EP0931137B1 - Process for producing a particulate washing or cleaning agent - Google Patents

Abstract

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

Description

The invention relates to a process for the production of rapidly soluble, compacted particulate Detergents or cleaning agents or compounds or treated Raw materials for this as well as detergents or cleaning agents or Compounds or treated raw materials for this, which from the perspective of the consumer have a significantly better quality.

Particulate detergents or cleaning agents with bulk weights above 600 g / l have been part of the state of the art for quite some time. In the past few years went with increasing the bulk density also a concentration of washing and active cleaning ingredients, so that the consumer not only less Dose volume, but also less mass per washing or cleaning process had to. The increase in the bulk weight and in particular the higher one Concentration of the detergent or cleaning substances was in the generally bought by a subjectively worse from the point of view of the consumer Solubility due to slower dissolution rate of the agent used. This undesired release delay is triggered, among other things, by a number practical anionic and nonionic surfactants and, above all, corresponding ones Surfactant mixtures tend to form gel phases when dissolved in water. Gelling of this type can already be carried out at a surfactant content of 10% by weight, based on the entire agent, that is to say in the case of detergents or cleaning agents which are customary Amounts of surfactant occur. Experience shows that the tendency to form gels decreases also with the increasingly compact grain structure of the particles.

EP-B-0 486 592 describes granular or extruded washing or Detergent 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 35% by weight contain. They are manufactured using a process in which a solid, free-flowing Premix, which is a plasticizer and / or lubricant, preferably aqueous Contains surfactant pastes and / or aqueous polymer solutions at high pressures between 25 and 200 bar extruded and the extrudate after exiting the hole shape cut to the predetermined granule dimension by means of a cutting device and is rounded. The premix consists at least partly of solid Ingredients that 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 are aqueous preparations used. However, there are also comparatively high-boiling organic ones Liquids, if necessary again in a mixture with water, in question. The patent but does not disclose any procedural conditions to be observed in the event of a anhydrous extrusion. The extrudates produced can either be used as washing or Detergent used or later with other granules or Powder components are processed into finished washing or cleaning agents. By the high compactness of the grain and the relatively high surfactant content, but also due to the desired spherical or pearl shape, which compared to conventional Granules have a much smaller surface area, it can depend on the chosen surfactant combinations come to 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 19 139.0 proposes to solve the conflict between high degree of compaction of the individual grain, especially the extrudate on the one hand and the required rapid and in particular non-gelatinous redissolubility of the finished washing or cleaning agents in aqueous liquors before, particulate detergents or cleaning agents with a Bulk density above 600 g / l, which contains anionic and / or nonionic surfactants Contain amounts of at least 15 wt .-%, such that at least two various granular components are used, of which at least one extruded and at least one is not extruded, the surfactant content being extruded Component including soaps a maximum of 15 wt .-%, based on the respective extruded component. Other surfactant components of the finished washing or Detergents are created by one or more non-extruded components introduced into the agent. This method does solve the problem of gelling highly compressed and high-tenside detergent or cleaning agent at Use in an aqueous liquor, but it also includes a number of new ones Problems. Separation processes and corresponding fluctuations can occur the reproducibility of the desired washing or cleaning result. In addition, the extruded portion of the media is not only of high density dried extrudates are also comparatively hard. Among the Conditions of transportation, storage and use can be the comparatively softer Granulate portion thus be exposed to mechanical forces that are proportional to its Reduction and thus lead to the formation of dust and fine particles through abrasion.

Conventional methods generally work with both fixed and Ingredients of washing or cleaning agents liquid at room temperature; also aqueous solutions and / or dispersions are used as granulation aids or as in Case of EP-B-0 486 592 as a plasticizer and / or lubricant in a wide range used. Such procedures have the risk that already during the Manufacture of detergents or cleaning agents, gel-like structures are created 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 quite coarse agglomerates obtained must be crushed and / or sieved (see also "Size Enlargement by Agglomeration", W. Pietsch, John Witey & Sons, 1990, page 180). Another disadvantage of this method is that it is more solid and soluble water-soluble components, especially under the influence of pressure during extrusion can lead to particle enlargements and crystallizations, which occur in the in general adversely affect the dissolving behavior of the finished agent.

A method for the production of heavy granules with the help of a aqueous granulation aid is the two-stage granulation, wherein initially in plastic primary agglomerates are still produced in a conventional mixer / granulator, which are then used in devices such as a rounder, rotocoater, marumerizer etc. liquid binder and / or dust subsequently treated and usually then be dried. The granulation and simultaneous rounding can for example in fluidized bed granulators that contain a rotating disk, be performed. Solid starting materials are initially in the Fluidized bed fluidized and then with liquid binder that is tangential aligned nozzles are fed into the fluidized bed, 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 (Melt coating method), but then the advantage of the equipment, a simultaneous To be able to effect drying, is not exploited.

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. It is about thereby for tableting in tablet presses and for roller compacting, whereby in latter methods are usually generated Schülpen, which subsequently granular but irregularly shaped products. For this For this reason, so-called pre-breakers are used in some systems to already Starting product for the actual granulation or grinding step from the shape to be more uniform. Subsequently, unwanted fine and / or Coarse-grained fractions of the granules produced in this way are screened off and optionally recycled become.

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 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 the structure breakers mentioned above, water is also described as a structure breaker which is suitable in principle, but its use is less preferred 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 the 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 structure 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-B-0 486 592) 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-A-0 337 330 describes a method for increasing the bulk density 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 compounds be used.

German patent application DE-A-43 19 666 discloses a process for the production washable or cleaning active extrudates of high density, being a homogeneous and solid Premix containing certain alkoxinated alcohols, pressed under pressure and then on Granule dimension is cut. Extrusion without the addition of Waser will not In the example section, the mixture contains, for example, almost 5% free water.

In the international patent application WO-A-92/02608 pourable and free-flowing Granules containing bleach activators and a mixture of anionic and nonionic Surfactant compounds that form a substantially anhydrous binder phase are disclosed. The surfactant mixture to be used preferably as a binder has up to the upper Limit temperatures of about 35 to 40 ° C solid character. At the working temperature of the However, the binder phase is granular or liquid without the addition of water plastically softens. The granules are consequently made accessible without being on the The use of water as a temporary liquid phase.

European patent application EP-A-0 711 828 describes a method for the production described by tablets, wherein a coated particulate product is pressed. The coating substance is a water-soluble binding or disintegrating agent Melting temperatures between 35 and 90 ° C. The main feature here, however indicated that the compacting / tableting are carried out at temperatures should at least at 28 ° C, but in any case 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 and 500 μm are used as solid feedstocks, with at least 15% by weight of the particles having a particle size above 50 μm, but with sufficiently small, fine particles so that a particularly high surface area 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 are, in particular, highly viscous anionic surfactant pastes, which can contain between 0 and 90% by weight of water. However, polymers such as polyethylene glycols with molecular weights between 1000 and 20,000 are also suitable, as are mixtures of these and customary nonionic surfactants such as C ₉ -C ₁₆ alcohols with 4 to 8 EO, as long as the 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 broad grain spectrum are obtained.

In contrast, the object of the invention was particulate washing or cleaning agents or to produce compounds or treated raw materials for this, which even with a reduced surface, especially with a spherical shape (pearl shape) an improved one Have disintegration in the dissolution in the aqueous liquor. Besides, should the process should be economical and avoid expensive drying steps can.

(a) der Gehalt an freiem Wasser, bezogen auf das Vorgemisch, unter 2 Gew.-% liegt und ein Gesamtwassergehalt von 15 Gew.-%, bezogen auf das Vorgemisch, nicht überschritten wird und

(b) im Vorgemisch ein oder mehrere Aniontenside in einer Mindestmenge von 0,5 Gew. -%, bezogen auf das Mittel, und mindestens ein Rohstoff oder Compound eingesetzt werden, der bzw. das bei einem Druck von 1 bar und Temperaturen unterhalb von 45 °C in fester Form vorliegt, unter den Verarbeitungsbedingungen aber als Schmelze vorliegt, wobei diese Schmelze als polyfunktioneller, in Wasser löslicher Binder dient, welche bei der Herstellung der Mittel sowohl die Funktion eines Gleitmittels als auch eine Kleberfunktion für die festen Wasch- oder Reinigungsmittelcompounds- bzw. -rohstoffe ausübt, bei der Wiederauflösung des Mittels in wäßriger Flotte hingegen desintegrierend wirkt und wobei dieser Rohstoff oder Compound ausgewählt ist aus der Gruppe lineare, verzweigte und modifizierte Polyethylenglycole, modifizierte Polypropylenglykole, 1,2-Polypropylenglycole, niedermolekulare Polyvinylpyrrolidone und Derivate von diesen mit relativen Molekülmassen bis maximal 30000, alkoxylierte Fett- und Oxoalkohole, Fettsäuremethylesterethoxylate, verzweigte und lineare ethoxylierte Fettsäuren mit 2 bis 100 EO, Hydroxymischether, wasserfreie gequollene Polymere, Alkylglycoside der Formel RO(G)_x, in welcher

R

primäres geradkettiges oder methylverzweigtes (C₈-C₂₂)-Alkyl

G

eine Glycoseeinheit mit 5 oder 6 Kohlenstoffatomen

x

eine Zahl zwischen 1 und 10 bedeuten,

The invention is therefore in a first embodiment of the invention a process for the production of particulate detergents or cleaning agents or compounds or treated raw materials for this purpose with bulk weights above 600 g / l by joining detergent or cleaning agent compounds and / or raw materials with simultaneous or subsequent shaping, characterized in that first a solid, free-flowing premix is produced which contains individual raw materials and / or compounds which are in the form of a solid at room temperature and a pressure of 1 bar and which have a melting point or softening point not below 45 ° C. and, if appropriate contain up to 10 wt .-% at temperatures below 45 ° C and a pressure of 1 bar liquid nonionic surfactants, the mixing process taking place at room temperature down to temperatures below the melting or softening points of the specified raw materials and / or compounds, and wherein this premix is converted into a grain using compression forces at temperatures of at least 45 ° C. and optionally subsequently processed or processed, with the provisos that

(a) the free water content, based on the premix, is below 2% by weight and a total water content of 15% by weight, based on the premix, is not exceeded and

(b) one or more anionic surfactants are used in the premix in a minimum amount of 0.5% by weight, based on the composition, and at least one raw material or compound which is at a pressure of 1 bar and temperatures below 45 ° C is in solid form, but is present as a melt under the processing conditions, this melt serving as a polyfunctional, water-soluble binder which, in the preparation of the agents, has both the function of a lubricant and an adhesive function for the solid detergent or cleaning agent compounds. exercises or raw materials, on the other hand, has a disintegrating effect when the agent is redissolved in an aqueous liquor, and this raw material or compound is selected from the group consisting of linear, branched and modified polyethylene glycols, modified polypropylene glycols, 1,2-polypropylene glycols, low molecular weight polyvinylpyrrolidones and derivatives thereof with relative molecular weights up to a maximum of 30,000, alkoxylated Fatty and oxo alcohols, fatty acid methyl ester ethoxylates, branched and linear ethoxylated fatty acids with 2 to 100 EO, hydroxy mixed ethers, anhydrous swollen polymers, alkyl glycosides of the formula RO (G) _x , in which

R

primary straight chain or methyl branched (C ₈ -C ₂₂ ) alkyl

G

a glycose unit with 5 or 6 carbon atoms

x

represent a number between 1 and 10,

Polyhydroxy fatty acid amides of the formula (I)

in der

R²CO

(C₆-C₂₂)-Acyl,

R³

Wasserstoff, (C₁-C₄)-Alkyl, (C₁-C₄)-Hydroxyalkyl,

[Z]

lineares oder verzweigtes (C₃-C₁₀)-Polyhydroxyalkyl mit 3 bis 10 Hydroxylgruppen bedeuten,

in the

R ² CO

(C ₆ -C ₂₂ ) acyl,

R ³

Hydrogen, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) hydroxyalkyl,

[Z]

mean linear or branched (C ₃ -C ₁₀ ) polyhydroxyalkyl having 3 to 10 hydroxyl groups,

Polyhydroxy fatty acid amides of the formula (II)

in der

R⁴

lineares oder verzweigtes (C₇-C₁₂)-Alkyl, lineares oder verzweigtes (C₇-C₁₂)-Alkyenyl,

R⁵

lineares oder verzweigtes (C₂-C₈)-Alkyl, Cycloalkyl mit 2 bis 8 Kohlenstoffatomen, Aryl mit 2 bis 8 Kohlenstoffatomen,

R⁶

lineares oder verzweigtes (C₁-C₈)-Alkyl, (C₁-C₈)-Oxyalkyl, Cycloalkyl mit 1 bis 8 Kohlenstoffatomen, Aryl mit 1 bis 8 Kohlenstoffatomen,

[Z']

ggf. alkoxyliertes lineares Polyhydroxyalkyl mit mindestens 2 Hydroxylgruppen in der Alkylkette bedeuten,

und deren Gemische.

in the

R ⁴

linear or branched (C ₇ -C ₁₂ ) alkyl, linear or branched (C ₇ -C ₁₂ ) alkylenyl,

R ⁵

linear or branched (C ₂ -C ₈ ) alkyl, cycloalkyl with 2 to 8 carbon atoms, aryl with 2 to 8 carbon atoms,

R ⁶

linear or branched (C ₁ -C ₈ ) alkyl, (C ₁ -C ₈ ) oxyalkyl, cycloalkyl with 1 to 8 carbon atoms, aryl with 1 to 8 carbon atoms,

[Z ']

optionally alkoxylated linear polyhydroxyalkyl with at least 2 hydroxyl groups in the alkyl chain,

and their mixtures.

The content of liquid, i.e. not in the form of water of hydration and / or constitutional water The water present is less than 2% by weight, preferably less than 1% by weight and in particular even less than 0.5% by weight, based in each case on the premix. Accordingly, water can essentially only in chemically and / or physically bound form or as Part of the solid at temperatures below 45 ° C at a pressure of 1 bar existing raw materials or compounds, but not as a liquid, solution or dispersion be introduced into the process for producing the premix. The premix has a total water content of not more than 15% by weight, this water So not in free liquid form, but chemically and / or physically bound is present, and it is particularly preferred that the content of not zeolite and / or Silicate-bound water in the solid premix not more than 10% by weight, preferably less than 7% by weight and with particular preference a maximum of 2 to 5% by weight is.

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 (pear-shaped) particles with a particle size distribution which at least Has 80 wt .-% particles between 0.8 and 2.0 mm.

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 compound, however, consists of at least 2 usually used in washing or cleaning agents components; Compounds are usually only mixed with others Ingredients, preferably used together with other compounds. On treated raw material is a relatively finely divided raw material in the context of this invention, the was converted into a coarser particle by the process according to the invention. Strictly speaking, a treated raw material in the context of the invention is a compound if the treatment agent is usually in detergents or cleaning agents ingredient used.

The ingredients used in the process according to the invention can - with the exception the possibly existing at temperatures below 45 ° C and a pressure of 1 bar liquid nonionic surfactants - separately manufactured Compounds, but also raw materials, which are powdery or particulate (fine particles to rough), but in any case at room temperature and a pressure of 1 bar in solid form available. Particulate particles can be produced, for example, by spray drying Beads or (fluidized bed) granules can be used. The Composition of the compounds per se is not essential for the invention with the Except for the water content, which must be such that the premix is like defined above is essentially anhydrous and preferably not more than 10% by weight contains water of hydration and / or constitutional water. In a preferred one In this embodiment, over-dried compounds are used in the premix. Such compounds can be obtained, for example, by spray drying, the temperature control being regulated so that the tower outlet temperatures above 100 ° C, for example at 110 ° C or above. It is the same possible that solid compounds are used in the premix, which as a carrier of Liquids, for example liquid nonionic surfactants or silicone oil and / or Paraffins. These compounds can contain water in the above Frame included, the compounds are free-flowing and even at higher Temperatures of at least 45 ° C remain free-flowing or at least conveyable. In particular it is preferred, however, that in the premix compound with a maximum of 10 wt .-% and with particular preference with a maximum of 7% by weight of water, based on the Premix, can be used. Free water, water that is not in any Form is bound to a solid 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, are sufficient to to dissolve the water-soluble binder. This would have the consequence that the Melting point or softening point lowered and the end product both Free flowing as well as bulk weight would lose.

Surprisingly, it has been shown that it is by no means indifferent to which solid raw material or in which solid compound the water is bound. So is the water that builders like zeolite or silicates (description of the Substances see below), especially if the water on Zeolite A, Zeolite P or MAP and / or Zeolite X is considered less critical. However, it is preferred that water, which on other solid constituents than those mentioned Builder substances is bound, preferably in amounts of less than 3 wt .-% in Premix is included. In one embodiment of the invention it is therefore preferred that the bound water content in the premix is not more than 10% by weight and / or the content of water not bound to zeolite and / or silicates is less than 7% by weight and in particular a maximum of 2 to 5% by weight. It is Particularly advantageous if the premix contains no water that does not adhere to the Builder substances is bound. However, this is difficult to achieve technically, because in usually at least always traces of water due to the raw materials and compounds be introduced.

The content of the solid compounds used in the premix at at temperatures below 45 ° C non-aqueous liquids is preferably also or additionally up to 10% by weight, advantageously up to 6% by weight, again based on the premix. In particular, solid compounds are used in the premix, which is usually liquid at temperatures below 45 ° C and a pressure of 1 bar contain non-ionic surfactants, which according to all known production methods - for example by spray drying, granulating or spraying carrier beads - were made separately. In this way, premixes can be made which for example up to about 10 wt .-%, preferably below, in particular up to a maximum of 8% by weight and, for example, between 1 and 5% by weight of nonionic Allow surfactants, based on the finished product.

Compounds that contain water in the form specified above and / or as Carrier for liquids, especially for non-ionic liquids which are liquid at room temperature Serve surfactants, i.e. they contain ingredients that are liquid at room temperature and can be used according to the invention in no case have a Softening point below 45 ° C. Likewise, the separately used Individual raw materials have a melting point of at least 45 ° C. Preferably, the Melting point or softening point of all used in the premix Individual raw materials and compounds above 45 ° C and advantageously at 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 the compounds and individual raw materials used in the premix much higher softening point or melting point than the temperatures can be achieved under the process conditions. In practice, the For economic reasons alone, process temperatures do not exceed 150 ° C, preferably not above 120 ° C. Thus at least 80% by weight of the compounds and individual raw materials used a softening point or Have a melting point above 150 ° C. As a rule, the softening point lies or the melting point even far above this temperature. If ingredients are used, which decompose under the influence of temperature, for example Peroxy bleaching agents such as perborate or percarbonate, the decomposition temperature of these is Ingredients at a pressure of 1 bar and especially at higher pressures, which in the extrusion processes according to the invention and preferred are also significant above 45 ° C.

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

However, the premix also contains at least one raw material or at least one compound, which or which serves as a binder is solid at room temperature, during the compression under the process conditions but liquid in the form of a Melt is present. The binder itself can be melted onto the premix once be sprayed on or added dropwise to the premix, but on the other hand it has also proven to be advantageous, the binder in solid form as a powder in the premix contribute. The melting point or softening point is at a pressure of 1 bar at at least 45 ° C and (especially for economic reasons) preferred below 200 ° C, in particular up to a maximum of 150 ° C. If the binder is in the form of a Introduced melt into the premix, the temperature in the Melting vessel also more than 45 ° C to a maximum of about 200 ° C, the temperature in the melting vessel, the melting temperature or the temperature of the Softening point of the binder or binder mixture is quite significant can exceed.

The type of suitable binder and the temperature in the compression step are interdependent. Since it has proven to be advantageous if the binder in the compression step as homogeneous as possible in the one to be compressed Temperature is well distributed in the compression process step are present in which the binder at least softens, but preferably completely and is not only partially in the molten form. So is a binder with high melting point or high softening point selected, so must Process step of the compression set a temperature that the Ensures melting of the binder. In addition, depending on the desired composition of the end product also temperature sensitive raw materials should be able to be processed. Here the upper temperature limit is determined by the Given the decomposition temperature of the sensitive raw material, it being preferred to work significantly below the decomposition temperature of this raw material. On the other hand the lower limit for the melting point or softening point is therefore of such a kind of great importance, as with melting points or softening points below 45 ° C Usually an end product is obtained that is already at room temperature and light increased temperatures by 30 ° C, i.e. in summer temperatures and under storage or transport conditions tend to stick. It has proven to be particularly advantageous if a few degrees, e.g. 2 to 20 ° C, above the melting point or working above the softening point

Without wishing to be limited to this theory, the applicant is of the opinion that due to the homogeneous distribution of the binder within the premix Process conditions of compression of the solid compounds and, if necessary existing individual raw materials in this way enclosed by the binder and then are glued together that the finished end products almost exactly from these many small individual particles that are built up by the binder that the Takes on the role of a preferably thin partition between these individual particles, be held together. In the idealized form, one can Honeycomb-like structure is assumed, these honeycombs with solids (Compounds or individual raw materials) are filled. In contact with water, also with cold Water, for example at the beginning of a machine wash, dissolves or these thin partitions disintegrate almost instantaneously; is surprisingly this is also the case if the binder itself at room temperature, due to a crystal structure, for example, is not readily soluble in water. Preferably, however, such binders are used, which are in a like test procedure given below in a concentration of 8 g of binder per 1 l Allow water to dissolve almost completely at 30 ° C within 90 seconds.

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

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

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

The binders according to the invention have already been mentioned. They are described in more detail below. Binders that can be used alone or in a mixture with other binders are polyethylene glycols, 1,2-polypropylene glycols and modified polyethylene glycols and polypropylene glycols. The modified polyalkylene glycols include in particular the sulfates and / or the disulfates of polyethylene glycols or polypropylene glycols with a relative molecular weight between 600 and 12000 and in particular between 1000 and 4000. Another group consists of mono- and / or disuccinates of the polyalkylene glycols, which in turn have relative molecular weights have between 600 and 6000, preferably between 1000 and 4000. For a more detailed description of the modified polyalkylene glycol ethers, reference is made to the disclosure of the international patent application WO-A-93/02176. In the context of this invention, polyethylene glycols include those polymers which, in addition to ethylene glycol, also use C ₃ -C ₅ glycols and glycerol and mixtures of these as starting molecules. Also included are ethoxylated derivatives such as trimethylol propane with 5 to 30 EO.

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

The particularly preferred polyethylene glycols include those with relative molecular weights between 2000 and 12000, advantageously around 4000, with polyethylene glycols with relative molecular weights below 3500 and above 5000 especially in Combination with polyethylene glycols with a molecular weight around 4000 can be used and such combinations advantageously to more than 50 % By weight, based on the total amount of polyethylene glycols, with polyethylene glycols have a relative molecular mass between 3500 and 5000. Can as a binder however, polyethylene glycols are also used, which in themselves at room temperature and a pressure of 1 bar in the liquid state; here is mostly from Polyethylene glycol with a relative molecular weight of 200, 400 and 600. However, these per se liquid polyethylene glycols should only be mixed with at least one further binder can be used, this mixture again must meet the requirements of the invention, i.e. a melting point or Must have a softening point of at least above 45 ° C.

The modified polyethylene glycols also include polyethylene glycols which are end group-capped on one or more sides, the end groups preferably being C ₁ -C ₁₂ -alkyl chains which can be linear or branched. In particular, the end groups have the alkyl chains between C ₁ and C ₆ , especially between C ₁ and C ₄ , isopropyl and isobutyl or tert-butyl also being possible alternatives.

Polyethylene glycol derivatives capped at one end can also satisfy the formula C _x (EO) _y (PO) _z , where C _{x can be} an alkyl chain with a C chain length of 1 to 20, y 50 to 500 and z 0 to 20. For z = 0 there are overlaps with connections in the previous paragraph.

EO-PO polymers (x = 0) can also serve as binders.

Low molecular weight polyvinylpyrrolidones and derivatives are also suitable as binders of these with relative molecular weights up to a maximum of 30,000. Preferred here relative molecular mass ranges between 3000 and 30,000, for example around 10,000. Polyvinylpyrrolidones are preferably not used as the sole binder, but in Combination with others, especially in combination with polyethylene glycols, used.

Other suitable binders have been found to be raw materials which, as raw materials, have washing or cleaning properties per se, for example nonionic surfactants with melting points of at least 45 ° C. or mixtures of nonionic surfactants and other binders. The preferred nonionic surfactants include alkoxylated fatty or oxo alcohols, in particular C ₁₂ -C ₁₈ alcohols. Degrees of alkoxylation, in particular degrees of ethoxylation of on average 18 to 100 AO, in particular EO per mole of alcohol and mixtures thereof, have proven to be particularly advantageous. In particular, fatty alcohols with an average of 18 to 35 EO, in particular with an average of 20 to 25 EO, show advantageous binder properties in the sense of the present invention. Binder mixtures may also contain ethoxylated alcohols with an average of fewer EO units per mole of alcohol, for example tallow fatty alcohol with 14 EO. However, it is preferred to use these relatively low ethoxylated alcohols only in a mixture with higher ethoxylated alcohols. The binder content of these relatively low ethoxylated alcohols is advantageously less than 50% by weight, in particular less than 40% by weight, based on the total amount of binder used. In particular, nonionic surfactants such as C ₁₂ -C ₁₈ alcohols with an average of 3 to 7 EO, which are usually used in washing or cleaning agents and which are liquid per se at room temperature, are preferably only present in the binder mixtures in such an amount that less than 10 % By weight, in particular less than 8% by weight and advantageously less than 2% by weight, of these nonionic surfactants, in each case based on the end product of the process. As already described above, however, it is less preferred to use nonionic surfactants which are liquid at room temperature in the binder mixtures. In a particularly advantageous embodiment, such nonionic surfactants are therefore not a constituent of the binder mixture, since they not only lower the softening point of the mixture, but can also contribute to the stickiness of the end product and, furthermore, also due to their tendency to cause gelling upon contact with water The requirement for rapid dissolution of the binder / partition in the end product often does not suffice to the desired extent. Likewise, it is not preferred that conventional anionic surfactants or their precursors, the anionic surfactant acids, which are deposited in washing or cleaning agents, are contained in the binder mixture. C ₁₂ -C ₁₈ fatty alcohols, C ₁₆ -C ₁₈ fatty alcohols or pure C ₁₈ fatty alcohol with more than 50 EO, preferably with about 80 EO, on the other hand, have proven to be excellently suitable binders, alone or in combination with other binders can be used.

Other nonionic surfactants which are suitable as binders are the fatty acid methyl ester ethoxylates which do not tend to gel, in particular those with an average of 10 to 25 EO (for a more detailed description of this group of substances, see below). Particularly preferred representatives of this group of substances are predominantly methyl esters based on C ₁₆ -C ₁₈ fatty acids, for example hardened beef tallow methyl esters with an average of 12 EO or with an average of 20 EO.

Another class of substances used as binders in the context of the present invention Suitable are ethoxylated fatty acids with 2 to 100 EO, their "fatty acid" residues can be linear or branched within the scope of this invention. Above all, preferred ethoxylates which have a narrowed homolog distribution (NRE) and / or have a melting point above 50 ° C. Such fatty acid ethoxylates can used as the sole binder or in combination with other binders are less preferred, while the non-ethoxylated sodium and potassium soaps and are only used in combination with other binders.

However, hydroxy mixed ethers which are, according to the teaching of European, also are Patent application EP-A-0 754 667 (BASF) by ring opening of unsaturated epoxides Fatty acid esters can be obtained as binders, especially in combination with Polyethylene glycols, the aforementioned fatty acid methyl ester ethoxylates or Fatty acid ethoxylates, suitable.

Surprisingly, anhydrous swollen polymers have also been found, in particular Starch disphosphate / glycerin, polyvinylpyrrolidone / glycerin and modified Cellulose / glycerin, for example hydroxypropyl cellulose / glycerin, as excellent proven binders. 5 to 20% by weight "solutions" are the Polymers in glycerin, especially about 10% by weight "solutions", especially advantageous.

In a preferred embodiment of the invention, a mixture is used as the binder which contains C ₁₂ -C ₁₈ fatty alcohol based on coconut or tallow with an average of 20 EO and polyethylene glycol with a relative molecular weight of 400 to 4000.

In a further preferred embodiment of the invention, a mixture is used as the binder which is predominantly methyl ester-based C ₁₆ -C ₁₈ fatty acids with an average of 10 to 25 EO, in particular hardened beef tallow methyl ester with an average of 12 EO or an average of 20 EO, and a C ₁₂ - Contains C ₁₈ fatty alcohol based on coconut or tallow with an average of 20 EO and / or polyethylene glycol with a relative molecular weight of 400 to 4000.

Particularly advantageous embodiments of the invention have been found to be binders which are based either solely on polyethylene glycols with a relative molecular weight of around 4000 or on a mixture of C ₁₂ -C ₁₈ fatty alcohol based on coconut or tallow with an average of 20 EO and one of the fatty acid methyl ester ethoxylates described above or based on a mixture of C ₁₂ -C ₁₈ fatty alcohol based on coconut or tallow with an average of 20 EO, one of the fatty acid methyl ester ethoxylates described above and a polyethylene glycol, in particular with a molecular weight of around 4000. Mixtures of polyethylene glycol with a molecular weight of around 4000 with the fatty acid methyl ester ethoxylates mentioned or with C ₁₆ -C ₁₈ fatty alcohol with 20 EO in a weight ratio of 1: 1 or above are particularly preferred.

Other raw materials such as trimethylolpropylene (commercial products from BASF, Federal Republic of Germany) can be found in binder mixtures, especially in Mixture with polyethylene glycols may be included; however, they cannot act alone Binders are used because they fulfill a binding / adhesive function, but have no disintegrating effect.

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

Also suitable as binders, in particular in combination with polyethylene glycols and / or alkyl glycosides, 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 up to 4 carbon atoms and [Z] represents a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.

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

in der R³ für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R⁴ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R⁵ 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-Arytoxy-substituierten Verbindungen können dann beispielsweise nach der Lehre der internationalen Patentanmeldung WO-A-95/07331 durch Umsetzung mit Fettsäuremethylestem in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden. Besonders bevorzugte Glucamide schmelzen bereits bei 95 bis 105 °C. Aber auch hier - wie bei den Alkylglykosiden - reichen im erfindungsgemäßen Verfahren normalerweise Arbeitstemperaturen aus, welche oberhalb der Erweichungstemperatur, aber unterhalb der Schmelztemperatur liegen.The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

in which R ^{3 is} a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{4 is} a linear, branched or cyclic alkyl radical or an aryl radical is 2 to 8 carbon atoms and R ^{5 is} 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-arytoxy-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. Particularly preferred glucamides already melt at 95 to 105 ° C. But here too - as with the alkyl glycosides - working temperatures which are above the softening temperature but below the melting temperature are normally sufficient in the process according to the invention.

The content of binder or binders in the premix is preferably at least 2% by weight, but less than 15% by weight, in particular less than 10% by weight particular preference of 3 to 6 wt .-%, each based on the premix. In particular, the water-swollen polymers are used in amounts below 10 % By weight, advantageously in amounts of 4 to 8% by weight, preferably 5 to 6 % By weight.

In a 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 below the Melting temperature or the softening point of the binder and especially at temperatures up to 35 ° C in a conventional mixing and / or Granulating device mixed together. These solids also include those which according to the European patent EP-B-0 486 592 as plasticizing and / or Lubricants can serve. These include anionic surfactants such as Alkylbenzenesulfonates and / or (fatty) alkylsulfates, but also polymers such as polymers Polycarboxylates. A more detailed description of the possible anionic surfactants and polymers occurs later in the list of possible ingredients. The function of a lubricant can also from the binder or binders or the Binder mixtures are perceived.

The binders are preferably added as the last component. Your encore can, as already explained above, as a solid, i.e. at a processing temperature, which is below its melting point or softening point, or as Melt. However, the admixture among such is advantageous Conditions carried out that a uniform, homogeneous distribution of the Binder is achieved in the solid mixture. With very finely divided binders this at temperatures below 40 ° C, for example at temperatures of the binder between 15 and 30 ° C. The binder advantageously has but temperatures at which it is already in the form of a melt, i.e. above the Softening point, in particular in the form of a complete melt. Preferred temperatures of the melt are below 60 to 150 ° C. Preference for the temperature range from 80 to 120 ° C. During the mixing process, the at room temperature to slightly elevated temperature, but below the Softening point or melting point of the binder takes place, the solidifies Melt almost instantaneously, and according to the invention the premix is in a solid, pourable form. The mixing process is advantageously as long in any case continued until the melt has solidified and the premix in solid, free-flowing form is present.

The assembly of the detergent or cleaning agent compounds and / or raw materials with simultaneous or subsequent shaping by conventional methods, in which use compaction forces such as granulating, compacting, for example roller compacting or extruding, or tableting, if appropriate with the addition of conventional explosives and pelleting. Here can be as Prefabricated compounds used in the premix also spray-dried granules the invention is in no way limited to this. Rather, it offers process according to the invention not to use spray-dried granules, since also very finely divided raw materials with dust-like fractions according to the invention without any problems can be processed without pre-compounding, for example spray-dried to become.

The actual granulation, compacting, tableting, pelleting or extrusion process takes place according to the invention at processing temperatures that at least in the compression step at least the temperature of the softening point, if not even correspond to the temperature of the melting point of the binder. In a preferred embodiment of the invention, the process temperature is significant above the melting point or above the temperature at which the binder as Melt is present. In particular, however, it is preferred that the process temperature in the Compression step not more than 20 ° C above the melting temperature or the upper one Limit of the melting range of the binder is. Technically, it is possible to set even higher temperatures; but it has been shown that a Temperature difference to the melting temperature or the softening temperature of the binder of 20 ° C is generally sufficient and even higher temperatures no additional benefits. That is why it is - especially from energetic Reasons - particularly preferred, above, but as close as possible to Melting point or at the upper temperature limit of the melting range of the binder to work. Such a temperature control has the further advantage that thermally sensitive raw materials, for example peroxy bleaching agents such as perborate and / or percarbonate, but also enzymes, increasingly without serious Active substance losses can be processed. The possibility of accurate Temperature control of the binder, especially in the crucial step of compaction, that is between the mixing / homogenization of the premix and the shaping, allows an energetically very cheap and for the temperature sensitive components of the premix extremely gentle procedure because the premix is only exposed to the higher temperatures for a short time. The duration is preferably the temperature effect between 10 seconds and a maximum of 5 minutes, in particular it is a maximum of 3 minutes.

The essentially water-free procedure not only enables that Peroxy bleach can be processed without loss of activity, it will also allows peroxy bleach and bleach activators (see description for details below) to process together without fear of serious loss of activity have to.

In a preferred embodiment of the invention, the invention Process carried out by means of an extrusion, such as in the European patent EP-B-0 486 592 or international patent applications WO-A-93/02176 and WO-A-94/09111. This creates a solid premix extruded under pressure 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 contains a plasticizer and / or lubricant, which causes the premix under the pressure or under the entry of specific work plastically softened and becomes extrudable. Preferred plasticizers and / or lubricants are Surfactants and / or polymers in the context of the present invention with Except for the non-ionic surfactants mentioned above, however, not in liquid and in particular not in an aqueous, but in solid form introduced into the premix become.

To explain the actual extrusion process, we hereby expressly refer to the referenced above patents and patent applications. In a preferred one Embodiment of the invention, the premix is preferably continuous a planetary roller extruder or a 2-shaft extruder or 2-screw extruder fed with co-rotating or counter-rotating screw guide, its housing and its extruder pelletizing head is heated to the predetermined extrusion temperature could be. The premix is made under the shear of the extruder screws under pressure, which is preferably at least 25 bar, at extremely high throughputs depending on the apparatus used, but can also be below it, compacted, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally preferably the extrudate by means of a rotating knife about spherical to cylindrical granules. The hole diameter the perforated nozzle plate and the strand cut length are selected Granule dimension matched. In this embodiment, the production of Granules of an essentially uniformly predeterminable particle size, wherein in particular, the absolute particle sizes adapted to the intended application could be. 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 of about 0.8 to 3 mm. The length / diameter ratio of the In an important embodiment, chipped primary granules lie in the Range from about 1: 1 to about 3: 1. It is also preferred to use the still plastic primary granulate to supply a further shaping processing step; be there edges present on the crude extrudate are rounded, so that ultimately spherical to approximately spherical extrudate grains can be obtained. If desired you can in this stage small amounts of dry powder, for example zeolite powder such as zeolite NaA powder can also be used. This shape can be found on the market Rondier devices take place. Care should be taken to ensure that only a small number at this stage Amounts of fine coma are created. A drying, which in the above Prior art documents are described as the preferred embodiment, is unnecessary in the context of the present invention, since the method According to the invention essentially water-free, that is to say without the addition of free, unbound Water takes place.

Alternatively, extrusions / pressings can also be carried out in low-pressure extruders, in the Kahl press or be carried out in the extruder.

In a particularly preferred embodiment, the invention now provides that the Temperature control in the transition area of the screw, the pre-distributor and the Nozzle plate is designed such that the melting temperature of the binder or upper limit of the melting range of the binder at least reached, preferably but is exceeded. The duration of the temperature influence is Compression range of the extrusion preferably less than 2 minutes and especially in a range between 30 seconds and 1 minute.

The low residence times associated with the water-free process management allow peroxy bleaching agents to be used together with Bleach activators can also be extruded at higher temperatures without suffer serious loss of activity.

In a particularly advantageous embodiment of the invention, the one used Binders have a melting temperature or melting range up to 75 ° C .; Process temperatures which are a maximum of 10 ° C and in particular a maximum of 5 ° C above the melting temperature or the upper temperature limit of the melting range of the Binder is then found to be particularly favorable.

Under these process conditions, the binder exercises in addition to those previously used mentioned modes of action also prevents and prevents the function of a lubricant or at least reduces the risk of sticking to apparatus walls and Compression tools. This applies not only to processing in the extruder, but also equally for processing, for example in continuously working Mixers / granulators or rollers.

The compressed material preferably points directly after it leaves the production apparatus Temperatures not above 80 ° C, with temperatures between 35 and 75 ° C are particularly preferred. It has been found that outlet temperatures - especially in the extrusion process - from 40 to 70 ° C, for example up to 60 ° C, especially are advantageous.

As in the extrusion process, it is also preferred in the other production processes the resulting primary granules / compactates give another shape To supply processing step, in particular to fillet, so that ultimately spherical to almost spherical (pearl-shaped) grains are obtained can.

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 contain coarse-grained fractions, but it is preferred that a premix with relatively broad particle size distribution and relatively high proportions of fine grain in one End product with a relatively narrow particle size distribution and relatively small proportions 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 also provided an ecologically valuable process because by not using one subsequent drying step not only saves energy but also emissions, as they occur predominantly with conventional types of drying can be avoided can.

It has been found that the redissolving behavior of those produced according to the invention Detergents or cleaning agents in contrast to conventionally produced Now essentially only from the detachment behavior of the individual components is dependent; the more components that are soluble relatively quickly, the more The finished agents are more soluble; the more relatively slowly soluble Components are included, the slower the means dissolve. unwanted Interactions during the redissolution such as gelling etc. play with the The method according to the invention also with washing or cleaning agents with very high Densities, for example above 750 and 800 g / l, obviously no longer matter. The Agents, compounds and raw materials treated in this way thus have a improved dissolving speed compared to such agents, compounds and treated raw materials, which have the same final composition, but were not produced by the method according to the invention, i.e. not by means of a melt were produced under anhydrous conditions.

Accordingly, another object of the invention is a particulate washing or Detergent, which was produced by the method according to the invention and its loosening behavior only depends on the loosening behavior of those used Individual raw materials and compounds. Without restricting yourself to this theory wanting, the applicant assumes that this special release behavior through a honeycomb-like structure of the particles is effected, these honeycombs with solid are filled.

In a preferred embodiment of the invention, a granular or extruded. Detergent provided that at least 80 wt .-% from the invention Compounds and / or treated raw materials. In particular consists of at least 80% by weight of a granular or extruded detergent a base granulate or base extrudate produced according to the invention. The remaining Ingredients can be prepared and mixed by any known method his. However, it is preferred that these remaining constituents, which Compounds and / or treated raw materials can be, according to the invention Processes were made. In particular, this enables basic granules and remaining components with approximately the same pourability, bulk density, size and To produce particle size distribution.

The invention further relates to compounds produced according to the invention and treated raw materials, for example builder granules (extrudates), Bleach activator granules (extrudates) or enzyme granules (extrudates). In particular Treated raw materials show an astonishingly high dissolution rate in water especially when the raw material itself is in a very finely divided, possibly ground Form was used.

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

Surprisingly, the end products of the process produced according to the invention a very high bulk density. The bulk density is preferably above 700 g / l, in particular between 750 and 1000 g / l. Even if the extrudates contain other ingredients, which have lower bulk weights are processed, this drops Bulk weight of the final product not to the extent normally expected would. It is believed that approximately spherical agents, and particularly extrudates, which were produced by the method according to the invention, rather the Ideally, a sphere with a smooth, "smeared" surface resembles the one after Agents and extrudates produced by conventional and in particular aqueous processes. This achieves a better space filling, which leads to a higher bulk density leads, even if components are mixed in, which are neither spherical nor have such a high bulk density.

The particulate process end products obtained can either be used directly as Detergents or cleaning agents are used or previously using customary methods aftertreated and / or processed. The usual post-treatments include for example powdering with finely divided ingredients of washing or Detergents, which generally further increases the bulk density. A preferred aftertreatment is also the procedure according to German patent applications DE-A-195 24 287 and DE-A-195 47 457, wherein dusty or at least finely divided ingredients (the so-called fines) to the Particulate process end products produced according to the invention, which as the core serve, be glued and thus means arise which these so-called Have fine particles as the outer shell. This is advantageously done by a melting agglomeration, the same binders as in the invention Procedures can be used. For melting agglomeration of the fines on the Basic granules according to the invention and produced according to the invention are expressly stated to the disclosure in German patent applications DE-A-195 24 287 and DE-A-195 47 457 referenced.

Processing is generally understood to mean that the invention produced particulate process end products serve as a compound to which other ingredients, possibly other compounds. Here be on the descriptions of the cited patent applications and patents, in particular to the European patent EP-B-0 486 592 and the German one Patent applications DE-A-195 19 139, DE-A-195 24 287 and DE-A-195 47 457 directed. In addition to enzymes, pond activators and foam inhibitors, above all Salts such as silicates (crystalline or amorphous) including metasilicate, carbonate, bicarbonate, Sulfate, bisulfate, citrate or other polycarboxylates, but also organic acids such as Citric acid (see below) mixed in the preparation. It is special preferred that the admixture components in granular form and with a Particle size distribution are used, based on the particle size distribution Agents and compounds produced according to the invention is coordinated.

There now follows a detailed description of the possible ingredients of the agents according to the invention and those used in the method according to the invention Ingredients.

Important ingredients of the agent and ingredients according to the invention Methods used are surfactants, especially anionic surfactants, at least in amounts of 0.5% by weight in the agents according to the invention or according to the invention manufactured means should be included. These include in particular Sulfonates and sulfates, but also soaps.

Preferred surfactants of the sulfonate type are C ₉ -C ₁₃ alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from C ₁₂ -C ₁₈ monoolefins with an end or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.

Also suitable are alkanesulfonates obtained from C ₁₂ -C ₁₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.

The esters of α-sulfo fatty acids (ester sulfonates), e.g. the α-sulfonated Methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids α-sulfonation of the methyl esters of fatty acids of plant and / or animal origin with 8 to 20 carbon atoms in the fatty acid molecule and subsequent neutralization water-soluble mono-salts are prepared. It is preferably are the α-sulfonated esters of hydrogenated coconut, palm, palm kernel or Tallow fatty acids, including sulfonation products of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3% by weight may be present. In particular, α-sulfofatty acid alkyl esters preferred, which is an alkyl chain with no more than 4 carbon atoms in have the ester group, for example methyl ester, ethyl ester, propyl ester and Butyl ester. The methyl esters of α-sulfofatty acids (MES), but also used their saponified salts.

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

The alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of 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 ^(R) , are also suitable anitone 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 used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

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 especially 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 in themselves are nonionic surfactants (description see below). 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.

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

Other anionic surfactants include, in particular, soaps, preferably in quantities from 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 from natural fatty acids, e.g. B. coconut, Palm kernel or tallow fatty acids, derived soap mixtures. Along with these soaps or the known alkenyl succinic acid salts can also be used as a substitute for soaps be used.

The anionic surfactants (and soaps) can be in the form of their sodium, potassium or ammonium salts as well 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 Process according to the invention preferably in amounts of 1 to 30 wt .-% and Contained or used in particular in amounts of 5 to 25 wt .-%.

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, as described above. 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 the alkyl glycosides of the general formula RO (G) _x and the polyhydroxy fatty acid amides of the formulas (I) and (II) which have already been described in detail above.

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 acid methyl esters with an average of 3 to 15 EO, in particular with an average of 5 to 12 EO, are preferred as nonionic surfactants, while, as described above, especially higher ethoxylated fatty acid methyl esters are advantageous as binders. In particular C ₁₂ -C ₁₈ fatty acid methyl esters with 10 to 12 EO can be used both as surfactants and as binders.

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

So-called gemini surfactants can be considered as further surfactants. Below are generally understood such compounds, the two hydrophilic groups and two have hydrophobic groups per molecule. These groups are usually by one so-called "spacers" 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 Micell concentration and the ability to greatly increase the surface tension of water reduce, out. In exceptional cases, however, the term gemini surfactants understood not only dimeric but also trimeric surfactants.

Suitable Gemini surfactants are, for example, sulfated hydroxy mixed ethers according to the German patent application DE-A-43 21 022 or dimeral alcohol bis and trimeral alcohol tris sulfates and ether sulfates according to German patent application DE-A-195 03 061. End group capped dimeric and trimeric mixed ethers according to the German Patent application DE-A-195 13 391 are particularly characterized by their bi- and Mommy functionality. For example, the end groups capped have surfactants good network properties and are low-foaming, so that they are particularly suitable for Suitable for use in machine washing or cleaning processes.

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 belong above all Builder substances for 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 ^(R) (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 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” also means “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 areas of size 10 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-A-44 00 024. 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 for ecological reasons should be avoided. The sodium salts are particularly suitable Orthophosphate, the pyrophosphate and especially the tripolyphosphate. Your salary generally not more than 25% by weight, preferably not more than 20% by weight, each based on the finished product. In some cases it has been shown that in particular tripolyphosphates in small amounts up to a maximum of 10% by weight, based on the finished agent, in combination with other builder substances to form one lead to synergistic improvement of secondary washing ability.

Suitable substitutes or partial substitutes for the zeolite are layered silicates natural and synthetic origin. Layered silicates of this type are known, for example, from US Pat Patent applications DE-B-23 34 899, EP-A-0 026 529 and DE-A-35 26 405 are known. Your Applicability is not based on a special composition or structural formula limited. 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 condition or the type of processing. Useful sheet silicates are known, for example, from US-A-3,966,629, EP-A-0 026 529 and EP-A-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.

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

The acids themselves can also be used. The acids have a builder effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH value of washing or Detergents. In particular, citric acid, succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these. These acids are preferred when they are in the premix according to the invention used and not subsequently mixed, used water-free.

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 described in British patent application 94 19 091. The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing 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-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 and international patent applications WO- A-92/18542, WO-A-93/08251, WO-A-94128030, WO-A-95/07303, WO-A-95/12619 and WO-A-95/20608. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Other suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate. Are particularly preferred in this context also glycerol disuccinates and glycerol trisuccinates, such as those found in the United States Patent specifications US 4,524,009, US 4,639,325 in the European patent application EP-A-0 150 930 and Japanese patent application JP 93/339896 become. Suitable amounts are in zeolite and / or formulations containing silicate at 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be present in lactone form and which have at least 4 carbon atoms and at least one hydroxy group as well contain a maximum of two acid groups. Such cobuilders are used, for example, in the international patent application WO-A-95/20029.

Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative Molecular mass from 800 to 150,000 (based on acid). Suitable copolymers Polycarboxylates are in particular those of acrylic acid with methacrylic acid and Acrylic acid or methacrylic acid with maleic acid. Have proven to be particularly suitable Copolymers of acrylic acid with maleic acid have proven to be 50 to 90% by weight of acrylic acid and contain 50 to 10% by weight of maleic acid. Their relative molecular mass, based on free acids is generally 5,000 to 200,000, preferably 10,000 to 120,000 and especially 50,000 to 100,000.

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

Also particularly preferred are biodegradable polymers made from more than two different ones Monomer units, for example those which according to DE-A-43 00 772 as Monomeric salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomer salts of acrylic acid and the 2-alkylallylsuifonic acid and sugar derivatives.

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

Other suitable builder substances are oxidation products of carboxyl-containing ones Polyglucosans and / or their water-soluble salts, such as those in the international patent application WO-A-93/08251 or their Manufactured, for example, in international patent application WO-A-93/16110 is described. Oxidized oligosaccharides according to the German patent application DE-A-196 00 018.

Likewise, further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors. Polyaspartic acids are particularly preferred or their salts and derivatives, of which in the German Patent application DE-A-195 40 086 discloses that in addition to cobuilder properties also have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which are obtained by converting Dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 Have hydroxyl groups, for example as in the European patent application EP-A-0 280 223 can be obtained. Preferred polyacetals will be from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and obtained 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 if a textile is soiled that has already been washed several times with one detergent according to the invention, which contains this oil and fat-dissolving component, was washed. 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 of 15 to 30 wt .-% and Hydroxypropoxyl groups from 1 to 15 wt .-%, each based on the nonionic Cellulose ether, as well as the polymers known from the prior art Phthalic acid and / or terephthalic acid or their derivatives, in particular Polymers from ethylene terephthalates and / or polyethylene tycoterephthalates or anionically 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 builder substance - generally up to 10% by weight and preferably between 2 and 8% by weight, otherwise more.

According to the teaching of international patent application WO-A-94/01222 can Alkali carbonates also by sulfur-free, 2 to 11 carbon atoms and optionally a further carboxyl and / or amino group having amino acids and / or by the salts of which are replaced. In the context of this invention, it is possible that a partial to complete replacement of the alkali carbonates by glycine or glycinate he follows.

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

Acid can also be used to reduce the pH of detergents or cleaning agents Salts or slightly alkaline salts can be used. Are preferred as Acidifying component bisulfates and / or bicarbonates or the above organic polycarboxylic acids, which are also used as builder substances can be. The use of citric acid, which is particularly preferred either added subsequently (customary procedure) or - in anhydrous form - Is used in a solid premix.

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. Substances containing O and / or N-acyl groups of the number of carbon atoms mentioned are suitable and / or optionally substituted benzoyl groups. Are preferred polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSi), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), Carboxylic anhydrides, especially phthalic anhydride, acylated polyvalent 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 or their in the European patent application EP-A-0 525 239 (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, Tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, which results from the 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 from the German patent application DE-A-196 16 769 known hydrophilically substituted acylacetals and those in the German Patent application DE-A-196 16 770 and international patent application WO-A-95/14075 Acyllactams described are also preferably used. Also the Combinations of conventional known from German patent application DE-A-44 43 177 Bleach activators can be used. Such bleach activators are in usual amount range, preferably in amounts of 1 wt .-% to 10 wt .-%, in particular 2 wt .-% to 8 wt .-%, based on the total, 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 wt .-% used.

Enzymes in particular come from the hydrolase class, such as Proteases, lipases or lipolytically active enzymes, amylases, cellulases or their Mixtures in question. Oxireductases are also suitable.

From bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens obtained enzymatic Agents. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used. Here are enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and Lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but especially protease- and / or lipase-containing mixtures or Mixtures with lipolytically active enzymes of particular interest. examples for such lipolytic enzymes are the well-known cutinases. Peroxidases too or oxidases have been found to be suitable in some cases. To the appropriate ones 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 cello bias, or mixtures of these used. Since the different cellulase types are characterized by their CMCase and Avicelase activities can be distinguished by targeted mixtures of the cellulases the desired activities are set.

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

In addition to phosphonates, the agents can also contain further enzyme stabilizers. For example, 0.5 to 1% by weight sodium formate can be used. 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 of cellulose or starch. Also water-soluble, acidic Group-containing polyamides are suitable for this purpose. Furthermore, use soluble starch preparations and starch products other than those mentioned above, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, cellulose ethers such as carboxymethyl cellulose (Na salt) are preferred, Methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and Polyvinylpyrrolidone, for example in amounts of 0.1 to 5 wt .-%, based on the Means used.

As optical brighteners, the agents can be derivatives of diaminostilbenedisulfonic acid or whose alkali metal salts contain. 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 similarly constructed Compounds which instead of the morpholino group a diethanolamino group, a Carry a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can be used.

Examples

Means M1 and M2 were produced according to the following procedure:

In a batch mixer (20 liters), the chopper (chopper) was equipped, a solid premix was made from the solid components, including the binder, which in this case was added in solid form, manufactured. (In an alternative embodiment, the binder was injected into the premix in the form of a sprayable melt; however, this did not result End products with significantly different properties. The melt froze application to the solid mixture within a short time. The usual dwell time in Mixer was sufficient for this.) The mixture was then homogenized for a further 2 minutes and then fed to a 2-screw extruder, the pelletizing head on Temperatures between 50 and 65 ° C, preferably to 62 ° C, was preheated. The Add the optionally existing at temperatures below 45 ° C and one Pressure of 1 bar of liquid non-ionic surfactants was introduced into the powder stream through the Spray through nozzles. Under the shear of the extruder screws, this was Plasticized premix and then at a pressure between 50 and 100 bar, preferably around 78 bar, through the extruder head perforated die plate into fine strands extruded with a diameter of 1.4 mm, which after the nozzle exit by means of a Tee knife were crushed into approximately spherical granules (Length / diameter ratio about 1, hot cut). The resulting warm granules was a minute in a standard rounder machine of the type Marumerizer® rounded and if necessary coated with a fine powder.

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

To produce the inventive agent M1, a homogeneous premix consisting of 61% by weight of spray-dried granules 1 (for composition see below), 6% by weight of C ₁₂ -C ₁₈ fatty alkyl sulfate (composition 92.00% by weight of active substance, 3 , 70% by weight sodium sulfate, 2.80% by weight other salts from raw materials and unsulfonated components and 1.50% by weight water), 3% by weight copolymeric sodium salt of acrylic acid and maleic acid (powder form), 20 % By weight of sodium perborate monohydrate and 6% by weight of polyethylene glycol as binder with a molecular weight of 4000. 4% by weight of C ₁₂ -C ₁₈ fatty alcohol with an average of 7 EO were sprayed into the powder stream. The premix was then extruded. In the sieve analysis given, the extrudate had a bulk density of 758 g / l and achieved a value of 8% in the solubility test (L test) described below. Sieve analysis M1: on sieve 1.60 mm 6% by weight 1.25 mm 76% by weight 1.00 mm 8% by weight 0.80 mm 4% by weight through sieve 0.80 mm 6% by weight

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

Note 1:

einwandfrei, keine erkennbaren Rückstände

Note 2:

tolerierbare, vereinzelte, noch nicht störende Rückstände

Note 3:

erkennbare, bei kritischer Beurteilung bereits störende Rückstände

ab Note 4:

deutlich erkennbare und störende Rückstände in steigender Anzahl und Menge

The tendency to gel when dissolved in the aqueous liquor was examined in a towel test and a bowl test: For this purpose, 25 g of M1 were sprinkled into 5 l of tap water (16 ° d, 30 ° C.) in a dark plastic wash bowl (for example dark red). After 15 seconds, the agent was spread by hand in the bowl. After a further 15 seconds, 1 blue terry towel was added to the wash liquor and moved as in a typical hand wash. After 30 seconds the wall of the bowl was wiped with the towel. Finally, after another 30 seconds, the towel was wrung out and visually graded. Mean:

Note 1:

flawless, no discernible residues

Grade 2:

tolerable, isolated, not yet disturbing residues

Note 3:

recognizable residues that are already annoying in the event of a critical assessment

from grade 4:

clearly recognizable and annoying residues in increasing number and quantity

Note 1:

einwandfrei, keine erkennbaren Rückstände

Note 2:

tolerierbare, vereinzelte, noch nicht störende Rückstände, sehr fein verteilt, bei Zugabe von Wasser nicht gelierend

Note 3:

erkennbare, bei kritischer Beurteilung bereits störende Rückstände,

ab Note 4:

deutlich erkennbare und störende Rückstände in steigender Anzahl und Menge, Agglomerat- bis Klumpenbildung, bei Zugabe von Wasser gelierend

The wash liquor was decanted off and the residue was also visually graded after treatment with 5 to 10 ml of water. Mean:

Note 1:

flawless, no discernible residues

Grade 2:

tolerable, isolated, not yet disturbing residues, very finely divided, non-gelling when water is added

Note 3:

recognizable residues that are already annoying in the event of a critical assessment,

from grade 4:

clearly recognizable and annoying residues in increasing number and quantity, agglomerate to lump formation, gelling when water is added

M1 scored 1-2 in both the towel test and the bowl test.

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

The detergent M2 turned out to be particularly cheap for washing colored textiles. For its preparation, 65.71% by weight of spray-dried granulate 2 (composition see below) was mixed with 11.83% by weight of an alkyl sulfate compound produced in the fluidized bed (composition: 75% by weight C ₁₂ -C ₁₈ - Alkyl sulfate, 17% by weight sodium sulfate, 3% by weight sodium carbonate, 1% by weight water, remainder salts from solutions), 2.96% by weight copolymeric sodium salt of acrylic acid and maleic acid (powder form), 6.99 % By weight of trisodium citrate dihydrate, 3.59% by weight of polyethylene glycol with a relative molecular weight of 4000 and 8.92% by weight of C ₁₂ -C ₁₈ fatty alcohol with an average of 7 EO, mixed to a premix as described above and extruded ,

In the sieve analysis given, the extrudate had a bulk density of 811 g / l and achieved a value of 2% in the solubility test (L test) described above. The bowl test gave a grade of 1-2. Sieve analysis M1: on sieve 1.60 mm 2% by weight 1.25 mm 90% by weight 1.00 mm 7% by weight 0.80 mm 0% by weight through sieve 0.80 mm 1% by weight

For comparison, an agent V2 was again produced, which has the same ingredients in the end product contained, but in which the copolymer is not in powder form, but as about 30 % By weight aqueous solution had been introduced into the process. The excess Water was then dried away in a fluidized bed. The bulk density of the Extrudate was well below 800 g / l, the L test showed a value above 20 %. If the alkyl sulfate compound was not co-extruded, but according to the teaching of German patent application DE-A-195 19 139 subsequently mixed, that was it Bulk weight of the extrudate at 780 g / l, the L test gave a value of 7% and the Bowl test a grade of 1-2.

After preparing 90 parts by weight of the extrudate M2 with 3 parts by weight Enzyme granules, 4 parts by weight of a foam inhibitor granulate, 2.5 parts by weight of one Polymers (Repelotex®, commercial product from Rhönen-Poulenc) and 0.5 part by weight Silicic acid (for subsequent surface treatment) was an agent A2 receive which has a bulk density of 820 g / l (bulk density increase!) with an L test value of 7% with the bowl test score remaining the same.

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

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

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

Products according to the invention were also prepared by using a sodium C ₉ -C ₁₃ -alkylbenzenesulfonate powder of 85% by weight alkylbenzenesulfonate, 4.5% by weight sodium carbonate, 3.5% by weight sodium sulfate, 2% by weight as alkylbenzenesulfonate. -% sodium chloride and 4 wt .-% water and unsulphated components were used in the premix. Depending on their other formulation, the extrudates had values in the described L test of less than 15% or less than 10%. If, instead of the alkylbenzenesulfonate powder, a concentrated aqueous alkylbenzenesulfonate paste was used in the comparative examples and the water was subsequently dried off, all the products in the L test had a value above 20%.

Composition of the spray-dried granules:

Spray dried granules 1 26.3D wt% C ₉ -C ₁₃ alkyl benzene sulfonate 1.10% by weight tallow fatty alcohol with an average of 5 EO 1.40% by weight of C ₁₂ -C ₁₈ sodium fatty acid soap 9.40% by weight sodium carbonate 4.00% by weight of the copolymer sodium salt of acrylic acid and maleic acid 39.50% by weight of zeolite A, based on anhydrous active substance) 2.80% by weight of amorphous sodium disilicate 13.60% by weight water Remaining salts from solutions Spray dried granules 2 12.07% by weight of C ₉ -C ₁₃ alkyl benzene sulfonate 3.00% by weight of C ₁₂ -C ₁₈ sodium fatty acid soap 0.03% by weight sodium hydroxide 4.15% by weight sodium carbonate 0.80% by weight phosphonate 0.80% by weight polyvinylpyrrolidone 57.75% by weight of zeolite A, based on anhydrous active substance 4.15 wt .-% copolymer sodium salt of acrylic acid and maleic acid 16.65 wt% water Remaining salts from solutions

Other agents M3 to M10 according to the invention had the following compositions and were prepared as described above: composition M3 M4 M5 M6 Spray dried granules 1 57 60 64 55 sodium perborate 20 23 - 25 Polyethylene glycol (4000) 5 - - - Polyethylene glycol (2000), capped on one side with methyl end groups - - - 7 Fatty acid methyl _ester C _16/18 + 12 EO - - 6 - C _12/18 fatty alcohol + 7 EO 6 6 7 7 C _12/18 fatty _alkyl sulfate (92% by weight of active substance, 3.70% by weight of sodium sulfate, 2.80% by weight of other salts from raw materials and unsulfated components, 1.50% by weight of water) 7 5 8th 6 Fatty alcohol C _12/14 polyglycoside (78% by weight active substance, 18% by weight water glass module 2.4, 5% by weight water) 5 - - - C _16/18 fatty acid ethoxylate + 80 EO - 6 - - trisodium - - 15 - composition M7 M8 M9 M10 Spray dried granules 1 72 51 54.5 52 sodium perborate - 20 20 20 Polyethylene glycol (4000) 6 - 5 - Polyethylene glycol (2000), methyl end groups capped on one side - 6 - 7 C _12/18 fatty alcohol + 7 EO 7 8th 7 - C _12/14 fatty alcohol + 5 EO - - - 7 C _12/18 fatty _alkyl sulfate (92% by weight of active substance, 3.70% by weight of sodium sulfate, 2.80% by weight of other salts from raw materials and unsulfated components, 1.50% by weight of water) - 15 5 10 Fatty alcohol C _12/14 polyglycoside (78% by weight active substance, 18% by weight water glass module 2.4, 5% by weight water) - - - 4 trisodium 15 - - - Tetraacethylethylene diamine (95% by weight TAED, 2% by weight carboxymethyl cellulose, 2.75% by weight salts, 0.25% by weight water) - - 8.5 -

Bowl test results for M3 to M10: M3 1-2 M4 1-2 M5 1 M6 1-2 M7 1 M8 1 M9 1-2 M10 1-2

Claims (24)

1. Process for producing particulate washing or cleaning agents or compounds or treated raw materials therefor having bulk densities above 600 g/l by combining washing or cleaning agent compounds and/or raw materials with simultaneous or subsequent shaping, characterized in that firstly a solid, flowable premix is produced 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 have a melting point or softening point not below 45°C, and optionally up to 10% by weight of nonionic surfactants which are liquid at temperatures below 45°C and a pressure of 1 bar, where the mixing operation takes place at room temperature up to temperatures below the melting or softening points of the described individual raw materials and/or compounds, and where this premix is converted to a particle with the use of compaction forces at temperatures of at least 45°C, and is optionally subsequently further treated or processed, with the provisos that

   a) the content of free water, based on the premix, is below 2% by weight and a total water content of 15% by weight, based on the premix, is not exceeded and

   b) in the premix one or more anionic surfactants are used in a minimum amount of 0.5% by weight, based on the agent, and at least one raw material or compound is used which is in solid form at a pressure of 1 bar and temperatures below 45°C, but is in the form of a melt under the processing conditions, where this melt serves as a polyfunctional, water-soluble binder which, during production of the agent, performs both the function of a lubricant and also an adhesive function for the solid washing or cleaning agent compounds or raw materials, but has a disintegrating effect when the agent is redissolved in an aqueous liquor, and where this raw material or compound is chosen from the group consisting of linear, branched and modified polyethylene glycols, modified polypropylene glycols, 1,2-polypropylene glycols, low molecular weight polyvinylpyrrolidones and derivatives of these with relative molecular masses up to at most 30 000, alkoxylated fatty and oxo alcohols, fatty acid methyl ester ethoxylates, branched and linear ethoxylated fatty acids having 2 to 100 EO, hydroxy mixed ethers, anhydrous swollen polymers, alkyl glycosides of the formula RO(G)_x, in which

   R

   is a primary straight-chain or methyl-branched (C₈-C₂₂)-alkyl

   G

   is a glycose unit with 5 or 6 carbon atoms

   x

   is a number between 1 and 10,

   polyhydroxy fatty acid amides of the formula (I)

   

   in which

   R²CO

   is (C₆-C₂₂)-acyl,

   R³

   is hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-hydroxyalkyl,

   [Z]

   is a linear or branched (C₃-C₁₀)-polyhydroxyalkyl having 3 to 10 hydroxyl groups,

   polyhydroxy fatty acid amides of the formula (II)

   

   in which

   R⁴

   is a linear or branched (C₇-C₁₂)-alkyl, linear or branched (C₇-C₁₂)-alkenyl,

   R⁵

   is a linear or branched (C₂-C₈)-alkyl, cycloalkyl having 2 to 8 carbon atoms, aryl having 2 to 8 carbon atoms,

   R⁶

   is a linear or branched (C₁-C₈) -alkyl, (C₁-C₈)-oxyalkyl, cycloalkyl having 1 to 8 carbon atoms, aryl having 1 to 8 carbon atoms,

   [Z']

   is an optionally alkoxylated linear polyhydroxyalkyl having at least 2 hydroxyl groups in the alkyl chain,

   and mixtures thereof.
2. Process according to Claim 1, characterized in that the content of water not bonded to zeolite and/or silicates in the premix is not more than 10% by weight and in particular less than 7% by weight.
3. Process according to Claim 1 or 2, characterized in that the premix has, in addition to the solid constituents, up to 10% by weight of nonionic surfactants which are liquid at temperatures below 45°C and a pressure of 1 bar, in particular the alkoxylated alcohols customarily used in washing or cleaning agents, such as fatty alcohols or oxo alcohols with a C chain length between 8 and 20 and in particular, on average, 3 to 7 ethylene oxide units per mole of alcohol, where the addition of the liquid nonionic surfactants and of the binder which has disintegrating effect to the premix preferably takes place separately.
4. Process according to one of Claims 1 to 3, characterized in that the melting point of the individual raw materials used in the premix or the, softening point of the compounds used in the premix is above 45°C and preferably at least 50°C.
5. Process according to one of Claims 1 to 4, characterized in that compounds and raw materials are used in the premix which, in an amount of 80% by weight, preferably in an amount of at least 85% by weight and with particular preference in an amount of at least 90% by weight, have a significantly higher softening point or melting point than the temperatures which are reached under the process conditions.
6. Process according to one of Claims 1 to 5, characterized in that in the compaction step, processing is carried out in a temperature range of a few degrees, for example 2 to 20°C, above the melting point or above the softening point.
7. Process according to one of Claims 1 to 6, characterized in that one or more binders are used which virtually completely dissolve in a concentration of 8 g of binder per 1 l of water at 30°C within 90 seconds.
8. Process according to one of Claims 1 to 7, characterized in that binders are used which are entirely in the form of melts even at temperatures up to at most 130°C, preferably up to at most 100°C and in particular up to 90°C.
9. Process according to one of Claims 1 to 8, characterized in that the solids for the production of the solid and flowable premix are initially introduced into a customary mixing and/or granulation device firstly at room temperature to slightly elevated temperatures, which are preferably below the melting temperature or the melting range of the binder and in particular at temperatures up to 35°C.
10. Process according to one of Claims 1 to 9, characterized in that the binders are added as the last component to the premix, where they are mixed in under conditions such that the greatest possible uniform, homogeneous distribution of the binder - as solidified melt or as powder - in the solid.mixture is achieved.
11. Process, according to one of Claims 1 to 10, characterized in that the binder is incorporated at temperatures at which the binder is in the form of a melt, preferred temperatures of the melt being 60 to 150°C, in particular in the temperature range from 80 to 120°C.
12. Process according to one of Claims 1 to 11, characterized in that the mixing operation is continued until the melt is solidified and the premix is in solid, flowable form.
13. Process according to one of Claims 1 to 12, characterized in that a premix is used whose content of binder or binders is at least 2% by weight, but less than 15% by weight, preferably less than 10% by weight and with particular preference is 3 to 6% by weight, in each case based on the premix.
14. Process according to one of Claims 1 to 13, characterized in that a process temperature in the actual granulation, compaction, tabletting, pelletting or extrusion operation is set above the melting point or above the temperature at which the binder (or the binders) is in the form of a melt, the process temperature preferably, however, not being more than 20°C above the melting temperature or the melting range of the binder.
15. Process according to one of Claims 1. to 14, characterized in that the binder has a melting temperature or a melting range up to at most 150°C, preferably up to at most 100°C and in particular up to 75°C, and the process temperature is 10°C and in particular at most 5°C above the melting temperature or the upper temperature limit of the melting range of the binder.
16. Process according to one of Claims 1 to 15, characterized in that the duration of the effect of temperature between the mixing/homogenization of the premix and the shaping, i.e. in the compaction region, is between 10 seconds and at most 5 minutes and in particular is at most 3 minutes.
17. Process according to one of Claims 1 to 16, characterized in that the production 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, and the temperature control in the transition region of the extruder screw, the predistributer and the die plate being such that the melting temperature of the binder or the upper limit of the melting range of the binder is at least reached, but is preferably exceeded.
18. Process according to Claim 17, characterized in that the duration of the effect of temperature in the compression region of the extrusion is at most 2 minutes and in particular is in a range between 30 seconds and 1 minute.
19. Process according to one of Claims 1 to 18, characterized in that the compressed article, directly after leaving the production apparatus, has temperatures not above 80°C, preferably between 35 and 75°C and in particular between 40 and 70°C, for example up to 60°C.
20. Process according to one, of Claims 1 to 19, characterized in that a premix with a relatively broad particle size distribution and relatively high fractions of fines is converted into an end product with a relatively narrow particle size distribution and relatively low fractions of fines.
21. Particulate washing or cleaning agent, compound or treated raw material therefor having bulk densities above 600 g/l, prepared according to one of Claims 1 to 20, where compounds and/or raw materials therefor are used to initially produce a solid, flowable premix 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 have a melting point or softening point not below 45°C, and optionally up to 10% by weight of nonionic surfactants which are liquid at temperatures below 45°C and a pressure of 1 bar, where the mixing operation takes place at room temperature up to temperatures below the melting or softening points of the described individual raw materials and/or compounds, and where this premix is converted to a particle with the use of compaction forces at temperatures of at least 45°C, and is optionally subsequently further processed or processed, with the proviso that the content of free water in the premix, based on the premix, is below 2% by weight and a total water content of 15% by weight in the premix, based on the premix, is not exceeded, characterized in that the premix comprises one or more anionic surfactants in a minimum amount of 0.5% by weight, based on the agent, at least one raw material or one compound which is introduced via the premix and is in solid form at a pressure of 1 bar and temperatures below 45°C, but is in the form of a melt under the processing conditions, where this melt serves as a polyfunctional, water-soluble binder which, during production of the agent, performs both the function of a lubricant and also an adhesive function for the solid washing or cleaning agent compounds or raw materials, but has a disintegrating effect when the agent is redissolved in an aqueous liquor, and where this raw material or compound is chosen from the group consisting of linear, branched and modified polyethylene glycols, modified polypropylene glycols, 1,2-polypropylene glycols, low molecular weight polyvinylpyrrolidones and derivatives of these with relative molecular masses up to at most 30 000, alkoxylated fatty and oxo alcohols, fatty acid methyl ester ethoxylates, branched and linear ethoxylated fatty acids having 2 to 100 EO, hydroxy mixed ethers, anhydrous swollen polymers, alkyl glycosides of the formula RO(G)_x, in which

    R

    is a primary straight-chain or methyl-branched (C₈-C₂₂)-alkyl

    G

    is a glycose unit with 5 or 6 carbon atoms

    x

    is a number between 1 and 10,

    polyhydroxy fatty acid amides of the formula (I)

    

    in which

    R²CO

    is (C₆-C₂₂)-acyl,

    R³

    is hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-hydroxyalkyl,

    [Z]

    is a linear or branched (C₃-C₁₀)-polyhydroxyalkyl having 3 to 10 hydroxyl groups,

    polyhydroxy fatty acid amides of the formula (II)

    

    in which

    R⁴

    is a linear or branched (C₇-C₁₂)-alkyl, linear or branched (C₇-C₁₂)-alkenyl,

    R⁵

    is a linear or branched (C₂-C₈)-alkyl, cycloalkyl having 2 to 8 carbon atoms, aryl having 2 to 8 carbon atoms,

    R⁶

    is a linear or branched (C₁-C₈)-alkyl, (C₁-C₈)-oxyalkyl, cycloalkyl having 1 to 8 carbon atoms, aryl having 1 to 8 carbon atoms,

    [Z']

    is an optionally alkoxylated linear polyhydroxyalkyl having at least 2 hydroxyl groups in the alkyl chain,

    and mixtures thereof, and also has a honeycomb-like structure, where the honeycombs are filled with solid.
22. Granulated or extruded washing agent according to Claim 21, characterized in that it consists, in an amount of at least 80% by weight, of compounds prepared according to the invention and/or treated raw materials and consists, in particular, in an amount of at least 80% by weight, of a base granulate or base extrudate prepared according to the invention, it being particularly advantageous if the remaining constituents are likewise compounds or treated raw materials which have been prepared according to one of Claims 1 to 20.
23. Agent according to one of Claims 21 or 22, characterized in that it has, as outer coating, dust-like or at least finely divided ingredients (the so-called fines), which have been stuck on by melt agglomeration.
24. Washing agent shaped body, in particular tablet, obtainable according to one of Claims 1 to 20, where compounds and/or raw materials therefor are.used to initially produce a solid, flowable premix 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 have a melting point or softening point not below 45°C, and optionally up to 10% by weight of nonionic surfactants which are liquid at temperatures below 45°C and a pressure of 1 bar, where the mixing operation takes place at room temperature up to temperatures below the melting or softening points of the described individual raw materials and/or compounds, and where this premix is converted to a particle with the use of compaction forces at temperatures of at least 45°C, and is subsequently further processed or processed, with the proviso that the content of free water in the premix, based on the premix, is below 2% by weight and a total water content of 15% by weight in the premix, based on the premix, is not exceeded, characterized in that the shaped body comprises one or more anionic surfactants in a minimum amount of 0.5% by weight, based on the agent, at least one raw material or one compound which is introduced via the premix and is in solid form at a pressure of 1 bar and temperatures below 45°C, but is in the form of a melt under the processing conditions, where this melt serves as a polyfunctional, water-soluble binder which, during production of the agent, performs both the function of a lubricant and also an adhesive function for the solid washing or cleaning agent compounds or raw materials, but has a disintegrating effect when the agent is redissolved in an aqueous liquor, and where this raw material or compound is chosen from the group consisting of linear, branched and modified polyethylene glycols, modified polypropylene glycols, 1,2-polypropylene glycols, low molecular weight polyvinylpyrrolidones and derivatives of these with relative molecular masses up to at most 30 000, alkoxylated fatty and oxo alcohols, fatty acid methyl ester ethoxylates, branched and linear ethoxylated fatty acids having 2 to 100 EO, hydroxy mixed ethers, anhydrous swollen polymers, alkyl glycosides of the formula RO(G)_x, in which

    R

    is a primary straight-chain or methyl-branched (C₈-C₂₂)-alkyl

    G

    is a glycose unit with 5 or 6 carbon atoms

    x

    is a number between 1 and 10,

    polyhydroxy fatty acid amides of the formula (I)

    

    in which

    R²CO

    is (C₆-C₂₂)-acyl,

    R³

    is hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-hydroxyalkyl,

    [Z]

    is a linear or branched (C₃-C₁₀)-polyhydroxyalkyl having 3 to 10 hydroxyl groups,

    polyhydroxy fatty acid amides of the formula (II)

    

    in which

    R⁴

    is a linear or branched (C₇-C₁₂) -alkyl, linear or branched (C₇-C₁₂)-alkenyl,

    R⁵

    is a linear or branched (C₂-C₈)-alkyl, cycloalkyl having 2 to 8 carbon atoms, aryl having 2 to 8 carbon atoms,

    R⁶

    is a linear or branched (C₁-C₈)-alkyl, (C₁-C₈)-oxyalkyl, cycloalkyl having 1 to 8 carbon atoms, aryl having 1 to 8 carbon atoms,

    [Z']

    is an optionally alkoxylated linear polyhydroxyalkyl having at least 2 hydroxyl groups in the alkyl chain,

    and mixtures thereof, and also one or more disintegrants.