tools. This applies not only to processing in the extruder, but equally also for processing, for example, in continuously operating mixers / granules or rollers.

The compacted material is preferred immediately after leaving the manufacturing apparatus show temperatures not above 60 ° C, with temperatures between 35 and 60 ° C are particularly preferred. It has been found that outlet temperatures - before especially in the extrusion process - from 40 to 55 ° C are particularly advantageous.

As in the extrusion process, it is also in the other manufacturing processes prefers the resulting primary granules / compactate another form Ver to carry out work step, in particular to round off, so that ultimately spherical to approximately spherical (pearl-shaped) grains can be obtained.

It is the essence of a preferred embodiment of the invention that the particle size The outer distribution of the premix is much broader than that of the invention according to the end product produced and according to the invention. The premix can we considerably larger fractions of fine grains, even dust, possibly also coarser Contain portions, but it is preferred that a premix with a relatively wide portion size distribution and relatively high proportions of fine grain in an end product with relative narrow particle size distribution and relatively small proportions of fine grain is transferred.

Because the process according to the invention is essentially anhydrous - that is, H. with off Taking water contents ("impurities") of the solid raw materials used water-free - is not only the risk of gelling the surfactant raw materials already minimized to excluded in the manufacturing process, in addition a Ecologically valuable process provided, because by not having one follow  the drying step not only saves energy but also emissions like they do mainly occur with conventional types of drying, can be avoided.

It has been found that the resolving behavior of the invention provided washing or cleaning agents in contrast to conventionally manufactured agents now essentially depends only on the detachment behavior of the individual components; the more components that are soluble relatively quickly, the faster the finished agents are also soluble; the more contain relatively slowly soluble components the slower the means are released. Unwanted interactions during the Redissolution such as gelling etc. also play a role in the method according to the invention for washing or cleaning agents with very high densities, for example above, from 750 and 800 g / l, obviously no longer matter. The means, compounds so produced and treated raw materials thus show an improved dissolution rate such agents, compounds and treated raw materials, which have the same end have composition, but not according to the inventive method were not produced by means of a melt under anhydrous conditions were.

Accordingly, another object of the invention is a particulate washing or cleaning agent which was produced by the method according to the invention and its dissolving behavior only depends on the dissolving behavior of the individual raw materials used and is dependent on compounds. Without wanting to limit yourself to this theory, it works Applicant assumes that this particular release behavior is due to a honeycomb-like Structure of the particles is effected, these honeycombs are filled with solid.

In a preferred embodiment of the invention, a granular or extruded Detergent provided, which at least 80 wt .-% produced from the invention compounds and / or treated raw materials. In particular, there is a granu Laral or extruded detergent to at least 80 wt .-% from an inventive produced basic granulate or basic extrudate. The remaining ingredients can be after any known method have been prepared and mixed. However, it is preferred that these remaining constituents, which compounds and / or behan delte raw materials can be produced by the method according to the invention. In particular, this enables basic granules and remaining constituents approaches the same pourability, bulk density, size and particle size distribution put.  

The invention further relates to compounds and treated raw materials, for example builder granules (extrudates), bleach activator granules latex (extrudates) or enzyme granules (extrudates).

Base granules, compounds and treated raw materials are particularly preferred provided fabrics that have spherical or pearl shape.

Surprisingly, the end products of the process produced according to the invention a very high bulk density. The bulk density is preferably above 700 g / l, in particular between 750 and 1000 g / l. Even if the extrudates with other In contents that have lower bulk densities are processed, this will decrease Bulk weight of the final product not to the extent normally expected that would be. It is believed that approximately spherical agents, and particularly extru date, which were produced by the method according to the invention, rather the ideal shape a ball with a smooth, "smeared" surface resemble that of conventional and agents and extrudates produced in particular by aqueous processes. This will make one achieved better space filling, which leads to a higher bulk density, even if Components are added that have neither spherical structure nor such a high bulk have weight.

The particulate process end products obtained can either be used directly as washing or cleaning agents used or previously treated according to conventional methods and / or processed. The usual post-treatments include, for example Powdering with finely divided ingredients from washing or cleaning agents, thereby the bulk density is generally further increased. A preferred after treatment however also presents the procedure according to German patent applications P 195 24 287.4 and P 195 47 457.0, with dusty or at least finely divided In Contents (the so-called fines) in the particles produced according to the invention shaped process end products, which serve as the core, are glued and thus Means are created which have these so-called fines as an outer shell. Advantage in turn, this is done by melting agglomeration, the same Binders can be used as in the inventive method. For Melt agglomeration of the fines on the inventive and inventive Base granules produced are expressly based on the disclosure in the German Pa tent registrations P 195 24 287.4 and P 195 47 457.0.  

Processing is generally understood to mean that those prepared according to the invention Particulate process end products serve as a compound to which other content substances, if necessary also other compounds. Here is on the Be descriptions of the cited patent applications and patent specifications, in particular on European patent EP-B-0 486 592 and German patent applications P 195 19 139.0, P 195 24 287.4 and P 19 54 7457.0.

There now follows a detailed description of the possible ingredients of the invention ß agents and the ingredients used in the inventive method.

Important ingredients of the agents and ingredients according to the invention, which in the inventions Processes used in accordance with the invention are surfactants, in particular anionic surfactants, which at least in amounts of 0.5 wt .-% in the inventive agents or inventions Agents manufactured in accordance with the invention should be included. These include Sul in particular fonate and sulfate, but also soaps.

Preferred surfactants of the sulfonate type are C₉-C₁₃ alkylbenzenesulfonates, olefin sulfonates, d. H. Mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as for example, from C₁₂-C₁₈ monoolefins with terminal or internal double bin by sulfonation with gaseous sulfur trioxide followed by alkaline or acidic hydrolysis of the sulfonation products is considered.

Also suitable are alkanesulfonates, which are derived from C₁₂-C₁ Alk alkanes, for example by sulfo Chlorination or sulfoxidation with subsequent hydrolysis or neutralization obtained will.

Also suitable are the esters of α-sulfo fatty acids (ester sulfonates), e.g. B. the α-sulfonated Methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids by α-sulfonation the methyl ester of fatty acids of plant and / or animal origin with 8 to 20 C- Atoms in the fatty acid molecule and subsequent neutralization to water-soluble mono- Salts are made into consideration. This is preferably the α-sul Formed esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids, whereby also Sulfonation products of unsaturated fatty acids, for example oleic acid, in low Amounts, preferably in amounts not above about 2 to 3% by weight, are present can. In particular, α-sulfofatty acid alkyl esters are preferred which have an alkyl chain have no more than 4 carbon atoms in the ester group, for example methyl esters,  Ethyl ester, propyl ester and butyl ester. The methyl esters of are particularly advantageous α-sulfo fatty acids (MES), but also their saponified disalts.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and Triester and their mixtures represent how they are produced by esterification by a monoglycerin with 1 to 3 moles of fatty acid or in the transesterification of triglycerides can be obtained with 0.3 to 2 mol of glycerol.

The alkali and, in particular, the sodium salts of sulfuric acid are used as alk (en) yl sulfates half-esters of the C₁₂-C₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, Lauryl, myristyl, cetyl or stearyl alcohol or the C₁₀-C₂₀ oxo alcohols and those Half-secondary alcohols of this chain length are preferred. Are also preferred Alk (en) yl sulfates of the chain length mentioned, which is a synthetic, based on petrochemical straight-chain alkyl radical containing an analogous degradation behavior Like the adequate compounds, they have compounds based on oleochemical raw materials. C₁₆-C₁₈-alk (en) yl sulfates are particularly preferred for washing technology reasons. It can also be of particular advantage and especially for machine washing agents be advantageous, C₁₆-C₁₈-alk (en) yl sulfates in combination with lower melting anion surfactants and especially those with anionic surfactants that have a lower Krafft point have and at relatively low washing temperatures of, for example, room temperatures to 40 ° C show a low tendency to crystallize. In a preferred one Embodiment of the invention, the agents therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C₁₂-C₁₄ fatty alkyl sulfates or C₁₂-C₁₈ fatty alkyl sulfates with C₁₆-C₁₈ fatty alkyl sulfates and especially C₁₂-C₁₆- Fatty alkyl sulfates with C₁₆-C₁₈ fatty alkyl sulfates. In a further preferred embodiment form of the invention are not only saturated alkyl sulfates, but also unsaturated used alkenyl sulfates with an alkenyl chain length of preferably C₁₆ to C₂₂. In particular, mixtures of saturated, consisting predominantly of C₁₆ sulfated fatty alcohols and unsaturated sulfates consisting predominantly of C₁₈ Fatty alcohols are preferred, for example those that differ from solid or liquid fatty alcohols Derive wood mixtures of the type HD-Ocenol® (commercial product of the applicant). Here are weight ratios of alkyl sulfates to alkenyl sulfates from 10: 1 to 1: 2 and in particular particularly preferred from about 5: 1 to 1: 1.

Also 2,3-alkyl sulfates, which, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 are manufactured and marketed by Shell Oil Company under the Suitable DAN® names are suitable anionic surfactants.  

Also the sulfuric acid monoesters of the straight chain ethoxylated with 1 to 6 moles of ethylene oxide gene or branched C₇-C₂₁ alcohols, such as 2-methyl branched C₉-C₁₁ alcohols with im An average of 3.5 moles of ethylene oxide (EO) or C₁₂-C₁₈ fatty alcohols with 1 to 4 EO are ge is suitable. Due to their high foaming behavior, they are only used relatively in detergents small amounts, for example in amounts of 1 to 5% by weight, are used.

Alkyl (en) sulfate mixtures in which the proportion of Al kyl (en) residues 15 to 40% by weight on C₁₂, 5 to 15% by weight on C₁₄, 15 to 25% by weight to C₁₆, 30 to 60 wt .-% on C₁₈, and less than 1 wt .-% are distributed on C₁₀.

Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also known as Sulfosuccinate or be called sulfosuccinate and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and represent in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C₈ to C₁₈ fatty alcohol residues or mixtures of these. Particularly preferred sulfo succinate contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which are non-ionic surfactants (see description below). Here are again sulfosuccinates, the fatty alcohol residues of which are different from ethoxylated fatty alcohols derived with narrow homolog distribution, particularly preferred. It is the same possible, alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the Use alk (en) yl chain or its salts.

Other anionic surfactants include fatty acid derivatives of amino acids, for example example of N-methyl taurine (tauride) and / or of N-methyl glycine (sarcoside). The sarcosides or sarcosinates are particularly preferred, and above all Sarcosinates of higher and optionally mono- or polyunsaturated fatty acids such as oleyl sarcosinate.

Other anionic surfactants include, in particular, soaps, preferably in amounts of 0.2 to 5% by weight. Saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated Erucic acid and behenic acid, and in particular from natural fatty acids, e.g. B. coconut, Palm kernel or tallow fatty acids, derived soap mixtures. Along with these soaps or as a substitute for soaps, the known alkenyl succinic acid salts can also be used be set.  

The anionic surfactants (and soaps) can be in the form of their sodium, potassium or ammo nium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine, available. The anionic surfactants are preferably in the form of their sodium or Ka lium salts, especially in the form of the sodium salts.

The anionic surfactants are in the agents according to the invention or are invented in the Process according to the invention preferably in amounts of 1 to 30 wt .-% and in particular contained or used in amounts of 5 to 25 wt .-%.

In addition to the ionic surfactants and the cationic, zwitterionic and amphoteric Surfactants, especially nonionic surfactants are preferred.

Preferred nonionic surfactants are alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 up to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical is linear or can preferably be methyl-branched in the 2-position or linear and methyl-branched radicals can contain in the mixture, as they are usually present in oxo alcohol residues. In particular, however, alcohol ethoxylates with linear residues from alcohols are native Ur jump with 12 to 18 carbon atoms, e.g. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol is preferred. Among the preferred ethoxylated Alcohols include, for example, C₁₂-C₁₄ alcohols with 3 EO or 4 EO, C₉-C₁₁ alcohols with 7 EO, C₁₃-C₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C₁₂-C₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C₁₂-C₁₄ alcohol with 3 EO and C₁₂-C₁₈ alcohol with 7 EO. The degrees of ethoxylation indicated are statistical Mean values that are an integer or a fraction for a specific product can. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants fatty alcohols with more than 12 EO can also be used. Examples include (tallow) Fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.

The nonionic surfactants also include the alkyl glycosides of the general formula RO (G) _x already described in detail above and the polyhydroxy fatty acid amides of the formulas (I) and (II).

Another class of preferred non-ionic surfactants, either alone total nonionic surfactant or in combination with other nonionic surfactants, esp especially used together with alkoxylated fatty alcohols and / or alkyl glycosides  are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated Fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular special fatty acid methyl esters, such as, for example, in the Japanese patent application JP 58/217598 are described or preferably according to the international Pa The method described in WO-A-90/13533 can be produced. Especially preferred are C₁₂-C₁₈ fatty acid methyl esters with an average of 3 to 15 EO, in particular others with an average of 5 to 12 EO.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-di methylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanol amides can be suitable. The amount of these nonionic surfactants is preferred not more than that of the ethoxylated fatty alcohols, especially not more than that Half of it.

So-called gemini surfactants can be considered as further surfactants. Below are in generally understood such compounds that two hydrophilic groups and two hy have drophobic groups per molecule. These groups are usually characterized by one called "spacer" separated from each other. This spacer is usually a coal material chain that should be long enough that the hydrophilic groups have a sufficient Have a distance so that they can act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In out However, under the term Gemini surfactants, not only dimeric but also also understood trimeric surfactants.

Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to the German patent application DE-A-43 21 022 or dimer alcohol bis and trimer alcohol tris sulfates and ether sulfates according to the earlier German patent application P 195 03 061.3. End group capped dimeric and trimeric mixed ethers according to the older German Patent application P 195 13 391.9 are particularly characterized by their bi- and multi-radio functionality. For example, the end-capped surfactants mentioned have a good network properties and are low-foaming, so that they are particularly suitable for use in machine washing or cleaning processes.

Gemini polyhydroxy fatty acid amides or Poly-Po can also be used lyhydroxy fatty acid amides, as described in international patent applications WO-A- 95/19953, WO-A-95/19954 and WO95-A- / 19955.  

In addition to the surfactants, the inorganic and organic builder substances belong above all zen about the most important ingredients of washing or cleaning agents.

The fine crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from Crosfield) and Zeolite NaP® (commercial product from Degussa) prefers. However, zeolite X and mixtures of A, X and / or P are also suitable. The zeolite can be used as a spray-dried powder or as an undried one still damp, stabilized suspension are used. In the event that the Zeolite is used as a suspension, these small additions of nonionic, Ten contain as stabilizers, for example 1 to 3% by weight, based on zeolite ethoxylated C₁₂-C₁₈ fatty alcohols with 2 to 5 ethylene oxide groups, C₁₂-C₁₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites white an average particle size of less than 10 µm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22 % By weight of bound water.

Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi _x O _{2x + 1} .yH₂O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to Is 20 and before preferred values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na₂Si₂O₅ · yH₂O are preferred.

The preferred builder substances also include amorphous sodium silicates with a Module Na₂O: SiO₂ from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which are delayed release and have secondary washing properties. The Delay in dissolution compared to conventional amorphous sodium silicates can occur different ways, for example by surface treatment, compounding, Compacting / compaction or caused by overdrying. in the Within the scope of this invention, the term “amorphous” is also understood to mean “X-ray amorphous” the. This means that the silicates do not have sharp X-rays in X-ray diffraction experiments deliver genre reflexes, as they are typical for crystalline substances, but at most one or several maxima of the scattered X-rays that are several degrees wide  units of the diffraction angle. However, it can very well be particularly good ten builder properties lead when the silicate particles in electron diffraction experiments mentally washed out or even sharp diffraction maxima. This is so interpre animals that the products have microcrystalline areas of size 10 to a few hundred nm indicate, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution have compared to conventional water glasses, for example in the German patent application DE-A-44 00 024. Are particularly preferred compacted / compacted amorphous silicates, compounded amorphous silicates and overdry X-ray amorphous silicates.

It goes without saying that the generally known phosphates are also used as buildersub punching possible, provided that such use is not avoided for ecological reasons should be. The sodium salts of orthophosphates, the py rophosphates and especially the tripolyphosphates. Your salary in general no longer than 25% by weight, preferably not more than 20% by weight, in each case based on the finished product Medium. In some cases it has been shown that tripolyphosphates in particular are already in small amounts up to a maximum of 10% by weight, based on the finished agent, in combination with other builder substances to a synergistic improvement of the secondary wash ability.

Suitable substitutes or partial substitutes for the zeolite are layered silicates natural and synthetic origin. Such layered silicates are for example from the patent DE-B-23 34 899, EP-A-0 026 529 and DE-A-35 26 405 are known. Your use Availability is not limited to a special composition or structural formula. Be However, smectites, in particular bentonites, are preferred here.

Suitable layered silicates, which belong to the group of water-swellable smectites, are for example montmorrilonite, hectorite or saponite. In addition, in the Kri Stall grid of the layered silicates according to the formulas above, small amounts of iron be installed. Furthermore, the layered silicates can, due to their ion exchange Properties contain hydrogen, alkali, alkaline earth ions, in particular Na⁺ and Ca⁺⁺. The amount of water of hydration is usually in the range from 8 to 20% by weight and is from the source status or depending on the type of processing. Usable layered silicates are included known for example from US-A-3,966,629, EP-A-0 026 529 and EP-A-0 028 432. Preferential Layered silicates are used, which are largely due to an alkali treatment are free of calcium ions and strongly coloring iron ions.  

Usable organic builders are, for example, those in the form of their sodium salts of polycarboxylic acids, such as citric acid, adipic acid, succinic acid, Glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and Mixtures of these. Preferred salts are the salts of polycarboxylic acids such as Citro Nenoic acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and Mi created from these.

The acids themselves can also be used. The acids have besides their buil the effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH value of washing or Detergents. In particular, citric acid, succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can be. The hydrolysis can be carried out according to conventional methods, for example acid or enzyme lysed procedures are carried out. It is preferably hydrolysis pro Products with average molecular weights in the range of 400 to 500,000. There is a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 preferred, DE being a common measure of the reducing effect of a Polysac charids compared to dextrose, which has a DE of 100. Both are usable Maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher moles masses in the range from 2000 to 30,000. A preferred dextrin is in the British Pa tent registration 94 19 091. In the oxidized derivatives of such dextrins are their reaction products with oxidizing agents, which are capable are, at least one alcohol function of the saccharide ring to the carboxylic acid function oxidize. Such oxidized dextrins and processes for their production are, for example from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A- 0 472 042 and EP-A-0 542 496 and the international patent applications WO-A- 92/18542, WO-A-93/08251, WO-A-94/28030, WO-A-95/07303, WO-A-95/12619 and WO-A- 95/20608 known. A product oxidized at C₆ of the saccharide ring can be particularly advantageous be clingy.

Other suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate. Are particularly preferred in this context  also glycerol disuccinates and glycerol trisuccinates, as described, for example, in the US American patents US 4,524,009, US 4,639,325, in European Pa tent application EP-A-0 150 930 and Japanese patent application JP 93/339896 be be written. Suitable amounts are in zeolite and / or silicate gene formulations at 3 to 15 wt .-%.

Other useful organic cobuilders are, for example, acetylated hydroxycarbon acids or their salts, which may optionally also be in lactone form, and which have at least 4 carbon atoms and at least one hydroxyl group and at most contain two acid groups. Such cobuilders are used, for example, in the internatio Nale patent application WO-A-95/20029 described.

Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylics acid or polymethacrylic acid, for example those with a relative molecular weight from 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are ins especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid have been found to be particularly suitable Maleic acid proved to be 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid contain. Their relative molecular weight, based on free acids, is in general 5000 to 200000, preferably 10000 to 120000 and in particular 50000 to 100000.

The content of (co) polymeric polycarboxylates in the compositions is in the usual range and is preferably 1 to 10% by weight.

Biodegradable polymers of more than two ver. Are also particularly preferred different monomer units, for example those which according to DE-A-43 00 772 as Monomeric salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol Derivatives or according to DE-C-42 21 381 as monomers salts of acrylic acid and 2- Contain alkylallylsulfonic acid as well as sugar derivatives.

Further preferred copolymers are those which are described in German patent applications DE- A-43 03 320 and DE-A-44 17 734 are described and preferably as monomers Have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Other suitable builder substances are oxidation products of carboxyl-containing ones Polyglucosans and / or their water-soluble salts, such as those in the international patent application WO-A-93/08251 can be described or their manufacturers For example, described in international patent application WO-A-93/16110  becomes. Oxidized oligosaccharides according to the older German are also suitable Patent application P 196 00 018.1.

Likewise, further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors. Poly are particularly preferred aspartic acids or their salts and derivatives, of which in the German patent application P 195 40 086.0 is disclosed that in addition to cobuilder properties, it also has a have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which are produced by the implementation of Dial dehydrogenated with polyol carboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups have pen, for example as in European patent application EP-A-0 280 223 described, can be obtained. Preferred polyacetals are made from dialdehydes such as Glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and made of polyolcarbon Acids such as gluconic acid and / or glucoheptonic acid obtained.

In addition, the agents can also contain components that contain the oil and fat positively affect washability from textiles. This effect is particularly evident when a textile is soiled that has previously been used several times with an inventive Detergent containing this oil and fat-dissolving component has been washed. To the preferred oil and fat-dissolving components include, for example, non-ionic 22505 00070 552 001000280000000200012000285912239400040 0002019638599 00004 22386che Cellu loose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of meth oxyl groups from 15 to 30% by weight and hydroxypropoxyl groups from 1 to 15% by weight, each based on the nonionic cellulose ether, and those from the prior art Technology known polymers of phthalic acid and / or terephthalic acid or de Ren derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol Kolterephthalaten or anionically and / or nonionically modified derivatives of these. Of these, particular preference is given to the sulfonated derivatives of phthalic acid and Terephthalic acid polymers.

Other suitable ingredients of the agents are water-soluble inorganic salts such as Bi carbonates, carbonates, amorphous silicates such as the above-mentioned dissolution-delayed silicates or mixtures of these; in particular, alkali carbonate and amorphous alkali silicate kat, especially sodium silicate with a molar Na₂O: SiO₂ ratio of 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5. The content of sodium carbonate in the agent preferably carries up to 20% by weight, advantageously between 5 and 15% by weight. The content of sodium silicate in the agent is - if it is not used as a builder  generally up to 10% by weight and preferably between 2 and 8% by weight, otherwise about it.

According to the teaching of international patent application WO-A-94/01222, alkali carbo nate also by sulfur-free, 2 to 11 carbon atoms and optionally one more Amino acids having carboxyl and / or amino groups and / or by their salts be replaced. In the context of this invention, it is possible that a partial to the alkali carbonates are completely replaced by glycine or glycinate.

The other detergent ingredients include graying inhibitors (dirt ger), foam inhibitors, bleaching agents and bleach activators, optical brighteners, enzymes, fabric softening agents, dyes and fragrances as well as neutral salts such as sulfates and Chlorides in the form of their sodium or potassium salts.

Acid can also be used to reduce the pH of detergents or cleaning agents Salts or slightly alkaline salts can be used. Are preferred as acidification component bisulfates and / or bicarbonates or the above-mentioned organic polycar bonic acids, which can also be used as builder substances at the same time.

Among the serving as bleaching agents, H₂O₂ in water compounds have that Sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other bleaches that can be used include sodium percarbonate and peroxypyrophos phates, citrate perhydrates and H₂O₂ delivering peracidic salts or peracids such as perben zoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedi acid. The bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20 wt .-%, advantageously perborate monohydrate or Per carbonate is used.

Compounds which are aliphatic under perhydrolysis conditions can be used as bleach activators cal peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms Atoms, and / or optionally substituted perbenzoic acid, who used the. Substances containing O and / or N-acyl groups of the number of carbon atoms mentioned are suitable and / or optionally substituted benzoyl groups. Multiple are preferred acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated Glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N- Nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonat (n- or iso-NOBS), carboxylic anhydrides, in particular  Phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol koldiacetate, 2,5-diacetoxy-2,5-dihydrofuran and those from the German patent applications DE-A-196 16 693 and DE-A-196 16 767 known enol esters and acetylated sorbitol and mannitol or their in the European patent application EP-A- 0 525 239 described mixtures (SORMAN), acylated sugar derivatives, in particular Pentaacetylglucose (PAG), Pentaacetylfruktose, Tetraacetylxylose and Octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N- acylated lactams, for example N-benzoylcaprolactam, which are derived from the international Pa Tent 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 are known. The from the German patent application dung DE-A-196 16 769 known hydrophilically substituted acylacetals and those in the German patent application DE-A-196 16 770 and the international patent application WO- A-95/14075 acyl lactams described are also preferably used. Also the known combinations from the German patent application DE-A-44 43 177 National bleach activators can be used. Such bleach activators are in usual amount range, preferably in amounts of 1 wt .-% to 10 wt .-%, esp contain in particular 2 wt .-% to 8 wt .-%, based on the total agent.

When used in machine washing processes, it can be of advantage to use the usual agents Add foam inhibitors. Soaps are suitable as foam inhibitors, for example natural or synthetic origin, which has a high proportion of C₁₈-C₂₄ fatty acids point. Suitable non-surfactant foam inhibitors are, for example, organopolysil oxanes and their mixtures with microfine, possibly silanized silica and paraffins, Waxes, microcrystalline waxes and their mixtures with silanized silica or bi stearylethylenediamide. Mixtures of different foams are also advantageous hibitors used, e.g. B. from silicone, paraffins or waxes. Preferably are the foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors ren, bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamides are in the offing moves.

The neutral-reacting Na are preferably used as salts of polyphosphonic acids trium salts of, for example, 1-hydroxyethane-1,1-diphosphonate, diethylene triamine penta methylenephosphonate or ethylenediaminetetramethylenephosphonate in amounts of 0.1 to 1.5 wt .-% used.  

Enzymes in particular come from the hydrolase class, such as the protea sen, lipases or lipolytically active enzymes, amylases, cellulases or their mixtures questionable. Oxireductases are also suitable.

From bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens obtained enzymati active ingredients. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used. There are Enzymmi creations, for example from protease and amylase or protease and lipase or lipoly table-acting enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic acting enzymes or protease, lipase or lipolytically acting enzymes and Cellu lase, but especially protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipoly Enzymes with a table effect are the well-known cutinases. Also peroxidases or oxidases have proven to be suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. As cellulases are preferably cellobiohydrolases, endoglucanases and β-glucosidases, which also Cellobiases are called, or mixtures of these are used. Since the ver distinguish different cellulase types by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases will.

The enzymes can be adsorbed on carriers and / or embedded in coating substances to protect them against premature decomposition. The proportion of enzymes, Enzymmi Schungen or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-%.

In addition to phosphonates, the agents can also contain further enzyme stabilizers. For example, 0.5 to 1% by weight sodium formate can be used. Is possible also the use of proteases with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme, are stabilized. Except Cal Magnesium salts also serve as magnesium stabilizers. However, it is particularly advantageous the use of boron compounds, for example boric acid, boron oxide, borax and others ren alkali metal borates such as the salts of orthoboric acid (H₃BO₃), metaboric acid (HBO₂) and pyrobic acid (tetraboric acid H₂B₄O₇).  

Graying inhibitors have the task of removing the dirt detached from the fiber in the Keep the liquor suspended and thus prevent the dirt from re-opening. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acid ren or ether sulfonic acids of starch or cellulose or salts of acid sulfur acid esters of cellulose or starch. Also contain water-soluble, acidic groups Polyamides are suitable for this purpose. Soluble starch preparations can also be used use parate and starch products other than the above, e.g. B. dismantled Starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. To be favoured however, cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyal kylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellu loose, methyl carboxymethyl cellulose and mixtures thereof, and polyvinyl pyrrolidone for example in amounts of 0.1 to 5 wt .-%, based on the agent used.

As optical brighteners, the agents can be derivatives of diaminostilbenedisulfonic acid or de contain alkali metal salts. Are suitable for. B. salts of 4,4'-bis (2-anilino-4-morpho lino-1,3,5-triazinyl-6-amino) stilbene-2,2′-disulfonic acid or a similarly constructed verb which replace the morpholino group with a diethanolamino group, a methylami no group, an anilino group or a 2-methoxyethylamino group. Furthermore, a brightener of the substituted diphenylstyryl type may be present, e.g. B. the alkali salts 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4- Chlorstyryl) -4 ′ - (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.

Examples

Means M1 and M2 were produced according to the following procedure:
In a batch mixer (20 liters) equipped with a cutter head chopper, a solid premix was made from the solid ingredients, including the binder, which in this case was added in solid form. (In an alternative embodiment, the binder was injected into the premix in the form of a sprayable melt; however, this did not lead to end products with significantly different properties. The melt solidified within a short time after application to the solid mixture. The usual residence time in the mixer was sufficient The mixture was then homogenized for a further 2 minutes and then fed to a twin-screw extruder, the pelletizing head of which had been preheated to temperatures between 50 and 65 ° C., preferably to 62 ° C. The non-ionic surfactants that were optionally present at temperatures below 45 ° C. and a pressure of 1 bar were added to the powder stream by spraying through nozzles. Under the shear action of the extruder screws, the premix was plasticized and then extruded at a pressure between 50 and 100 bar, preferably around 78 bar, through the extruder head perforated die plate into fine strands with a diameter of 1.4 mm, which, after the die outlet, was removed by means of a knife were crushed into approximately spherical granules (length / diameter ratio about 1, hot cut). The resulting warm granules were rounded off for one minute in a Marumerizer® type rounding machine and, if necessary, coated with a fine-particle powder.

The bulk density of the extrudates produced was 800 ± 50 g / l.

A homogeneous premix was produced to produce agent M1 according to the invention 61% by weight of spray-dried granules 1 (composition see below), 6% by weight C₁₂-C₁₈ fatty alkyl sulfate (composition 92.00% by weight of active substance, 3.70% by weight Sodium sulphate, 2.80% by weight of other salts from raw materials and unsulphated parts and 1.50 wt .-% water), 3 wt .-% copolymer sodium salt of acrylic acid and malein acid (powder form), 20% by weight sodium perborate monohydrate and 6% by weight Po as a binder made of polyethylene glycol with a molecular weight of 4000. In the powder stream were 4 wt .-% C₁₂-C₁₈ fatty alcohol sprayed with an average of 7 EO. The pre Mix was then extruded. The extrudate showed in the sieve analysis given  a bulk density of 758 g / l and achieved in the solubility test described below (L- Test) a value of 8%.

Sieve analysis M1:

on sieve

1.60 mm 6% by weight
1.25 mm 76% by weight
1.00 mm 8% by weight
0.80 mm 4% by weight

through sieve

0.80 mm 6% by weight.

To determine the residue behavior or the solubility behavior (L test), in a 2 l beaker 8 g of the agent to be tested with stirring (800 rpm with La borrührer / propeller stirring head 1.5 cm from the beaker bottom centered) and stirred at 30 ° C for 1.5 minutes. The test was carried out with water with a hardness of 16 ° d carried out. The wash liquor was then poured off through a sieve (80 μm). The beaker was rinsed over the sieve with very little cold water. It he a double determination followed. The screens were in the drying cabinet at 40 ° C ± 2 ° C to dried to constant weight and the detergent residue weighed out. The back is given as the average of the two individual determinations in percent. At Deviations of the individual results by more than 20% from each other are common further tests carried out; this was not the case in the present investigations required.

The tendency to gel when dissolved in the aqueous liquor was examined in a towel test and a bowl test: For this purpose 25 g of M1 were placed in 5 l of tap water (16 ° d, 30 ° C) in a dark plastic wash basin (for example dark red) interspersed. After 15 seconds, the agent was distributed in the bowl by hand. After a further 15 seconds, 1 blue terry towel was added to the wash liquor and moved as in a typical hand wash. After 30 seconds the wall of the bowl was wiped with the towel. Finally, after another 30 seconds, the towel was wrung out and visually graded. Here mean:
Grade 1: flawless, no discernible residues
Grade 2: tolerable, isolated, not yet disturbing residues
Grade 3: recognizable residues that are already annoying when critically assessed
from grade 4: clearly recognizable and annoying residues in increasing number and quantity

The wash liquor was decanted off and the residue was also visually graded after treatment with 5 to 10 ml of water. Here mean:
Grade 1: flawless, no discernible residues
Grade 2: tolerable, isolated, not yet disturbing residues, very finely divided, non-gelling when water is added
Grade 3: recognizable residues that are already annoying in the event of a critical assessment,
from grade 4: clearly recognizable and annoying residues in increasing number and quantity, agglomerate to lump formation, gelling when water is added.

M1 achieved grades of 1-2 in both the towel test and the bowl test.

For comparison, an agent V1 was produced, which has the same ingredients in the end product contained, but in which the copolymer is not in powder form, but as about 30 wt .-% aqueous solution had been introduced into the process. The excess water was then dried away in a fluidized bed. The bulk density of the extrudate was 770 g / l, the L test gave a value of 28%. In the towel test, V1 got the grade 3-4. in the bowl test even the grade 4.

The detergent M2 turned out to be particularly cheap for washing colored textiles lien. 65.71% by weight of the spray-dried granulate 2 were used to produce it (For composition see below) with 11.83% by weight of one produced in the fluidized bed Alkyl sulfate compounds (composition: 75% by weight C₁₂-C₁₈ alkyl sulfate, 17% by weight Sodium sulfate, 3% by weight sodium carbonate, 1% by weight water, remainder salts from solutions), 2.96% by weight of copolymeric sodium salt of acrylic acid and maleic acid (powder form), 6.99% by weight trisodium citrate dihydrate, 3.59% by weight polyethylene glycol with a relative Molecular mass of 4000 and 8.92 wt .-% C₁₂-C₁₈ fatty alcohol with an average of 7 EO mixed into a premix as described above and extruded.

In the sieve analysis given, the extrudate had a bulk density of 811 g / l and achieved a value of 2% in the solubility test (L test) described above. The bowl test gave a grade of 1-2.

Sieve analysis M1:

on sieve

1.60 mm 2% by weight
1.25 mm 90% by weight
1.00 mm 7% by weight
0.80 mm 0% by weight

through sieve

0.80 mm 1% by weight

For comparison, an agent V2 was again produced, which has the same ingredients in the end Product contained, but in which the copolymer is not in powder form, but as about 30 % By weight aqueous solution had been introduced into the process. The excess Water was then dried away in a fluidized bed. The bulk density of the Extrudate was well below 800 g / l, the L test showed a value above 20 %. The alkyl sulfate compound was not co-extruded, but according to the teaching of German added to the patent application P 195 19 139.0, the bulk density was of the extrudate at 780 g / l, the L test gave a value of 7% and the bowl test gave one Grade of 1-2.

After the preparation of 90 parts by weight of extrudate M2 with 3 parts by weight of enzyme gra nulate, 4 parts by weight of a foam inhibitor granulate, 2.5 parts by weight of a polymer (Repelotex®, commercial product from Rhône-Poulenc) and 0.5 part by weight of silica (for subsequent surface treatment) an agent A2 was obtained, which a Bulk weight of 820 g / l (increase in bulk weight!) With an L test value of 7% had the same bowl test score.

In contrast, 90 parts by weight of the comparative extrudate with admixed alkyl sulfate Compound prepared accordingly, the L test rose to 12%, while the bulk weight dropped to 735 g / l.

Agents according to the invention were also produced by introducing 3 to 5% by weight non-ionic surfactant over a spray-dried compound, which then with the nonionic surfactant had been processed.

Agents according to the invention were also produced, for example, by using a bin demixture of polyethylene glycol with a molecular weight of 4000 and a cetylstearyl alcohol with an average of 20 EO in a weight ratio of 1: 2 to 5: 1.

Products according to the invention were also manufactured by using as an alkylbenzenesulfonate Sodium C₉-C₁₃ alkylbenzenesulfonate powder of 85% by weight alkylbenzenesulfonate, 4.5% by weight Sodium carbonate, 3.5% by weight sodium sulfate, 2% by weight sodium chloride and 4% by weight What ser and unsulphated components were used in the premix. The extrudates showed in Ab depending on their other formulation values in the described L test of less than 15%  or less than 10%. Was used in the comparative examples instead of the alkylben zolsulfonat powder used a concentrated aqueous alkylbenzenesulfonate paste and the water then dried away, so all products showed a value in the L test above 20%.

Compositions of the spray-dried granules

Spray-dried granules 1:

26.30% by weight of C₉-C₁₃ alkylbenzenesulfonate
1.10% by weight tallow fatty alcohol with an average of 5 EO
1.40% by weight of C₁₂-C₁₈ sodium fatty acid soap
9.40% by weight sodium carbonate
4.00 wt .-% copolymer sodium salt of acrylic acid and maleic acid
39.50% by weight of zeolite A, based on anhydrous active substance)
2.80% by weight of amorphous sodium disilicate
13.60% by weight water
Remaining salts from solutions.

Spray-dried granules 2:

12.07% by weight of C₉-C₁₃ alkylbenzenesulfonate
3.00% by weight of C₁₂-C₁₈ sodium fatty acid soap
0.03% by weight sodium hydroxide
4.15% by weight sodium carbonate
0.80% by weight phosphate
0.80% by weight polyvinyl pyrrolidone
57.75% by weight of zeolite A, based on anhydrous active substance
4.15 wt .-% copolymer sodium salt of acrylic acid and maleic acid
16.65 wt% water
Remaining salts from solutions

Claims (24)

1. A process for the production of particulate detergents or cleaning agents or compounds or treated raw materials for this purpose with bulk weights above 600 g / l by joining detergent or cleaning agent compounds and / or raw materials with simultaneous or subsequent shaping, characterized in that initially a solid premix is produced which contains individual raw materials and / or compounds which are in the form of a solid at room temperature and a pressure of 1 bar and which have a melting point or softening point not below 45 ° C. and optionally up to 10% by weight at temperatures below 45 ° C and a pressure of 1 bar contains liquid nonionic surfactants, and using compression forces at temperatures of at least 45 ° C converted into a grain and, if necessary, then further processed or processed, with the provisos that

• - The premix is essentially anhydrous and
• - In the premix, at least one raw material or compound which is in solid form at a pressure of 1 bar and temperatures below 45 ° C but is present as a melt under the processing conditions, this melt serving as a polyfunctional, water-soluble binder Which, in the preparation of the agents, performs both the function of a lubricant and an adhesive function for the solid detergent or cleaning agent compounds or raw materials, but has a disintegrating effect when the agent is dissolved in an aqueous liquor.

2. The method according to claim 1, characterized in that the premix as a whole has a water content of not more than 15% by weight, this water not is in free form and preferably the content of non-zeolite and / or Silicate bound water not more than 10 wt .-% and in particular less than Is 7% by weight. 3. The method according to claim 1 or 2, characterized in that the premix in addition to the solid components up to 10 wt .-% at temperatures below 45 ° C and a pressure of 1 bar liquid nonionic surfactants, especially the alkoxylated alcohols usually used in washing or cleaning agents, such as fatty alcohols or oxo alcohols with a C chain length between 8 and 20 and ins particular has an average of 3 to 7 ethylene oxide units per mole of alcohol, wherein  the addition of the liquid nonionic surfactants and the disintegrant Binder in the premix is preferably carried out separately. 4. The method according to any one of claims 1 to 3, characterized in that the melting point of the individual raw materials used in the premix or the expansion point of the compounds used in the premix above 45 ° C and above preferably at least 50 ° C. 5. The method according to any one of claims 1 to 4, characterized in that in the pre Mixed compounds and raw materials are used, preferably 80% by weight at least 85% by weight and with particular preference at least 90% by weight have a significantly higher softening point or melting point than below the process conditions are achieved. 6. The method according to any one of claims 1 to 5, characterized in that in the compression step in a temperature range of a few degrees, for example 2 to 20 ° C, above the melting point or above the softening point. 7. The method according to any one of claims 1 to 6, characterized in that one or several binders are used, which are in a concentration of 8 g Bin Dissolve almost completely in 1 liter of water at 30 ° C within 90 seconds. 8. The method according to any one of claims 1 to 7, characterized in that the binder are used, which are preferably at temperatures up to 130 ° C up to a maximum of 100 ° C and in particular up to 90 ° C completely as a melt. 9. The method according to any one of claims 1 to 8, characterized in that the hard materials for the production of the solid and free-flowing premix initially in the room temperature to slightly elevated temperatures, preferably below the enamel temperature or the melting range of the binder and in particular Temperatures up to 35 ° C, in a conventional mixing and / or granulating device be placed. 10. The method according to any one of claims 1 to 9, characterized in that the bin demittel be added as the last component in the premix, their Zumi Research is carried out under such conditions that one is as equal as possible  moderate, homogeneous distribution of the binder - as a solidified melt or as a powder - Is reached in the solid mixture. 11. The method according to any one of claims 1 to 10, characterized in that the unit Processing of the binder takes place at temperatures at which the binder is in the form a melt is present, preferred temperatures of the melt being from 60 to 150 ° C, especially in the temperature range of 80 to 120 ° C. 12. The method according to any one of claims 1 to 11, characterized in that the Mixing is continued until the melt has solidified and the pre is present in solid, free-flowing form. 13. The method according to any one of claims 1 to 12, characterized in that a pre is used, the content of binder or binders at least 2 % By weight, but less than 15% by weight, preferably less than 10% by weight and below particular preference is 3 to 6 wt .-%, each based on the premix. 14. The method according to any one of claims 1 to 13, characterized in that a Ver driving temperature in the actual granulation, compacting, tableting, Pelleting or extrusion process above the melting point or above the Temperature at which the binder (or binders) is in the form of a melt is set, the process temperature but preferably not more than 20 ° C. is above the melting temperature or the melting range of the binder. 15. The method according to any one of claims 1 to 14, characterized in that the bin a melting temperature or a melting range up to a maximum of 150 ° C preferably up to 100 ° C and in particular up to 75 ° C and the method temperature 10 ° C and in particular a maximum of 5 ° C above the melting temperature or the upper temperature limit of the melting range of the binder. 16. The method according to any one of claims 1 to 15, characterized in that the duration the temperature effect between the mixing / homogenization of the premix and the shape, ie in the compression range between 10 seconds and is a maximum of 5 minutes and in particular is a maximum of 3 minutes. 17. The method according to any one of claims 1 to 16, characterized in that the Her position is carried out by extrusion, the premix compressed under pressure, plasti  extruded in the form of fine strands through the perforated die plate in the extruder head and finally by means of a rotating knife, preferably to a ball shaped (pearl-shaped) to cylindrical granules, is reduced and the Temperature control in the transition area of the extruder screw, the pre-distributor and the nozzle plate is designed such that the melting temperature of the binder or at least reaches the upper limit of the melting range of the binder, preferably wise but is exceeded. 18. The method according to claim 17, characterized in that the duration of the tempera impact in the compression area of the extrusion is a maximum of 2 minutes and in particular lies in a range between 30 seconds and 60 minutes. 19. The method according to any one of claims 1 to 18, characterized in that the ver Good did not seal temperatures immediately after leaving the manufacturing apparatus above 60 ° C, preferably between 35 and 60 ° C and especially between Have 40 to 55 ° C. 20. The method according to any one of claims 1 to 19, characterized in that a pre mixture with a relatively broad particle size distribution and relatively high proportions of fine grain into an end product with a relatively narrow particle size distribution and relatively small Shares in fine grain is transferred. 21. Particulate detergent or cleaning agent, compound or treated raw material for this purpose with bulk weights above 600 g / l, produced according to one of claims 1 to 20, with compounds and / or raw materials initially being used as a fixed is mixed, which individual raw materials and / or compounds that are available at room Temperature and a pressure of 1 bar as a solid and a melting point or softening point not below 45 ° C, and possibly up to 10 % By weight at temperatures below 45 ° C and a pressure of 1 bar liquid contains ionic surfactants, and using compression forces at temperatures converted into a grain at a temperature of at least 45 ° C. and then optionally further is processed or prepared, with the provisos that the premix is essentially Chen is anhydrous and in the premix at least one raw material or compound that or at a pressure of 1 bar and temperatures below 45 ° C in solid Form is present, but is present as a melt under the processing conditions, wherein the melt serves as a polyfunctional, water-soluble binder, which is used in the manufacture position of the means both the function of a lubricant and an adhesive function  for the solid detergent or cleaning agent compounds or raw materials, at which Redissolution of the agent in an aqueous liquor, however, has a disintegrating effect characterized in that the dissolving behavior of the particulate washing or cleaning agent from the dissolving behavior of the individual raw materials and compounds used is dependent. 22. Composition according to claim 21, characterized in that it is a honeycomb-like structure TUR has, the honeycombs are filled with solid. 23. Granulated or extruded detergent according to claim 21 or 22, characterized ge indicates that it is at least 80 wt .-% made according to the invention Compounds and / or treated raw materials and in particular at least 80% by weight of a base granulate or base extrudate produced according to the invention exists, it being particularly advantageous if the remaining constituents are also present Compounds or treated raw materials, which according to one of claims 1 to 20 were manufactured. 24. Agent according to one of claims 21 to 23, characterized in that it as Outer shell dusty or at least finely divided ingredients (the so-called Fine parts), which were adhered by melting agglomeration.