EP1012221B1 - Method for producing particulate detergents - Google Patents

Abstract

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

Description

The invention relates to a method for producing particulate detergents or cleaning agents or of multi-component components that are mixed with other Ingredients such agents result with the help of a specially adapted Granulation process and detergents or cleaning agents produced in this way.

Particulate detergents or cleaning agents with bulk weights above 600 g / l belong 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 go hand in hand, so that the consumer not only less volume, but also less Mass had to be dosed per washing or cleaning process. The increase in Bulk density and in particular the higher concentration of the detergent or cleaning-active substances were generally bought through from the point of view of the Consumers subjectively worse solubility due to the generally slower Dissolving speed of the agent used was caused. This unwanted The release delay is triggered, among other things, by the fact that a number of common practice anionic and nonionic surfactants and, above all, appropriate surfactant mixtures tend to form gel phases when dissolved in water. Such retribution can already with tenside contents of 10 wt .-%, based on the total agent, at usual amounts of surfactants occur in washing or cleaning agents. The inclination Experience has shown that the formation of gels also increases with the increasingly compact grain structure of the particles.

European patent EP 0 486 592 B1 describes granular or extruded Detergents or cleaning agents with bulk weights above 600 g / l, the anionic and / or nonionic surfactants in amounts of at least 15% by weight and up to about Contain 35 wt .-%. They are manufactured using a process in which a firm, free-flowing premix, which is preferably a plasticizer and / or lubricant contains aqueous surfactant pastes and / or aqueous polymer solutions at high pressures between 25 and 200 bar extruded and the strand after exiting the Hole shape by means of a cutting device to the predetermined granule dimension is cut and rounded. The premix consists at least in part solid ingredients, which may contain liquid ingredients such as at room temperature liquid nonionic surfactants are added. As said above, as plasticizers and / or In preferred embodiments, lubricants used aqueous preparations. However, there are also comparatively high-boiling organic liquids, if appropriate again in admixture with water, in question. The patent does not disclose any process conditions to be observed in the case of an anhydrous extrusion. The Extrudates produced can either already be used as washing or cleaning agents or afterwards with other granules or powder components to produce washing or Detergents are processed. Due to the high compactness of the grain and the relatively high surfactant levels, but also by the ball or Pearl shape, which is much smaller than conventional granules Depending on the surfactant combinations selected, it may have a surface the difficulties mentioned above.

From international patent application WO-A-93/15180 it is known that the dissolving speed of such extruded agents can be improved by using short-chain alkyl sulfates, in particular C ₈ - to a maximum of C ₁₆ -alkyl sulfates, which are specific to a particular mixture, in the solid premix Way into the premix. However, this measure is not sufficient in all cases to increase the dissolving speeds of the entire agent to the desired extent.

The German patent application DE 195 19 139 A1 proposes to solve the conflict between high degree of compaction of the individual grain, especially the extrudate, on the on the one hand and the rapid and, in particular, non-reworking requirements that are 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, at least one extruded and at least one not extruded , the maximum surfactant content of the extruded component including the soaps 15% by weight, based on the respective extruded component, should be. Further Surfactant components of the finished detergent or cleaning agent are by or several non-extruded component (s) introduced into the agent. This procedure solves the problem of gelling highly compressed and high-surfactant detergents or cleaning agents when used in an aqueous liquor, but it also contains one Series of new problems. There can be segregation processes and corresponding fluctuations in the reproducibility of the desired washing or cleaning result occur. In addition, the extruded portion of the media is not only of high density dried extrudates are also comparatively hard. Under the conditions the comparatively softer granulate content can be used for transport, storage and use the non-extruded component (s) are thus exposed to mechanical forces that partly to reduce it and thus to form dust and fine particles lead through abrasion.

Conventional methods generally work with both fixed and Ingredients of washing or cleaning agents liquid at room temperature; also watery Solutions and / or dispersions are used as granulation aids or as in the case of the European Patent EP 0 486 592 B1 as a plasticizer and / or lubricant in broad Scope used. Such procedures have the risk that already during the Production of detergents or cleaning agents can result in gel-like structures which Delay in dissolving contributes to redissolving in the aqueous liquor. Moreover own in particular the processes in which water, aqueous solutions or aqueous Dispersions are used as pelletizers, the disadvantage that in most Cases an energetically unfavorable drying must be followed in order to to obtain free-flowing or storage-stable end product, and also often very coarse agglomerates obtained must be crushed and / or sieved (see also "Size Enlargement by Agglomeration", W. Pietsch, John Wiley & Sons, 1990, page 180). On Another disadvantage of this method is that it is more solid and water-soluble constituents due to the water contained, especially under the Influence of pressure during extrusion for particle enlargement and crystallization can come, which in turn adversely affects the dissolving behavior of the finished funds impact.

A method for the production of heavy granules with the help of an aqueous Granulation aid is the two-stage granulation, initially in a conventional Mixer / granulator still plastic primary agglomerates are generated, which then in devices such as a rounder, rotocoater, marumerizer etc. with liquid Binder and / or dust subsequently treated and then usually dried become. The granulation and simultaneous rounding can, for example, in fluidized bed granulators, which contain a rotating disc. Solid starting materials are first fluidized in the fluidized bed and then with liquid binder that is fed into the fluidized bed via tangentially aligned nozzles is 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 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 anhydrous. These are for tableting in tablet presses and for roller compaction, the latter Processes are usually produced, which subsequently become granular, but irregular shaped products are broken. For this reason, in In some systems, so-called prebreakers are used to create the starting product for the The actual granulation or grinding step is more uniform in shape shape. Subsequently, unwanted fine and / or coarse particles of the so produced can Granules are sieved and optionally recycled.

International patent application WO-A-93/02176 describes a process for the production of solid detergents or cleaning agents with high bulk densities by combining solid and liquid detergent or cleaning agent raw materials with simultaneous or subsequent shaping, the solid constituents being, for example, anionic surfactants and builder substances and liquid ones Components nonionic surfactants are used, the latter being provided in an intimate mixture with a structure breaker such as polyethylene glycol or polypropylene glycol or ethoxylated C ₈ -C ₁₈ fatty alcohols with 20 to 45 ethylene oxide groups (EO). Preferred liquid nonionic surfactants are ethoxylated linear or methyl-branched alcohols in the 2-position which have 8 to 20 carbon atoms in the carbon chain and an average of 1 to 15 moles of ethylene oxide per mole of alcohol. In addition to such structure-breaking substances, water is also described as a structure breaker which is suitable in principle, the use of which is less preferred, however, since the agents can become poor in water during storage due to the internal drying of the agents and therefore no longer have the desired effect of improved dissolution rate by using a structure breaker or would no longer be fully effective. According to the teaching of this international patent application, the mixtures of nonionic surfactants and structural breakers, which are present either as a solution or as a dispersion, can be used in all known granulation processes in which separately produced compounds and / or raw materials are used. Use in an extrusion process according to international patent application WO-A-91/02047 (or European patent EP 0 486 592 B1) is also possible and even preferred. Accordingly, the use of aqueous solutions, pastes or aqueous dispersions is also suggested, the water, as stated above, not being used as a structure breaker and usually being dried off after the extrusion. Extrusion without the addition of water is not explicitly suggested; Even in the example section, aqueous solutions are added in addition to and separately from the nonionic surfactant / structure breaker mixture; above all, however, this document does not list any process conditions under which an anhydrous extrusion can be carried out.

European patent application EP 0 337 330 describes a method for increasing the Bulk weight of a spray-dried detergent by granulation in a mixer with the addition of nonionic 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 added in the mixer become. Ethylene glycols and propylene glycols can also be used as nonionic Connections are used.

European patent application EP 0 711 828 describes a process for the production of Tablets described, wherein a coated particulate product is pressed. The Wrapping substance is a water-soluble binder or disintegrant with melting temperatures between 35 and 90 ° C. It is stated here as an essential feature that the compacting / tableting is to be carried out at temperatures which at at least 28 ° C, but below the melting temperature of the binder.

From the international patent application WO-A-96/10071 a process for the production of granules with bulk densities of at least 650 g / l and surfactant contents of at least 40% by weight is known, the granulation process being carried out in one step in a mixer with a high shear rate Temperatures between room temperature and 60 ° C is carried out. Particles with a particle size between 0.1 µm and 500 µm serve as solid feedstocks, with at least 15% by weight of the particles having a particle size above 50 µm, but sufficiently small, fine particles are present so that a particularly large surface area is present of the solid feedstock results. Surfactant mixtures of anionic surfactants and nonionic surfactants in weight ratios of 2: 8 to 8: 2, which can have up to 20% by weight of water, serve as binders. Primary C ₁₂ -C ₁₅ alcohols with 3 to 7 EO are specified as nonionic surfactants. Surfactant mixtures which contain up to 20% by weight of water are particularly advantageous in the context of the stated process, since this increases the viscosity of the mixture and makes the process more controllable. In addition, the surfactant mixture can also contain polyethylene glycols.

The production of builder agglomerates is described in US Pat. No. 5,108,646, 50 to 75 parts by weight of aluminosilicates or crystalline phyllosilicates being agglomerated with 20 to 35 parts by weight of a binder. Suitable binders there are primarily highly viscous anionic surfactant pastes, which can contain up to 90% by weight of water. However, polymers such as polyethylene glycols with molecular weights between 1000 and 20,000 are also possible, as are mixtures of these and customary nonionic surfactants such as C ₉ -C ₁₆ alcohols with 4 to 8 EO, as long as their melting range is not below 35 ° C or below 45 ° C begins. The agglomeration takes place in a so-called intensive mixer with a very specific, relatively high energy input. With energy inputs above the specified values, over-agglomeration up to a dough-like mass occurs; with lower energy inputs, only finely divided powders or very light agglomerates with an undesirably wide grain spectrum are obtained.

In contrast, the object of the invention was particulate washing or Detergents or multi-component components that are mixed with other Ingredients such agents produce, which even when reduced Surface, especially with a spherical shape (pearl shape) an improved disintegration have in the dissolution in the aqueous liquor. The procedure should also be economical and can do without costly drying steps.

The invention therefore relates to a process for the production of particulate Detergents or cleaning agents or multi-component components or treated Raw materials that result in such agents when mixed with other ingredients Bulk weights above 600 g / l by assembling washing or Detergent compounds and / or raw materials with simultaneous or subsequent Shaping, whereby one first produces a premix, which individual raw materials and / or compounds that are solid at room temperature and a pressure of 1 bar are present, and then this premix using compression forces converted into a grain and, if necessary, subsequently processed or processed, which is characterized in that the premix essentially is anhydrous and one under the shaping conditions, in particular with Room temperature and a pressure of 1 bar, liquid molding aid in the form of a polymer swollen in non-aqueous solution, the non-aqueous Liquid component of the shaping aid from the following liquid at room temperature, di- or trihydric alcohols with boiling points (at 1 bar) above 80 ° C selected: n-propanol, iso-propanol, n-butanol, s-butanol, iso-butanol, Ethylene glycol, 1,2- or 1,3-propylene glycol, glycerin, di- or Triethylene or propylene glycol or mixtures thereof.

In the context of this invention, a condition is "substantially water-free" understand, in which the content of liquid, that is, not in the form of water of hydration and / or constitutional water less than 2% by weight, preferably less than 1% by weight and in particular even less than 0.5% by weight, in each case based on the premix, lies. Accordingly, water can essentially only be chemically and / or physically bound form or as part of the at temperatures below 45 ° C. a pressure of 1 bar as raw materials or compounds, but not as a liquid, solution or dispersion in the process of making the Premix are introduced. The premix advantageously has one overall Water content of not more than 15 wt .-%, so this water is not in liquid free form, but is chemically and / or physically bound, and it in particular it is preferred that the content of water not bound to zeolite and / or silicates in the solid premix not more than 10% by weight, preferably less than 7% by weight and with particular preference is a maximum of 2 wt .-% to 5 wt .-%.

Particulate detergents or cleaning agents are used in the context of the invention preferably understood those that have no dust-like portions and in particular none Have particle sizes below 200 microns. Such particle size distributions are in particular preferred, which at least 90 wt .-% particles with a Have a diameter of at least 400 µm. In a particularly preferred embodiment The laundry or cleaning agents and compounds produced consist of the invention or treated raw materials to at least 70 wt .-%, advantageously at least 80% by weight and, with particular preference, up to 100% by weight spherical (pearl-shaped) particles with a particle size distribution which at least Has 80 wt .-% particles between 0.8 and 2.0 mm. For particulate washing or Cleaning agents in the sense of the present invention can also be tablets with usual for washing or cleaning agent tablets for household applications Dimensions, for example with weights from 15 g to 40 g, in particular from 20 g to 30 g, with a diameter of about 35 mm to 40 mm.

Anhydrously swollen polymers which, in the context of the present invention, are Shaping aids used are those that are found in non-aqueous liquids lead gel-like conditions. Systems from non-aqueous systems are particularly suitable Liquid and polymer which is a at room temperature in the presence of the polymer have at least 20 times, in particular 300 to 5000 times higher viscosity than that non-aqueous liquid alone. The viscosity of the molding aid, that is Combination of non-aqueous liquid and polymer, is preferably at room temperature in the range from 200 mPas to 10,000 mPas, in particular from 400 mPas to 6,000 mPas, measured for example using a Brookfield rotary viscometer. at higher temperature, for example 60 ° C, the viscosity is preferably only relatively little from the values at room temperature and is preferably in the range of 250 mPas up to 2500 mPas. The liquids include the following liquid at room temperature, di- or trihydric alcohols with boiling points (at 1 bar) above 80 ° C, especially above 120 ° C; n-propanol, iso-propanol, n-butanol, s-butanol, iso-butanol, ethylene glycol, 1,2- or 1,3-propylene glycol, glycerin, di- or triethylene or propylene glycol or their mixtures, in particular glycerol and / or ethylene glycol. As polymers that swell into such anhydrous liquids lead, are suitable polyvinylpyrrolidone, polyacrylic acid, copolymers of acrylic acid and Maleic acid, polyvinyl alcohol, xanthan, partially hydrolyzed starches, alginates, amylopectin, Methyl ether, hydroxyethyl ether, hydroxypropyl ether and / or hydroxybutyl ether group-bearing Starches or celluloses, but phosphated starches such as starch disphosphate also inorganic polymers such as layered silicates and their mixtures. Among the Polyvinylpyrrolidones are those with a molecular weight of up to 30,000 prefers. Relative molecular mass ranges between are particularly preferred 3000 and 30,000, for example around 10,000. Among the preferred polymers also include hydroxypropyl starch and starch diphosphate. The concentration of the polymers in the anhydrous liquids is preferably 5% to 20% by weight. in particular about 6% to 12% by weight.

The content of shaping aids, based on the premix to be compressed, is preferably at least 2% by weight, but less than 20% by weight, in particular less than 15% by weight, with particular preference for amounts in the range from 3% by weight to 10% by weight. as the description of this invention proceeds, for convenience only one or the shaping aid. In doing so, however it should be made clear that the use of several different shaping aids is always inherent and mixtures of different shaping aids is possible.

Detergents or cleaning agents are understood to mean such compositions which are used for Washing or cleaning can be used without usually other ingredients must be added. A multi-substance mixture or compound, however, consists of at least 2 commonly used in washing or cleaning agents components; Compounds are usually only mixed with others Ingredients, preferably used together with other compounds. A treated one In the context of this invention, raw material is a relatively finely divided raw material which is characterized by the The inventive method was converted into a coarser particle. Is strictly a treated raw material in the context of the invention a compound if the Treatment agent a usually used in detergents or cleaning agents Ingredient is.

The ingredients used in the process according to the invention can be produced separately Compounds, but also raw materials, which are powdery or particulate (finely divided to coarse), but in any case at room temperature and a pressure of 1 bar - with the exception the possibly existing at temperatures below 45 ° C and a Pressure of 1 bar liquid non-ionic surfactants - in solid form. As a particular Particles can be, for example, beads or agglomerates produced by spray drying a granulation process etc. are used. The composition of the compounds in itself is not essential to the invention except for 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 constitutional water contains. In a preferred embodiment, over-dried compounds are used the premix. Such compounds can, for example, by Spray drying can be obtained, the temperature control being regulated so that the Tower outlet temperatures above 100 ° C, for example at 110 ° C or above lie. It is also possible that solid compounds are used in the premix as a carrier of liquid components, for example liquid nonionic surfactants or Silicone oil and / or paraffins. These compounds can contain water in the above Contain frames, the compounds are free-flowing and preferably also at higher temperatures of at least 45 ° C free-flowing or at least remain eligible. In particular, however, it is preferred that compounds with a maximum of 12% by weight and, with particular preference, a maximum of 9% by weight of water, based on the premix. Free water, i.e. water that is not in is bound to a solid in some form and is therefore "in liquid form" preferably not at all in the premix, since very small amounts are already present, for example by 0.2 or 0.5% by weight, based on the premix, is sufficient to achieve this to dissolve water-soluble shaping agents. This would have the consequence that the The melting point or softening point of the end product is reduced and it would lose both flow and bulk weight.

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. So is the water that is present on builder substances such as zeolite or silicates, 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 bound Water in the premix is not more than 10% by weight and / or the content of water not bound to zeolite and / or silicates less than 7% by weight 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 45 ° C non-aqueous liquid components, excluding those at room temperature liquid shaping aid, is preferably up to 10% by weight, advantageously up to 6% by weight, based in each case on the premix. In particular solid compounds are used in the premix, which are customary at temperatures contain liquid nonionic surfactants below 45 ° C and a pressure of 1 bar and according to all known types of production - for example by spray drying, Granulation or spraying of carrier beads - were produced separately. In this way premixes can be produced, 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.

Compounds that contain water in the form specified above and / or as a carrier for Liquids, in particular for nonionic surfactants which are liquid at room temperature, thus contain these ingredients which are liquid at room temperature and according to the invention can preferably be used have no softening point below 45 ° C. The separately used raw materials also have a melting point of preferably at least 45 ° C. Preferably the melting point is respectively the softening point of all individual raw materials and compounds used in the premix above 45 ° C and advantageously at least 50 ° C.

In a preferred embodiment of the invention, at least 80% by weight, in particular at least 85% by weight and with particular preference at least 90% by weight of all compounds and individual raw materials used in the premix with the exception of Room temperature liquid shaping aid a significantly higher softening point or melting point on than the temperatures under the process conditions the shape can be achieved. In practice, the molding temperatures for economic reasons alone not above 150 ° C, preferably not above 120 ° C. Thus at least 80% by weight of the used compounds and individual raw materials a softening point respectively Have a melting point above 150 ° C at normal pressure (1 bar).

The premix can be in addition to the solid components and at room temperature liquid shaping aid up to 10 wt .-% at temperatures below 45 ° C. and a pressure of 1 bar liquid non-ionic surfactants, especially those usually in Detergents or cleaning agents used alkoxylated alcohols, such as fatty alcohols or Oxo alcohols with a C chain length between 8 and 20 and especially an average of 3 up to 7 ethylene oxide units per mole of alcohol. The addition of the liquid nonionic Surfactants can be used in amounts that still ensure that the premix in pourable form is present. If such liquid nonionic surfactants in the premix are introduced, it is preferred that liquid nonionic surfactants and disintegrating acting molding aids are introduced separately from one another in the process. In a preferred embodiment of the invention, the liquid surfactants are in one continuous production process, in particular by means of nozzles on the powder stream applied and absorbed by the latter.

However, the premix also contains at least one raw material or at least one compound, which, as stated above, serves as a shaping aid. The Shaping aid in the form of the water-free swollen polymer can before Shaping step are mixed with the other components of the premix. This is particularly preferred if the shaping by an extrusion step or with the help of a tableting or other pressing process. It can also be used during the Shaping are sprayed onto the premix or added dropwise to the premix, which is particularly preferred for shaping by means of build-up granulation. The temperature during the shaping step is preferably at room temperature respectively the temperature resulting from the energy input of the shaping device, es However, it is also possible to premix and, if necessary, separately during the Shaping aids to be added at higher temperatures, for example 35 ° C to 80 ° C to heat, with temperatures in the range of 45 ° C to 65 ° C can be particularly advantageous.

It has also proven to be advantageous if the shaping aid in the Process step of the compression molding as homogeneous as possible in the one to be compressed Is well distributed. Without wishing to limit yourself to this theory, the applicant is believes that through a homogeneous distribution of the shaping aid in the sense of a binder within the premix under the process conditions of Compression of the solid compounds and any existing raw materials so enclosed by the binder and then glued together that the finished products are made almost exactly from these many small individual particles are built up by the binder, which is preferably thin Partition between these individual particles takes over, are held together. In the idealized form can be assumed to have a honeycomb-like structure, these honeycombs are filled with solids (compounds or individual raw materials). at Contact with water, also with cold water, for example at the beginning of a automatic washing process, these thin partitions loosen or disintegrate almost instantaneously; Surprisingly, this is also the case if that Shaping aid itself is not quickly soluble in water at room temperature. Preferably, however, such shaping aids are used, which are in a test procedure as given below in a concentration of 8 g Shaping aids to 1 liter of water at 30 ° C almost within 90 seconds let it solve completely. In some cases, however, it may be beneficial to have an additive to adjust the solubility in a controlled manner, i.e. to delay it.

The molding aid must be of the type that the adhesive properties the temperatures of the shape come into play. On the other hand, it is also essential for the choice of the type and the amount of shaping aid used, that the binding properties after the shaping step within the end product lost, the cohesion of the end product is thus ensured, however, that The end product itself is not glued under normal storage and transport conditions. It must be surprising that when using the liquid at room temperature Shaping aid is still obtained an end product that is neither at room temperature still at slightly elevated temperatures around 30 ° C, i.e. at summer temperatures and under storage or transport conditions, tends to stick.

The assembly of the detergent or cleaning agent compounds and / or raw materials under Simultaneous or subsequent shaping can be carried out by conventional methods in which Compaction forces such as granulating, compacting, for example Roll compacting or extruding, or tableting, optionally with addition usual explosives, and pelleting. It can be used as a prefabricated compound spray-dried granules can also be used in the premix, the invention is based on this however, in no way limited. Rather, the method according to the invention offers do not use spray-dried granules, since very fine-particle raw materials are also included Dust-like parts can be processed without problems according to the invention without first pre-compounded, for example to be spray dried.

The essentially water-free procedure not only enables that Peroxy bleach can be processed without loss of activity, it will also enables peroxy bleach and bleach activators to be combined in one particle process without fear of serious loss of activity.

In a preferred embodiment of the invention, the condensing shape of the Process carried out with the aid of an agglomeration step, wherein the Premix in a suitable device agglomerating granulated and the above defined shaping aids take on the role of a binder. The Granulation processes can be carried out continuously or batchwise. there one preferably proceeds in such a way that the solid components of the to be compressed Premixed in a granulator, which can also be used as a mixer, submitted, if necessary by adding a liquid nonionic surfactant existing dust binds and introduces the shaping aid into the granulator. The Desired average particle size of the granulate can be determined by the type and amount of shaping aid and about the machine and operating parameters, such as Speed and dwell time as well as temperature can be set. As suitable granulators can for example pelletizing plates, rotary drums, ploughshare mixers with chopper Lödige® company, high-performance mixer with rotating mixing tank and swirler for Example from the companies Laeis Bucher® or Eirich®, intensive mixer with shaving heads for Example of the company LIPP Mischtechnik® or Imcatec®, Drais®, Fukae® or Forberg® mixer as well as the so-called Rotorcoater® from Glatt® with horizontal and with inclined turntable up to 50 °. Lödige® CB mixers, zig-zag mixers are less suitable from PK-Niro®, a Ballestra® chain mix and Hosokawa® or Schugi® mixers. A fluid bed or a horizontal mixer, for example a Nautamixer® also less suitable. Within the scope of this embodiment of the invention It is preferred method at room temperature or by the Energy input of the mixer or granulator resulting temperature, that is to work without a separate heating step, such as in the international one Patent application WO 94/13779 and the prior art cited therein. An advantage of the method according to the invention is that one does not rely on one for example, the two-stage described in European patent application EP 0 367 339 Pelletizing process, in which pellets first in a high speed mixer and then compressed in a slow-running mixer and granulator, is instructed, but using the water-swollen polymer, the compressing Can perform granulation in just one step.

Agents in tablet form according to the invention can be produced by means of conventional tablet presses, for example eccentric presses or rotary presses, with compression pressures in the range from, for example, 200 · 10 ⁵ Pa to 1 500 · 10 ⁵ Pa.

In a further preferred embodiment of the method according to the invention the solids for the preparation of the solid and free-flowing premix initially at room temperature to slightly elevated temperatures, preferably in the range of room temperature are up to 35 ° C in a conventional mixing and / or granulating with each other mixed. The compression step of the method according to the invention is then carried out using an extrusion of the premix obtained in this way, for example in the European patent EP 0 486 592 B1 or international patent applications WO-A-93/02176 and WO-A-94/09111. The premix is under pressure extruded and the strand after exiting from the hole shape by means of a Cutting device tailored to the predeterminable granule dimension. The homogeneous and solid premix usually contains a plasticizer and / or lubricant, which causes the premix under the pressure or under the entry specific work is plastically softened and becomes extrudable. According to the European patent EP 0 486 592 B1 particularly includes anionic surfactants such as alkylbenzenesulfonates and / or (fatty) alkyl sulfates, but also polymers such as polymeric polycarboxylates. With help the method according to the invention, however, it is possible to fully known on such fixed To dispense with plasticizers and / or lubricants, since the function of a lubricant from the Shaping aids defined above can be perceived. The shaping aid prevents or at least reduces sticking Apparatus walls and compaction tools. This does not only apply to processing in the Extruder, but equally for processing, for example, in continuous working mixers / granulators or rollers ..

To explain the actual extrusion process, we hereby expressly refer to the referenced above patents and patent applications. In a preferred embodiment the invention, the premix is preferably continuously one Planetary roller extruder or a 2-shaft extruder or 2-screw extruder fed with co-rotating or counter-rotating screw guide, its housing and whose extruder pelletizing head must be heated to the predetermined extrusion temperature can. The premix is mixed in under the shear of the extruder screws Pressure, which is preferably at least 25 bar, at extremely high throughputs in Depending on the apparatus used, however, it can also be below that, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally the extrudate, preferably by means of a rotating knife, approximately reduced spherical to cylindrical granules. The hole diameter of the Perforated nozzle plate and the strand cut length are set to the selected one Granule dimension matched. In this embodiment, the production of Granules of a substantially uniformly predeterminable particle size, in which individual absolute particle sizes can be adapted to the intended application. In general, particle diameters up to at most 0.8 cm are preferred. Important Embodiments see the production of uniform granules in the Millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from about 0.8 to 3 mm. The length / diameter ratio of the chipped primary In an important embodiment, granules are in the range from about 1: 1 to about 3: 1. Alternatively, extrusions / pressings can also be carried out in low-pressure extruders Kahl press or in the Bextruder®.

It is further preferred that the still plastic primary granules give a further shape To supply processing step; the primary granulate after the compression step any edges present are rounded, so that ultimately spherical to approximately spherical grains can be obtained if they are not already compacting in the first Shaping step arise. If desired, small amounts of can be added at this stage Dry powder, for example zeolite powder such as zeolite NaA powder, can also be used.

This shape can be done in standard rounding machines. It is towards make sure that only small amounts of fine grain are produced in this stage. A drying, which are preferred in the aforementioned prior art documents Embodiment is described, but is unnecessary in the context of the present Invention, since the method according to the invention is essentially anhydrous, that is, without the Free, unbound water is added.

It is the essence of a preferred embodiment of the invention that the particle size distribution of the premix is much broader than that of the invention manufactured and end product according to the invention. The premix can be essential Larger fractions of fine grain, even dust, possibly also coarser-grained fractions included, but it is preferred that a premix with a relatively broad particle size distribution and relatively high levels 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 of the invention is essentially anhydrous - i.e. with the exception water-free ("impurities") of the solid raw materials used - is carried out 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 omitting a subsequent one 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 redissolving behavior of those produced according to the invention Detergents or cleaning agents, in contrast to conventionally manufactured agents, are now available in the is essentially only dependent on the dissolving behavior of the individual components; the more Components that are soluble relatively quickly are included, the faster they are finished agent soluble; the more relatively slowly soluble components are contained, the more The means are also slowing down more slowly. 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 750 and 800 g / l, obviously no longer matter. The agents, compounds and treated raw materials thus show an improved dissolving speed such agents, compounds and treated raw materials, which have the same final composition have, but not produced by the inventive method were not swollen under anhydrous conditions using an anhydrous one Polymers were used as shaping aids.

The dissolving behavior of the particulate washing or Cleaning agent which was produced by the method according to the invention, is only of the dissolving behavior of the individual raw materials and Compounds dependent. Without wanting to limit yourself to this theory, it works The 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.

The invention further relates to the method according to the invention Compounds and treated raw materials, such as builder granules, Bleach activator granules or enzyme granules. Especially show treated raw materials an astonishingly high dissolution rate in water, especially when the raw material is on was used in a very finely divided, optionally ground form.

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

The bulk density of process end products produced according to the invention is preferably meadow above 700 g / l, in particular between 750 and 1000 g / l. Even if the granules with other ingredients, which have lower bulk weights, are reduced the bulk density of the final product is not as normal as expected would have been. It is believed that approximately spherical agents, and particularly extrudates, 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 a spherical structure nor such a high bulk density exhibit.

The particulate process end products obtained can be used either directly as washing or Detergents used or previously treated by conventional methods and / or be processed. The usual aftertreatments include, for example, powdering with finely divided ingredients of washing or cleaning agents, for example zeolites, whereby the bulk density may be increased further. A preferred one Post-treatment, however, also represents the procedure according to the German one Patent applications DE 195 24 287 and DE 195 47 457 are dusty or at least finely divided ingredients (the so-called fines) to the invention manufactured particulate process end products, which serve as a core, glued are and thus arise means that these so-called fines as an outer shell exhibit. This is advantageously done in turn by an agglomeration step, where the shaping aids of the process according to the invention are used as binders can be used. For also possible melting agglomeration of the fines to the base granules according to the invention and produced according to the invention expressly to the disclosure in the German patent applications DE 195 24 287 A1 and DE 195 47 457 A1.

Processing is generally understood to mean that those prepared according to the invention Particulate process end products serve as a compound, to which other ingredients, if necessary, other compounds can also be added. Here is the description of the cited patent applications and patent specifications, in particular on the European patent EP 0 486 592 B1 and the German patent applications DE 195 19 139, DE 195 24 287 and DE 195 47 457 referenced. In addition to enzymes, Bleach activators and foam inhibitors are mainly salts such as silicates (crystalline or amorphous) including metasilicate, carbonate, bicarbonate, sulfate, bisulfate, citrate or others Polycarboxylates, but also organic acids such as citric acid in the processing admixed. It is particularly preferred that the admixing components in granular Shape and are used with a particle size distribution that on the Particle size distribution of the agents and compounds produced according to the invention is coordinated.

In a preferred embodiment of the invention, a particulate detergent provided that at least 80 wt .-% of compounds produced according to the invention and / or treated raw materials. In particular, there is at least 80% by weight from a base granulate produced according to the invention. The remaining ingredients can be prepared and mixed by any known method. However, it is preferred that also these remaining constituents, which compounds and / or treated Raw materials can be produced by the method according to the invention. In particular, this enables basic granules and remaining components to be approximated to produce the same pourability, bulk density, size and particle size distribution. It is also possible to mix the mixtures prepared according to the invention Compounds and / or treated raw materials with the remaining ingredients mentioned to produce larger moldings, for example tablets. As a special advantage, however to evaluate that it is actually possible using the method according to the invention all components of a complete washing or cleaning agent as a premix insert and granulate water-free into beads.

There now follows a detailed description of the possible ingredients of the invention Agents and the components used in the process according to the invention.

Important ingredients of the agent and ingredients according to the invention Methods used are surfactants, especially anionic surfactants preferably at least in amounts of 0.5% by weight in the agents according to the invention or the agents produced according to the invention are included. Which includes especially sulfonates and sulfates, but also soaps.

Preferred surfactants of the sulfonate type are C ₉ -C ₁₃ alkylbenzenesulfonates, olefin sulfonates, that is to say mixtures of alkene and hydroxyalkanesulfonates, and also disulfonates of the kind obtained, for example, from C ₁₂ -C ₁₈ monoolefins having an end or internal double bond by sulfonating Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C ₁₂ -C ₁₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Also suitable are the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, which by α-sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin with 8 to 20 C- Atoms in the fatty acid molecule and subsequent neutralization to form water-soluble mono-salts are considered. These are preferably the α-sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids, with sulfonation products of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3% by weight. %, can be present. In particular, α-sulfofatty acid alkyl esters are preferred which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters. The methyl esters of α-sulfofatty acids (MES), but also their saponified disalts, are used with particular advantage. Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters as well as their mixtures, such as those produced by esterification by a monoglycerol with 1 to 3 mol fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol glycerol be preserved. As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid half esters of the C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are particularly preferred from the point of view of washing technology. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants. The sulfuric acid monoesters of the straight-chain or branched C ₇ -C ₂₁ alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl branched C ₉ -C ₁₁ alcohols with an average of 3.5 mol of ethylene oxide (EO) or C ₁₂ -C ₁₈ -Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are normally used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight. Further preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ to C ₁₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which are nonionic surfactants in themselves. Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof. Fatty acid derivatives of amino acids, for example of N-methyl taurine (taurides) and / or of N-methyl glycine (sarcosides) are suitable as further anionic surfactants. The sarcosides or sarcosinates, and in particular sarcosinates of higher and optionally mono- or polyunsaturated fatty acids such as oleyl sarcosinate, are particularly preferred. Other suitable anionic surfactants are, in particular, soaps, preferably in amounts of 0.2 to 5% by weight. Saturated fatty acid soaps are particularly suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. The known alkenylsuccinic acid salts can also be used together with these soaps or as a substitute for soaps.

The anionic surfactants (including the soaps) can be in the form of their sodium, potassium or Ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine, available. The anionic surfactants are preferably in the form of their sodium or Potassium salts, especially in the form of the sodium salts. The anionic surfactants are in the agents according to the invention or are in the inventive Process preferably in amounts of 1 to 30% by weight and in particular in amounts of 5 contain up to 25 wt .-% or used.

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

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ alcohols with 3 EO or 4 EO, C ₉ -C ₁₁ alcohols with 7 EO, C ₁₃ -C ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -C ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₁₂ -C ₁₄ alcohol with 3 EO and C ₁₂ -C ₁₈ alcohol with 7 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.

The nonionic surfactants also include alkyl glycosides of the general formula RO (G) _x , 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 C atoms and G is the symbol is 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. Also suitable are polyhydroxy fatty acid amides of the formula (I) in which R ² CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{3 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.

in der R⁴ für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R⁵ für einen linearen, verzweigten oder cyclischen Alkylenrest oder einen Arylenrest mit 2 bis 8 Kohlenstoffatomen und R⁶ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C₁-C₄-Alkyl- oder Phenylreste bevorzugt sind, und [Z] für einen linearen Polyhydroxyalkylrest, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes steht. [Z] wird auch hier vorzugsweise durch reduktive Aminierung eines Zuckers wie Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose erhalten. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können dann beispielsweise nach der Lehre der internationalen Patentanmeldung WO-A-95/07331 durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden. Eine weitere Klasse bevorzugt eingesetzter nichtionischer Tenside, die entweder als alleiniges nichtionisches Tensid oder in Kombination mit anderen nichtionischen Tensiden, insbesondere zusammen mit alkoxylierten Fettalkoholen und/oder Alkylglykosiden, eingesetzt werden, sind alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette, insbesondere Fettsäuremethylester, wie sie beispielsweise in der japanischen Patentanmeldung JP 58/217598 beschrieben sind oder die vorzugsweise nach dem in der internationalen Patentanmeldung WO-A-90/13533 beschriebenen Verfahren hergestellt werden. Als Niotenside sind C₁₂-C₁₈-Fettsäure. methylester mit durchschnittlich 3 bis 15 EO, insbesondere mit durchschnittlich 5 bis 12 EO bevorzugt. Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokosalkyl-N,N-dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid, und der Fettsäurealkanol-amide können geeignet sein. Die Menge derartiger nichtionischer Tenside beträgt vorzugsweise nicht mehr als die der ethoxylierten Fettalkohole, insbesondere nicht mehr als die Hälfte davon.The polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose. The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

in which R ^{4 represents} a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{5 represents} a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R ^{6 represents} a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C ₁ -C ₄ -alkyl or phenyl radicals being preferred, and [Z] for a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical. [Z] is also preferably obtained here by reductive amination of a sugar such as glucose, fructose, 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, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst. Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols 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 fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533. C ₁₂ -C ₁₈ fatty acids are nonionic surfactants. methyl ester with an average of 3 to 15 EO, in particular with an average of 5 to 12 EO preferred. Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanol amides can also be suitable. The amount of such nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

So-called gemini surfactants can be considered as further surfactants. Below are in generally understood such compounds, the two hydrophilic groups and two hydrophobic Have groups per molecule. These groups are usually characterized by a so-called "Spacer" separated from each other. This spacer is usually a carbon chain, which should be long enough that the hydrophilic groups have a sufficient 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. out. In exceptional cases 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 German patent application DE 43 21 022 A1 or Dimer alcohol bis and trimer alcohol tris sulfates and ether sulfates according to the German Patent application DE 195 03 061 A1. End-capped dimers and trimers Mixed ethers according to German patent application DE 195 13 391 stand out especially by their bi- and multifunctionality. So have the named endgroup-sealed surfactants have good wetting properties and are low-foaming, so that they are particularly suitable for use in machine washing or cleaning processes suitable. Gemini polyhydroxy fatty acid amides or poly polyhydroxy fatty acid amides can also be used. as described in international patent applications WO-A-95/19953, WO-A-95/19954 and WO95-A- / 19955 can be described.

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

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, for example, zeolite MAP® (commercial product from Crosfield) is used. 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 stabilized suspension which is still moist from its production. In the event that the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to Is 20 and 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 Na ₂ Si ₂ O ₅ .yH ₂ O are preferred. The preferred builder substances also include amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ 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 be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions with a size of 10 nm to a few hundred nm, 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 compared to conventional water glasses, are described, for example, in German patent application DE 44 00 024 A1. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

It goes without saying that the generally known phosphates are also used as builder substances possible, provided that such use is not avoided for ecological reasons should be. The sodium salts of orthophosphates, pyrophosphates, are particularly suitable 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 washing ability to lead.

Suitable substitutes or partial substitutes for the zeolite are also layer silicates of natural and synthetic origin. Layered silicates of this type are known, for example, from patent applications DE 23 34 899, EP 0 026 529 and DE 35 26 405. Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here. Suitable sheet silicates, which belong to the group of water-swellable smectites, are, for example, montmorrilonite, hectorite or saponite. In addition, small amounts of iron can be incorporated into the crystal lattice of the layered silicates according to the above formulas. Furthermore, due to their ion-exchanging properties, the layered silicates can 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 depends on the swelling state or the type of processing. Layer silicates which can be used are known, for example, from US Pat. No. 3,966,629, EP 0 026 529 and EP 0 028 432. Layered silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.

Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these. The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular. These acids are preferably used in anhydrous form if they are used in the premix according to the invention and are not subsequently added. Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure for is the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Both 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 molar masses in the range from 2000 to 30000 can be used. A preferred dextrin is in European patent application EP 0 703 292 A1 described. The oxidized derivatives of oligosaccharides, for example of such dextrins, are their reaction products with oxidizing agents which are able to oxidize at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP 0 232 202, EP 0 427 349, EP 0 472 042 and EP 0 542 496 and international patent applications WO 92/18542, WO 93/08251, WO 94/28030 , WO 95/07303, WO 95/12619 and WO 95/20608. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous. Oxidized oligosaccharides according to German patent application DE 196 00 018 are also suitable. Other suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate. Also particularly preferred in this context are glycerol disuccinates and glycerol trisuccinates, as described, for example, in US Pat. Nos. 4,524,009, 4,639,325, European Patent Application EP 0 150 930 and Japanese Patent Application JP 93/339896. Suitable amounts used in formulations containing zeolite and / or silicate are from 3 to 15% by weight. Further useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Such cobuilders are described, for example, in international patent application WO 95/20029. Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. The content of (co) polymeric polycarboxylates in the compositions is within the usual range and is preferably 1 to 10% by weight. %. Also particularly preferred are biodegradable polymers composed of more than two different monomer units, for example those which, according to German patent application DE 43 00 772, are salts of acrylic acid and maleic acid, as well as vinyl alcohol or vinyl alcohol derivatives, or according to German patent DE 42 21 381 Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives. Other preferred copolymers are those which are described in German patent applications DE 43 03 320 and DE 44 17 734 and which preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers. Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE 195 40 086 that, in addition to cobuilder properties, they also have a bleach-stabilizing effect. Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP 0 280 223. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

In addition, the agents can also contain components that make the oil and fat washable made of 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 cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups from 15 to 30% by weight and from 1 to 15% by weight of hydroxypropoxyl groups, in each case based on the nonionic cellulose ether, and those from the prior art Polymeric esters of phthalic acid and / or terephthalic acid known in the art monomeric and / or polymeric diols or their derivatives, in particular Polymers made from ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionically modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic acid and terephthalic acid polymers.

Other suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates such as the above-mentioned dissolving-delayed silicates or mixtures thereof; In particular, alkali carbonate and amorphous alkali silicate, especially sodium silicate with a molar ratio Na ₂ O: SiO ₂ of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used. The sodium carbonate content of the agents is preferably up to 20% by weight, advantageously between 5 and 15% by weight. The content of sodium silicate in the agents is, if it is not to be used as a builder, in general up to 10% by weight and preferably between 2 and 8% by weight, otherwise it can be higher. According to the teaching of international patent application WO 94/01222, alkali metal carbonates can also be replaced by sulfur-free amino acids and / or salts thereof having 2 to 11 carbon atoms and optionally a further carboxyl and / or amino group. In the context of this invention, it is possible for the alkali metal carbonates to be partially or completely replaced by glycine or glycinate.

Other detergent ingredients include graying inhibitors, foam inhibitors, Bleaching agents and bleach activators, optical brighteners, enzymes, fabric softening agents Substances, colors 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 acidifying components Bisulfates and / or bicarbonates or the above-mentioned organic polycarboxylic acids, which can also be used as builder substances at the same time. Particularly preferred is the use of citric acid, which is either subsequently admixed (usual procedure) or - in anhydrous form - in a solid premix is used.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. The bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, advantageously using perborate monohydrate or percarbonate.

Compounds which are aliphatic under perhydrolysis conditions can be used as bleach activators Peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid can be used. Suitable are substances which contain O- and / or N-acyl groups of the number of carbon atoms mentioned and / or where appropriate carry substituted benzoyl groups. Multi-acylated alkylenediamines are preferred, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular Tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and those from German patent applications DE-A-196 16 693 and DE-A-196 16 767 known enol esters and acetylated sorbitol and mannitol respectively their mixtures described in European patent application EP-A-0 525 239 (SORMAN), acylated sugar derivatives, in particular pentaacetyl glucose (PAG), pentaacetyl fructose, Tetraacetylxylose and Octaacetyllactose as well as acetylated, optionally N-alkylated Glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, from international patent applications WO-A-94/27970, WO-A-94/28102, WO-A-94/28103, WO-A-95/00626, WO-A-95/14759 and WO-A-95/17498 are known. The hydrophilic known from German patent application DE-A-196 16 769 substituted acylacetals and those in German patent application DE-A-196 16 770 and the international patent application WO-A-95/14075 described acyllactams also preferably used. Also from the German patent application DE-A-44 43 177 known combinations of conventional bleach activators can be used become. Such bleach activators are in the usual range, preferably in Amounts from 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight. related to total means included.

When used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C ₁₈ -C ₂₄ fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of different foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes. The foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.

The salts of polyphosphonic acids are preferably the neutral sodium salts for example, 1-hydroxyethane-1,1-diphosphonate, diethylenetriaminepentamethylenephosphonate or ethylenediaminetetramethylenephosphonate in amounts of 0.1 to 1.5 % By weight used.

In particular, enzymes from the hydrolase class, such as proteases, Lipases, cutinases, amylases, cellulases or their mixtures in question. Also Oxireductases are suitable. From bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens obtained enzymatic active ingredients. Proteases of the subtilisin type are preferred and in particular proteases derived from Bacillus lentus are used. Are there Enzyme mixtures, for example from protease and amylase or protease and lipase or Protease and cellulase or from cellulase and lipase of particular interest. Also Peroxidases or oxidases have proven to be suitable in some cases. To the Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and Pectinases. Cellobiohydrolases, endoglucanases and β-glucosidases are preferably used as cellulases, which are also called cellobiases, or mixtures of these used. Because the different cellulase types are characterized by their CMCase and Avicelase activities can distinguish them by targeted mixtures of the cellulases desired activities. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules can, for example, be approximately 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-%.

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

Graying inhibitors have the task of removing the 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 acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters cellulose or starch. Also water-soluble containing acidic groups Polyamides are suitable for this purpose. Soluble starch preparations and use starch products other than the above, e.g. degraded starch, Aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, are preferred Cellulose ethers, such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methylhydroxyethyl cellulose, methyl hydroxypropyl cellulose, Methyl carboxymethyl cellulose and mixtures thereof, and also polyvinyl pyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition.

As optical brighteners, the agents can be derivatives of diaminostilbenedisulfonic acid or their Contain alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similar connections, which instead of the morpholino group is a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group. Can continue Present brighteners of the substituted diphenylstyryl type, e.g. the alkali salts 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) -diphenyls. Mixtures of the aforementioned brighteners can also be used.

Examples example 1

Agents E1 to E5, as well as agents V1 and V2 not according to the invention (for composition, see Table 1), were prepared as follows:

In a batch mixer (Lödige® ploughshare mixer 20 liters) with a cutter head shredder (Chopper) was equipped, a premix from the in Table 1 specified ingredients, with the addition of the nonionic surfactant in the powder stream made by spraying through nozzles. Then the mixture became 2 Homogenized for minutes and then fed to a 2-screw extruder, whose pelletizing head was preheated to temperatures between 50 ° C and 65 ° C. Under The premix was plasticized under the shear action of the extruder screws and at given by the extruder head perforated die plate in Table 1 fine strands with a diameter of 1.4 mm extruded, which after the Nozzle outlet to a roughly spherical granulate using a knock-off knife were crushed (length / diameter ratio about 1, hot cut). The accruing warm granules were used for one minute in a rounder of the type available on the market Marumerizer® rounded and, if necessary, coated with a fine powder.

The bulk density of the extrudates produced as well as their respective values in the below Solubility test (L test) described are also given in Table 1.

It can be seen that when using the water-free swollen polymers according to the invention WQPI to WQP 4, even if they are used in smaller quantities than one usual plasticizing agent, with significantly (at least 30%) lower extrusion pressures high quality products can be obtained.

To determine the residue or solubility behavior (L test) in a 2 l beaker 8 g of the agent to be tested with stirring (800 rpm with laboratory stirrer / propeller stirring head Centered 1.5 cm from the beaker bottom) 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 would be rinsed over the sieve with very little cold water. The sieves were dried in a drying cabinet at 40 ° C ± 2 ° C to constant weight and the Balanced detergent residue. There was a double determination; the backlog will expressed as a percentage as the mean of the two individual determinations. In the event of deviations of the individual results by more than 20% of one another are usually further attempts carried out; however, this was not necessary in the present investigations.

For comparison, a further agent V3 was prepared which contained the same ingredients in the end product as E2 , but in which the copolymer had not been introduced into the process in an anhydrous, swollen form, but rather as an approximately 30% by weight aqueous solution. The excess water was then dried off in a fluidized bed. The bulk weight of extrudate V3 was 770 g / l, the L test gave a value of 28%.

Compositions of the spray-dried powders SP1 and SP2:

Spray-dried powder 1:

26.00% by weight of C ₉ -C ₁₃ alkylbenzenesulfonate
8.50% by weight sodium carbonate
41.33% by weight of zeolite A, based on anhydrous active substance
9.50% by weight of copolymeric sodium salt of acrylic acid and maleic acid
1.00% by weight phosphonate
12.00% by weight of water
0.42% by weight of optical brighteners
Remaining salts from solutions

Spray dried powder 2:

26.00% by weight of C ₉ -C ₁₃ alkylbenzenesulfonate
42.83% by weight of zeolite A, based on anhydrous active substance
5.50% by weight of copolymeric sodium salt of acrylic acid and maleic acid
1.00% by weight phosphonate
5.00% by weight sodium carbonate
6.00% by weight sodium sulfate
12.00% by weight of water
0.42% by weight of optical brighteners
Remaining salts from solutions

composition E1 E2 E3 E4 E5 V1 V2 Spray dried powder 1 62 - 62 62 64 62 - Spray dried powder 2 - 62 - - - - 62 C _12/18 fatty alcohol + 7 EO 6 6 6 6 5 6 6 sodium perborate 20 20 20 20 20 20 20 C _12/18 fatty _alkyl sulfate 7 7 7 7 6 7 7 Salt Compound - - - - 7 - - WQP 1 5 - - - - - - WQP 2 - 5 - - - - - WQP 3 - - 5 - - - - WQP 4 - - - 4 6 - - Polyethylene glycol (4000) - - - - - 7.5 7.5 Extrusion pressure [bar] 70 70 70 60 50 120 100 Bulk density [g / l] 780 790 780 810 800 780 790 L-test 8th 7 4 12 9 7 5 Example 2

In a ploughshare mixer with chopper (manufactured by Lödige), the constituents specified in Table 2 (with the exception of the water-free swollen polymers, WQP) were initially charged and mixed with one another at the temperature (temperature "Rest") specified in Table 2, the liquid being used to bind dust nonionic surfactant was entered as the last component. The respective water-free swollen polymer, which also had the temperature (temperature WQP) given in Table 2, was then mixed in, after which the agglomerating granulation of the material began after about 2 minutes. After a further 8 minutes to 10 minutes mixing time, the granules G1 to G11 listed in Table 2 were obtained with the bulk densities and solubilities also given there (determination as in Example 1) and with the grain size distributions given in Table 3. It is particularly noteworthy that all components of common detergent formulations, including enzyme, soil release polymer, foam regulator and bleach activator (TAED) granules, can be incorporated ( G10 and G11 ) composition G1 G2 G3 G4 G5 G6 G7 G8 G9 G10 G11 SP 1 ^a) 55 56 60 58 60 58 59 52 52 45 45 Na perborate 1 H ₂ O 19 19 20 20 20 20 20 17 18 15 15 C _12/18 fatty _alkyl sulfate ^a) 7 7 7 7 7 7 7 7 7 8th 8th Fatty alcohol + 7 EO 5 5 6 5 6 5 6 5 5 5 5 Zeolite Na-A (powder) 3 3 - - - - - 3 3 3 3 enzyme granules - - - - - - - - - 2 2 Soil-release polymer - - - - - - - - - 1 1 foam regulator - - - - - - - - - 4 4 bleach - - - - - - - - - 7 7 Perfume - - - - - - - - - 1 1 WQP 5 - - - - - 10 - - - - - WQP 4 11 - 7 9 7 - - 16 - - - WQP 6 - - - - - - 8th - - - - WQP 7 - 10 - - - - - - 15 9 9 Temperature WQP 20 20 59 40 20 20 20 20 20 20 68 Temperature "rest" 20 20 20 20 58 20 20 45 45 20 68 Bulk density [g / l] 661 650 710 690 740 680 690 783 790 748 730 L-test 7.6 15.9 3.9 7.9 7.6 4.3 6.8 5.4 5.4 10.0 5.5 Sieve analysis to determine the grain size distribution G1 G2 G3 G4 G5 G6 G7 G8 G9 G10 G11 on sieve 1.6 mm [%] 16 16 3 6 7 7 8th 9 5 5 5 on sieve 1.25 mm [%] 24 27 11 16 14 19 16 13 10 15 8th on sieve 1.0 mm [%] 16 22 11 14 12 16 12 13 13 29 18 on sieve 0.8 mm [%] 21 21 23 22 22 24 24 22 16 28 26 on sieve 0.4 mm [%] 19 13 47 38 41 29 38 39 49 22 40 through sieve 0.4 mm [%] 4 1 5 4 4 5 2 4 7 1 3

Example 3

The procedure for producing further granular detergents G12 to G14 was as in Example 2, but instead of the ploughshare mixer, an intensive mixer with an inclined plate and a swirler (manufacturer Eirich) was used as the granulation device. composition G12 G13 G14 SP 1 47 47 45 Na perborate 1 H ₂ O 16 16 15 C _12/18 fatty _alkyl sulfate 8th 8th 8th C _12/18 fatty alcohol + 7 EO 6 6 6 Zeolite Na-A (powder) 3 3 4 enzyme granules 3 3 3 Soil release polymer 1 1 1 foam regulator 4 4 4 Bleach activator TAED 7 7 - Bleach activator TAED - - 7 WQP 7 5 5 7 Temperature WQP 20 48 20 Temperature "rest" 20 48 20 Bulk density [g / l] 813 784 737 L-test 3.8 3.6 4.9 Sieve analysis to determine the grain size distribution G1 G2 G3 on sieve 1.6 mm [%] 4 5 5 on sieve 1.25 mm [%] 8th 10 13 on sieve 1.0 mm [%] 12 15 20 on sieve 0.8 mm [%] 17 17 20 on sieve 0.4 mm [%] 47 41 35 through sieve 0.4 mm [%] 12 12 7

Claims (15)

1. Process for the preparation of particulate detergents or cleaners or multi-substance components or treated raw materials which, in a mixture with further ingredients, produce compositions of this type, with bulk densities above 600 g/l by combining detergent or cleaner compounds and/or raw materials with simultaneous or subsequent shaping, where a premix is firstly prepared which comprises individual raw materials and/or compounds which are in the form of solids at room temperature and a pressure of 1 bar, and then this premix is converted to a particle with the use of compaction forces, and is optionally subsequently further treated or processed, characterized in that the premix is essentially anhydrous, and a shaping auxiliary which is liquid under the shaping conditions, in particular also at room temperature and a pressure of 1 bar in the form of a polymer swollen in a nonaqueous solution is used, where the nonaqueous liquid component of the shaping auxiliary is chosen from the following mono-, di- or trihydric alcohols which are liquid at room temperature and have boiling points (at 1 bar) above 80°C: n- propanol, isopropanol, n-butanol, s-butanol, isobutanol, ethylene glycol, 1,2- or 1,3-propylene glycol, glycerol, di- or triethylene or -propylene glycol or mixtures thereof.
2. Process according to Claim 1, characterized in that the anhydrously swollen polymer is a system of nonaqueous liquid and polymer which, at room temperature, in the presence of the polymer has an at least 20-fold, in particular 300-fold to 5000-fold, higher viscosity than the nonaqueous liquid on its own.
3. Process according to Claim 1 or 2, characterized in that the viscosity of the shaping auxiliary at room temperature is in the range from 200 mpas to 10 000 mpas, in particular from 400 mpas to 6000 mpas.
4. Process according to Claim 3, characterized in that, at 60°C, the viscosity of the shaping auxiliary is in the range from 250 mpas to 2500 mpas.
5. Process according to one of Claims 1 to 4, characterized in that the nonaqueous liquid component of the shaping auxiliary is chosen from the mono-, di- or trihydric alcohols which are liquid at room temperature and have boiling points (at 1 bar) above 120°C.
6. Process according to one of Claims 1 to 6, characterized in that the polymer which leads to a swollen system in the anhydrous liquid is chosen from polyvinylpyrrolidone, polyacrylic acid, the copolymers of acrylic acid and maleic acid, polyvinyl alcohol, xanthan, partially hydrolyzed starches, alginates, amylopectin, celluloses or starches carrying methyl ether, hydroxyethyl ether, hydroxypropyl ether and/or hydroxybutyl ether groups, phosphated starches, such as starch diphosphate, and inorganic polymers, such as sheet silicates, and mixtures thereof.
7. Process according to one of Claims 1 to 7, characterized in that, in the shaping auxiliary, the concentration of the polymers in the anhydrous liquids is 5% by weight to 20% by weight, in particular 6% by weight to 12% by weight.
8. Process according to one of Claims 1 to 8, characterized in that the content of shaping auxiliaries, based on the premix to be compacted, is from 2% by weight to less than 20% by weight, in particular from 3% by weight to 10% by weight.
9. Process according to one of Claims 1 to 9, characterized in that a shaping auxiliary is used which dissolves at least virtually completely in a concentration of 8 g per 1 litre of water at 30°C within 90 seconds.
10. Process according to one of Claims 1 to 10, characterized in that the premix has a total water content of not more than 15% by weight, where this water is not present in free form and preferably the content of water not bonded to zeolite and/or silicates is not more than 10% by weight and in particular less than 7% by weight.
11. Process according to one of Claims 1 to 11, characterized in that the compacting shaping is carried out using an agglomeration step, where the premix is granulated by agglomeration in a device suitable for this purpose and the shaping auxiliary, in the form of the anhydrously swollen polymer, takes on the role of a binder.
12. Process according to Claim 12, characterized in that the solid constituents of the premix to be compacted are initially introduced into a granulator, as which a mixer may also be used, any dusts present are bound, where necessary by adding a liquid nonionic surfactant, and the shaping auxiliary is introduced into the granulator.
13. Process according to Claim 12 or 13, characterized in that the agglomeration process is carried out with regard to the machine and operating parameters, and also the type and amount of shaping auxiliary in the form of the anhydrously swollen polymer such that spatially at least approximately spherical (bead-like) granulate particles are produced.
14. Process according to one of Claims 1 to 11, characterized in that the shaping takes place by extrusion, where the premix is compacted under pressure, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally comminuted by means of a rotating chopping knife, preferably to give approximately spherical (bead-like) to cylindrical granulate particles.
15. Process according to one of Claims 1 to 15, characterized in that a premix with a relatively broad particle size distribution and relatively high proportions of fines is converted to an end product with a relatively narrow particle size distribution and relatively low proportions of fines.