SK35299A3 - 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

Process for preparing particulate detergents or cleaning agents

Technical field

BACKGROUND OF THE INVENTION The present invention relates to a process for the preparation of rapidly soluble, compacted particulate laundry detergent or cleaning compositions or compositions, or treated raw materials for said compositions, as well as prepared laundry detergent or cleaning compositions or compositions or compositions herein. .

BACKGROUND OF THE INVENTION

Particulate washing or cleaning agents having a bulk density of more than 600 g.dm &^lt; ^{3 >} have long been known in the art. In recent years, as the bulk density has increased, the concentration of active laundry detergents and cleaners has increased so that the consumer has to dispense not only a smaller volume but also a smaller product weight for washing or cleaning. The increase in bulk density and, in particular, the higher concentration of detergents or cleaning active ingredients in the composition at their general sale is accompanied, from a subjective point of view of the consumer, by poor solubility, since the composition used dissolves more slowly. This undesired retardation of solubility is solved, inter alia, by the use of a variety of conventional anionic or nonionic surfactants, in particular by the use of suitable surfactant mixtures which tend to form gel phases when dissolved in water. Gelling can occur at a surfactant content of from 10% (w / w), based on the total weight of the composition, that is to say with the customary surfactant contents in detergents or cleaning compositions. The tendency to form gels has also been reported to increase with increasing compactness of the particle structure of the composition.

EP-B-0 486 592 discloses a granular or extruded detergent or cleaning composition having a bulk density of more than 600 g.dm ³ containing anionic and / or nonionic surfactants in amounts of at least 15% by weight up to about 35% by weight ). The composition is produced by a process which solidifies a

-2sypká premix which comprises a plasticizer and / or lubricant, preferably an aqueous surfactant paste and / or the aqueous polymer solution, at high pressures between 25.10 ⁵ Pa and 200.10 ⁵ Pa (25 and 200 bar) is extruded as a thin beam; the bundle is cut off at the outlet of the press by means of a cutting device and rounded to the required granulate dimensions. The masterbatch consists, at least in part, of solid components, optionally mixed with liquid components, such as nonionic surfactants, liquid at room temperature. As mentioned above, aqueous solution formulations are preferably used as plasticizer and / or glidant. Also suitable are organic liquids with a relatively high boiling point, in this case mixed with water. However, the patent for water-free extrusion does not disclose any data on the preparation conditions. The prepared extrudate can either be used directly as a laundry or cleaning agent, or in admixture with other granules or powdered ingredients can be used to complete the preparation of laundry or cleaning agents. Due to the high compactness of grains and relatively high levels of surfactants, but also because of pre-required ball or bead ^with shapes that compared with previous granulates have a significantly smaller surface may, depending on the selected combinations of surfactants occur above difficulties.

It is known from WO-A-93/15 180 that the dissolution rate of such extruded compositions can be increased by adding to the premix short chain alkyl sulfates, especially C ₈ - to at most C ₁₆ - alkyl sulfates. However, this measure does not in all cases ensure an increase in the dissolution rate of the finished composition to the required extent.

German patent application DE 195 19 139.0 proposes to solve the discrepancies between the high degree of compaction of individual grains, in particular extrudates, on the one hand, and the simultaneous required rapid and especially gel-free solubility of ready-to-use detergents. ) detergents with a bulk density of more than 600 g.dm ^'3, containing at least 15% (by weight) anionic and / or nonionic surfactants; said compositions comprising at least two different granulated components, at least one of which is extruded and at least one is not extruded, the surfactant content including

-3 soaps in the extruded component are at most 15% (by weight) based on the extruded component. Additional proportions of surfactants are incorporated into the detergent or cleaning compositions in the second or more non-extruded components. This method, while solving the problem of gelling highly compacted high surfactant detergents and cleaning agents when used in a water bath, also presents a number of new problems. Stirring processes and associated fluctuations in repeatability of the set wash or cleaning results can occur in the compositions. In addition, the extruded component of the composition does not only have a high density, but also the dried extrudate is relatively hard. Under conditions of transport, storage and use, a relatively softer granular fraction of detergent or cleaning agent may be subjected to the mechanical effects of a harder extruded fraction, which may result in partial crumbling and abrasion of the softer particles and the formation of dust and very fine fractions.

The prior art methods generally employ both solid and room temperature liquid detergent ingredients; aqueous solutions and / or dispersions have also been widely used as granulating auxiliaries or, as mentioned in EP-B-0 486 592, also as plasticizers and / or as glidants. The prior art processes are associated with the risk that gel-like structures may already be formed during the preparation of said detergents and cleaning agents, which contribute to retarding dissolution upon re-dissolution in the aqueous wash liquor. Moreover, these methods of preparation, and in particular those in which water, aqueous solutions or aqueous dispersions are used, have the disadvantage that in most cases they require energy-intensive drying in order to achieve free-flowing and shelf-life; in addition, they often form coarse particle agglomerates that must be crumbled and / or sieved (see also: Size Enlargement by Agglomeration, Pietsch, W., John Wiley & Sons, page 180, 1990). A further disadvantage of said process may be that, particularly under the effect of pressure during extrusion, partial dissolution of the water-soluble fractions can occur, which can lead to particle enlargement as well as crystallization; these phenomena are generally disadvantageous in terms of dissolution rate of the finished composition. One method of preparing heavy granules with the aid of water-containing granulating excipients is a two-stage granulation process in which

First, a plastic primary agglomerate is prepared in a conventional mixer / granulator, which is then treated together with a liquid binder and / or powder in a second stage, in a device such as a rounder, a Rotocoater, a marumerizer and similar devices. The granulation and simultaneous rounding can be carried out, for example, in fluidized bed granulators which operate with a rotating disc. In this process, starting solid materials are initially introduced into the fluidized bed and then agglomerated with a liquid binder which is introduced into the fluidized bed by tangential nozzles (see also: Size Enlargement by Agglomeration, Pietsch, W., John Wiley & Sons, pages 450 and 451, 1990) ). In principle, the method can also be used as the anhydrous method (melt coating method), but does not take advantage of the possibility of a device for simultaneous batch drying.

In the literature (Size Enlargement by Agglomeration, Pietsch, W., John Wiley & Sons, pages 440 and 441, 1990), only two high pressure granulation processes are known which are carried out entirely without the use of water. These are tabletting in tablet presses and compacting on cylindrical presses, the latter method usually producing scales, which are subsequently broken into granular but irregularly shaped products by breaking. On this basis, so-called "Pre-breakers" are used in individual systems, in which the shape of the product can be individually adjusted in the granulation or crushing step itself. Consequently, undesirable fine and / or coarse fractions can be desulphurized from the granules thus obtained and optionally recycled to the production process.

International patent application WO-A-93/02 176 describes a process for the preparation of high bulk density solid detergents or cleaners by combining the raw solid and liquid detergents or cleaners with simultaneous or subsequent shaping, wherein, for example, solids may be used anionic surfactants and detergent adjuvants and nonionic surfactants may be used as the liquid fractions, the latter being prepared in the form of a intimate mixture with a substance which prevents the formation of particle agglomerates such as polyethylene glycol or polypropylene glycol or ethoxylated C8-C18 - fatty alcohols with 20 to 45 EO. Preferred nonionic liquid

The -5-surfactants are ethoxylated unbranched or in the 2-position with a methyl group branched alcohols having 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 foregoing, water is also described as a substance to prevent agglomeration; however, its use is less advantageous as the composition may have a lack of water due to internal storage drying and therefore its anti-agglomeration effect only partially or does not appear at all in the required direction for an improved dissolution rate. As described in said international patent application, mixtures of non-ionic surfactants with agglomeration suppressors, which can be added in liquid form or as dispersions, can be used in all known granulation methods using separately prepared mixtures and / or raw materials. According to the international patent application WO-A-91/02 047 (or European patent EP-B-0 486 592 respectively), the process can also be used in the extrusion process and this use is advantageous. Accordingly, the use of aqueous solutions, pastes, or aqueous dispersions is recommended, the water not being used as a clotting agent as described above and is usually dried at the exit of the extrusion. Extrusion without the addition of water was not explicitly stated; the addition of aqueous solutions is found in the Examples section as a supplement and separately from the mixture of the nonionic surfactant with the anti-clotting agent; in particular, that specification does not indicate any conditions of the preparation process in which extrusion without water is possible.

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

European patent application EP-A-0 711 828 discloses a process for preparing tablets in which a coated particulate product is compressed. Coating agent is a water-soluble binder or disintegrant with a melting point between 35

-6 and 90 ° C. As an essential feature of this process, it is stated that the compacting / granulating is carried out at a temperature of at least 28 ° C, which in any case is below the melting point of the binder.

WO-A-96/10 071 discloses a process for the preparation of granulates having a bulk density of at least 650 g.dm &^lt; ^{-3 >} and a surfactant content of at least 40% by weight, wherein the granulation process is carried out in one step in a high speed mixer at temperatures at room temperature and 60 ° C. Particles between 0.1 and 500 µm are used as solid starting materials, with at least 15% by weight of the particles being greater than 50 µm, but small, fine particles are useful, since the solid input material has a preferred large surface area. The binder is a mixture of surfactants consisting of anionic surfactants and nonionic surfactants in weight ratios of from 2: 8 to 8: 2; the binder content may be up to 20% (w / w). As the nonionic surfactant mentioned C 12 C ₁₅ primary alcohols containing 3-7 * EO groups. Particularly preferred surfactant compositions which contain up to 20% (by weight) of water are preferred in the above preparation processes, since the viscosity of the composition increases and the process is easier to control. The surfactant composition may additionally also contain polyethylene glycols.

U.S. Pat. No. 5,108,646 describes the preparation of detergent or agglomerates of laundry adjuvants in which 50 to 75 parts by weight of aluminosilicates or crystalline layered silicates are agglomerated with 20 to 35 parts by weight of a binder. Particularly suitable binders are highly viscous pastes of anionic surfactants, which may contain between 0 and 90% by weight of water. Polymers such as polyethylene glycols having a molecular weight between 1000 and 2000, as well as mixtures of said polymers with conventional nonionic surfactants such as C ₉ - C ₁₆ - alcohols with 4 to 8 EO groups, may also be used as long as their melting range does not start below 35. ° C, optionally below 45 ° C. The agglomeration takes place in a so-called intensive mixer with quite a certain and relatively high energy consumption.

If the energy expended is higher than the specified value, pre-agglomeration to the paste takes place, with the energy expended below the specified value, only a fine powder or only a very light agglomerate is obtained which, moreover, does not have the required grain size spectrum.

The purpose of this patent, on the other hand, is to provide a particulate laundry detergent or cleaning composition, or mixtures or treated raw materials, the particles of which have a relatively small surface area, especially if they are bead-shaped, for improved disintegration when dissolved in a water wash. In addition, the method of preparation must be economically favorable, with the possibility of avoiding the costly degree of drying.

SUMMARY OF THE INVENTION

According to one embodiment of the present invention, there is provided a process for preparing particulate laundry detergents or cleaning compositions, or mixtures, or treated raw materials for said compositions, having bulk densities of more than 600 g.dm &^lt; ^-3 &^gt; subsequent molding, having first prepared a masterbatch which each raw material and / or the composition are used at room temperature and at a pressure of 10 ⁵ Pa (1 bar) as a solid-having a melting point or softening point not below 45 ° C, and the optionally containing up to 10% non-ionic surfactants, which are liquid at temperatures below 45 ° C and a pressure of 10 ⁵ Pa (1 bar); by mechanical compacting action at temperatures of at least 45 ° C, the mixture is converted into a granular form and optionally further processed or treated, whereby

the premixture is essentially free of water, and

- in the premix, at least one raw material or mixture at a pressure of 10 ⁵ Pa (1 bar) and a temperature below 45 ° C are in solid form, but which under the conditions of preparation is as a melt, wherein the melt serves as a polyfunctional, in a water-soluble binder which, in the manufacture of the composition, also functions as a glidant as well as an adhesive (grains) of the granular detergent / detergent ingredients, but facilitates the disintegration of the grains when dissolving the composition in a water wash or cleaning bath.

In the context of the present invention, the term "substantially free of water" or "substantially anhydrous" means a condition in which the water content is in a liquid state, i.e. in a state not in the form of hydrate and / or constitutional water, less than 2% %, preferably less than 1% and especially less

-8 as 0.5% (w / w); the percentages are based on the weight of the masterbatch. In the premix process, water can be essentially introduced only in a chemically and / or physically bound form, optionally as a constituent of raw materials or mixtures which are solid at a temperature below 45 ° C and at a pressure of 10 ⁵ Pa (1 bar). but not as a liquid, solution or dispersion. Preference is given to a masterbatch having a total water content of not more than 15% by weight, which water is also not chemically and / or physically bound in liquid free form; it is particularly preferred that the content of non-zeolite and / or not in the bound water silicates in the solid premix is not more than 10% by weight, more preferably less than 7% and most preferably not more than 2 to 5% by weight.

In the context of the present invention, the term "particulate" laundry or cleaning compositions preferably means those compositions which do not have dust fractions and in particular have no particles smaller than 200 µm. Particularly preferred is a particle size distribution in which at least 90% by weight of the particles have a diameter of at least 400 µm. In one very preferred embodiment of the present invention, the prepared laundry or cleaning composition, composition, or treated raw materials consists of at least 70% by weight, more preferably at least 80% by weight and most preferably up to 100% by weight of spherical particles with such a distribution sizes that at least 80% by weight of the particles have a size between 0.8 and 0.2 mm.

In the present invention, the term "laundry or cleaning agents" refers to compositions which can be used for washing or cleaning without the need for admixture with other conventional ingredients in use. The composition, on the other hand, comprises at least 2 ingredients commonly used in detergents or cleaners; however, the mixtures are normally used only mixed with other components, preferably mixed together with other mixtures. The treated feedstock within the scope of the present invention is a relatively fine feedstock which is converted into coarser particles by the process of the present invention. More specifically, the treated raw material within the scope of the present invention is a composition that is added as a component of conventional detergents or cleaners.

The components used in the process according to the invention can be separately prepared mixtures, but also raw materials which are powdered or particulate, with the exception of nonionic surfactants which are liquid at temperatures below 45 ° C and a pressure of 10 ⁵ Pa (1 bar).

-9 (fine to coarse), but in each case at room temperature under 10 ⁵ Pa (1 bar) in solid form. As the particulate components, for example, spray-dried beads or a fluidized-bed granulate and the like can be used. The composition of the compositions is irrelevant to the present invention except for the water content, which must be such that the above-mentioned premix is substantially anhydrous and preferably does not contain more than 10% by weight of hydrate and / or constitutional water. In one preferred embodiment, the dried mixtures are used in the masterbatch. Said compositions may be prepared, for example, by spray drying, wherein the temperature is controlled such that the material at the outlet of the spray dryer is at or above 100 ° C, for example 110 ° C. It is also possible to use solid mixtures in the masterbatch which serve as carriers for liquids, for example liquid nonionic surfactants or silicone oil and / or paraffins. These compositions may contain water in the above range, said compositions being free-flowing and remaining free-flowing, or transportable, even at higher temperatures, at least 45 ° C. It is, however, very advantageous to use in the masterbatch mixtures having a water content of not more than 7% by weight, expressed on the masterbatch weight. It is preferred that the masterbatch does not contain free water, i.e., water which is not bound in any form in a solid and is therefore "in liquid form" or contains only a very limited amount of free water, for example about 0.2 or 0 5% by weight, expressed on the weight of the masterbatch; the presence of water results in a lowering of the melting point or softening point, and the final product will have less flowability and also bulk density.

It has unexpectedly been found that it is by no means indifferent to which solid feedstock or in which solid mixture the water is bound. For example, water bound to excipients such as zeolite or silicates (for a description of excipients see below), but especially if the water is bound to zeolite A, zeolite P or MAP and / or zeolite X, its content is considered to be less critical . On the other hand, it is preferred that the water content, which is bound to solids other than said excipients, be less than 3% by weight in the masterbatch. Therefore, in one embodiment of the present invention, it is preferred that the bound water content of the masterbatch is not more than 10% (w / w) and / or the water content bound other than zeolite and / or silicates is less than 7% (w / w). up to 5%

- 10 (w / w). In this case, it is preferred that the premix does not at all contain water which is not bound to the auxiliaries. This is technically very difficult to carry out, since the raw materials and mixtures generally bring at least trace amounts of water with them.

The content of solid mixtures used in the masterbatch that is not liquid at temperatures below 45 ° C is similarly, optionally additionally, up to 10% (w / w), more preferably up to 6% (w / w), again expressed with respect to the total amount of masterbatch. Preference is given to using solid mixtures which contain nonionic surfactants which are usually liquid at temperatures below 45 ° C and at a pressure of 1 bar, which can be prepared separately by any of the known methods, for example by spray drying, granulation or coating of nasal beads. In this way, masterbatches can be prepared which contain, for example, up to 10% (w / w), preferably less, in particular at most 8% (w / w), for example between 1 and 5% (w / w) nonionic surfactants.

Compositions which contain water in the above form and / or serve as carriers for liquid substances, in particular for nonionic surfactants, which are liquid at room temperature, may also contain liquid components at room temperature and may be used according to the invention if in any they do not have a softening temperature below 45 ° C. Likewise, the individual raw materials used separately have a melting point of at least 45 ° C. It is preferred that the melting point or the softening point of all of the individual raw materials and mixture used is more than 45 ° C, more preferably at least 50 ° C.

In one preferred embodiment of the invention, at least 80% (w / w), preferably at least 85% (w / w), and most preferably at least 90% (w / w) of the blends used in the masterbatch and the individual raw materials have significantly higher softening or melting points than in production. For purely economic reasons, in practice the operating temperatures do not exceed 150 ° C, preferably not higher than 120 ° C. Therefore, at least 80% (by weight) of the mixture used and the individual raw materials have a softening or melting point higher than 150 ° C. The softening or melting point is

-11 as a rule well above these temperatures. In the case of the use of temperature-decomposing components, for example peroxide bleaching agents such as perborate or percarbonate, the decomposition temperature of the component at 1 bar and in particular at the higher pressures expected in the extrusion process according to the invention is equally significant higher than 45 ° C.

In addition to the basic ingredients, the masterbatch may additionally contain up to 10% by weight of nonionic surfactants which are liquid at a temperature below 45 ° C and a pressure of 1 bar, in particular alkoxylated alcohols such as fatty alcohols or carbon-chain oxoalcohols commonly used in detergents. having a length of between 8 and 20 carbon atoms, and in particular having an average of three to seven ethylene oxide units per mole of alcohol (for more details see below). The addition of liquid nonionic surfactants can be chosen to a height as long as it is ensured that the premix is still free-flowing. If liquid nonionic surfactants are used in the masterbatch, it will be preferred that the liquid nonionic surfactants and the disintegrating binder are used separately in the preparation process. In one preferred embodiment of the invention, in the continuous manufacture, liquid nonionic surfactants are applied, in particular by means of nozzles, to the flow of powdered material which absorbs the liquid component.

However, the masterbatch comprises at least one feedstock or at least one mixture which also serves as a binder; although solid (s) at room temperature; however, they are liquid in the form of melt when compacted under production conditions. Said binder may also be separately melted and sprayed onto the masterbatch or dropwise into the masterbatch; it is preferred to introduce the binder into the masterbatch in solid form as a powder. The melting or softening temperature at a pressure of 1 bar is at least 45 ° C, preferably (especially for economic reasons) below 200 ° C, most preferably at most 150 ° C. If the binder is introduced into the masterbatch in the form of a melt, then the temperature in the melting vessel is similarly higher than 45 ° C, up to a maximum of about 200 ° C, and the temperature in the melting vessel can significantly exceed the melting point or softening point of the binder or binder mixture. .

The type of suitable binder and processing temperature during compaction are interdependent. It will be preferred that the binder be in the processing step

The compaction is best dispersed throughout the batch and temperatures such that the binder at least softens must be used in this step, preferably if the binder is wholly and not only partially in the molten form. Thus, a binder with a high melting point or a softening point is selected and the temperature in the compaction step must be adjusted so that the binder melts with certainty, depending on the desired composition of the final product, and the need to process higher temperature sensitive raw materials. In such cases, the upper temperature limit is given by the decomposition temperature of the sensitive feedstock, and it is preferable to operate at a significantly lower temperature than said decomposition temperature. On the other hand, the lower limit for melting point or softening point is therefore of such great importance that at melting points or softening temperatures below 45 ° C, a finished product is generally obtained which is already at room temperature or at slightly elevated temperatures of about 30 ° C, also at summer temperatures and in storage or transport conditions, it tends to stick to aggregates. It has proven to be very advantageous if temperatures of only a few degrees above the melting point or above the softening point are employed, for example by 2 to 20 ° C.

Without intending to be limited to the following theory, the present inventors are of the opinion that by uniformly distributing the binder in the masterbatch in the compacting step of the solid mixtures and any other individual raw materials, the binder is wrapped and subsequently bonded together that many individual small particles evenly form end products; The fine particles together hold together by the action of a binder which takes on the role of a preferred thin separating wall (layer) between the glued particles. In an idealized form, it is possible to start from similar shapes of honeycomb construction, these honeycomb cells being filled with solids (mixture or individual raw materials). In contact with water, as well as in contact with cold water, such as at the beginning of an automatic washing machine program, said thin separating walls dissolve or disintegrate almost immediately; this is unexpected if the binder itself is not readily soluble in water at room temperature, for example because of its crystalline structure. It will then be preferable to use binders which are used in the following test procedure

A concentration of 8 g of binder in 1000 ml of water at 30 ° C almost completely dissolves within 90 seconds.

The binder or binders must be such that their tack properties are maintained even at temperatures significantly higher than their melting or softening point. On the other hand, it is also important for the choice and amount of binder (s) used that the bonding properties do not deteriorate when the final product is cooled again, and that the cohesiveness of the final product is ensured in such a way that larger units.

Hereinafter, the description per single binder is simplified. It is obvious that several different binders and / or mixtures of different binders can also be used.

In one preferred embodiment of the present invention, a binder is used which is present as a melt at temperatures up to at most 130 ° C, preferably at most 100 ° C, and in particular up to 90 ° C. The binder must be chosen according to the manufacturing process and conditions for the preparation of the detergent or detergent, or the manufacturing process and the preparation conditions, in particular the operating temperature, must be adjusted if the use of a particular binder is required to allow its use.

Preferred binders, alone or in admixture with other binders that may be used, include polyethylene glycols, 1,2-polypropylene glycols as well as modified polyethylene glycols and polypropylene glycols. Modified polyalkylene glycols include sulfates and / or disulfates of polyethylene glycols or polypropylene glycols having a molecular weight of between 600 and 12,000, in particular between 1,000 and 4,000. and 6000, preferably between 1000 and 4000. For a more detailed description of the modified polyalkylene glycol ethers, reference is made to the published international patent application WO-A-93/02 176. Within the scope of this invention, polymers are included among the polyethylene glycols for the preparation of which C ₃ to C ₅ glycols as well as glycerol and mixtures thereof. In addition, ethoxylated derivatives such as trimethylolpropane with 5 to 30 EO groups are also included.

The preferred polyethylene glycols used may have a straight or branched structure, with unbranched polyethylene glycols being particularly preferred.

Highly preferred polyethylene glycols include those having a molecular weight of between 2000 and 12,000, preferably about 4000, and polyethylene glycols with a molecular weight below 3500 and above 5000 can also be used, especially in combination with polyethylene glycols with a molecular weight of about 4000; Such a combination is preferred that the combination of more than 50% (wt), based on the total amount of polyethylene glycols, poyetylénglykolov to the relative molecular mass between 3500 and 5000. The binder may also be used also polyethylene glycols, which are at room temperature and a pressure of 1.10 ⁵ Pa (1 bar) in the liquid state; in particular polyethylene glycol having a relative molecular weight of 200, 400, and 600. The liquid polyethylene glycols must, of course, only be used in a mixture with at least one other binder, and this mixture must again satisfy the requirement of the present invention. was more than 45 ° C.

I

Modified polyethylene glycols also include end-capped polyethylene glycols on one or more sides, wherein the end-groups may preferably be C 1 -C 12 -alkyl chains, either unbranched or branched. Particularly preferred as end groups are alkyl chains between C 1 -C ₆ -, most preferably C 1 -C ₄ -, with isopropyl and isobutyl or tertiary butyl being possible alternatives.

Polyethylene glycol derivatives with unilaterally end-capped groups may also conform to formula C _x (EO) _y (PO) _z , wherein C _x may be an alkyl chain of 1 to 20 carbon atoms in length, y may be 50 to 500 and z may be 0 to 0 20. For z = 0, these compounds overlap with those of the preceding paragraphs.

EO - PO - polymers can also serve as a binder (x is equal to 0).

Also suitable as binders are low molecular weight polyvinylpyrrolidones and derivatives thereof with relative molecular weights up to a maximum of 30,000. Preferred molecular weight weights are between 3000 and 30,000, for example about 10,000. It is preferred that said polyvinylpyrrolidones are not used as a binder.

- separately, but in combination with other binders, especially in combination with polyethylene glycols.

Other suitable binders have proved to be raw materials which themselves exhibit washing or cleaning properties, for example nonionic surfactants having a melting point of at least 45 ° C, or mixtures of nonionic surfactants and other binders. Preferred nonionic surfactants include alkoxylated fatty or oxo-alcohols, especially C12-C18-alcohols. Particular preference is given to those alcohols whose alkoxylation stage, in particular the ethoxylation stage, is on average 18 to 100 AO, in particular EO, per mole of alcohol, and mixtures of these surfactants are particularly preferred. In view of the present invention, the preferred binder properties are in particular fatty alcohols having an average of 18 to 35 EO, in particular an average of 20 to 25 EO. Alternatively, ethoxylated alcohols with an average smaller number of EO units per mole of alcohol, for example, a tallow fatty alcohol of 14 EO, may also be used in the binder mixtures. However, it is preferred that these relatively low ethoxylated alcohols be used only in mixtures with higher ethoxylated alcohols. The preferred proportion of these relatively low ethoxylated alcohols is less than 50% by weight, in particular less than 40% by weight, based on the total amount of binder used. Commonly used non-ionic surfactants such as C ₁₂ - C ₁₈ - alcohols with an average of 3 to 7 EO, which are liquid at room temperature, are preferably used in the binder mixtures according to the invention only in amounts which are less than 10% (w / w), in particular less than 8% (w / w) and most preferably less than 2% (w / w) of these nonionic surfactants, based on the final product of manufacture. As mentioned above, the addition of nonionic surfactants liquid at room temperature is naturally less preferred. Therefore, in one preferred embodiment, said nonionic surfactants do not form part of the binder mixture, since these nonionic surfactants not only lower the softening point of the mixture, but can also lead to tackiness of the final product; furthermore, their tendency to form gels in contact with water also does not meet the requirement of rapid dissolution of the binder / separating layer of the final product to the desired extent. Likewise, it is not preferred that the binder mixtures contain the customarily used anionic surfactants or their precursors, anionic acid surfactants in detergents or cleaners. Fatty alcohols, C 12 to C ₈ -, fatty alcohol C ₆ - to C ₈ -, C ₈ or a net - fatty alcohol

16 s of more than 50 EO, preferably with about 80 EO, are referred to as an excellent binder which can be used either alone or in combination with other binders.

Other nonionic surfactants which are suitable as binders are fatty acid methyl esteroxylates which do not tend to gel, especially those containing 10-25 EO (a detailed description of this class of substances is given below). Particularly preferred representatives of this group of substances are predominantly methyl esters based on fatty acids C ₆ - to C ₈ -, e.g., fatty acid methyl ester hardening beef tallow, an average of 12 EO, or with an average of 20 EO.

Another group of substances which are suitable as binders within the scope of the present invention are fatty acids with 2 to 100 EO, whose "fatty acid" residues may be unbranched or branched within the scope of the present invention. Particularly preferred are those ethoxylates having a narrow homologous distribution (NRE) and / or a melting point above 50 ° C. These fatty acid ethoxylates may also be used alone as a binder or in combination with other binders; unethoxylated sodium and potassium soaps are less preferred and are used only in combination with other binders.

Mixed hydroxyethers as described in European patent application EP-A-0 754 667 (BASF), which can also be obtained by ring opening of epoxides of unsaturated fatty acid esters, in particular in combination with polyethylene glycols, the abovementioned fatty acid methyl ester ethoxylates or fatty acid ethoxylates.

Unexpectedly, anhydrous swellable polymers, in particular starch diphosphate / glycerol, polyvinylpyrrolidone / glycerol and modified celluloses / glycerol, for example hydroxypropylcellulose / glycerol, have also proved to be excellent binders. Particularly preferred are 5 to 20% (w / w) solutions of said polymers in glycerol, especially about 10% (w / w) solutions.

In a preferred embodiment of the invention it is used as the binder mixture consists of C 12 to C ₈ - fatty alcohol derived from a basket or tallow, an average of 20 EO, and polyethylene glycol to the relative molecular weight of 400-4000.

-17V another preferred embodiment of the invention the binder is a mixture which comprises in particular the methyl ester, based on the fatty acids C ₁₆ - to the targeted for approximately 10 to 25 EO groups, especially the methyl ester of hydrogenated beef tallow with an average of 12 EO, or with an average of 20 EO, and a C12- to C18-fatty alcohol derived from coconut fat or tallow with an average of 20 EO and / or polyethylene glycol having a molecular weight of from 400 to 4000.

In very preferred embodiments of the invention, suitable binders have been found to be based either on polyethylene glycols alone having a relative molecular weight of about 4,000 or a mixture of C12- to C14-fatty alcohol derived from coconut fat or tallow, with an average of 20 EO and the above-described fatty acid methyl esteroxylates and polyethylene glycol, in particular having a molecular weight of about 4000. Most preferred are mixtures of polyethylene glycol having a molecular weight of about 4000 with the abovementioned fatty acid methyl esteroxylates or a C16- to C16-8 fatty acid alcohol in 20 EO. ratio of 1: 1 or higher.

The binder mixture may further comprise other raw materials such as trimethylolpropylene etc (Product of BASF, BRD), in particular in a mixture of polyethylene glycols; however, they cannot be used as a binder alone, although they function as a binder / adhesive, but have no effect on the disintegration of the product in water.

Alkyl glycosides having the general formula RO (G) _X , in which R represents a primary unbranched or methyl branched, in particular at the 2-position, a methyl branched aliphatic radical having a radical of 8, can be used as further binders alone or in combination with other binders. and G is a symbol which represents a glycose unit having 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, which indicates the relative proportions of monoglycosides and oligoglycosides, is arbitrarily selected from the numbers 1 to 10; a preferred value of x is about 1.2 to 1.4. Particularly suitable are those alkyl glycosides having a softening point above 80 ° C and a melting point above 140 ° C. Highly concentrated mixtures containing at least 70% by weight of alkyl glycosides, preferably at least 80% by weight, of alkyl glycosides are also suitable. When using higher shear loads, melt-agglomeration and especially melt-extrusion can be

- 18 concentrated mixtures can be carried out just at temperatures which are above the softening point but are still below the melting point of the mixtures. Although the alkyl glycosides can be used alone as a binder, it is preferable to use mixtures of alkyl glycosides with other binders. Particularly preferred are mixtures of polyethylene glycols and alkyl glycosides, preferably in weight ratios of 25: 1 to 1: 5, in particular from 10: 1 to 2: 1.

Polyhydroxy fatty acid amides having the general formula (I) in which R ² CO represents an aliphatic acyl radical having 6 to 22 carbon atoms, R ³ represents hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Zj denotes unbranched or branched a polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups is also suitable as a binder, especially in combination with polyethylene glycols and / or alkyl glycosides.

R ³ R ² -CO-N- [Z] (O

The polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular glucose.

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

R ⁴ -OR ⁵

I

R ³ -CO-N- [Z] (N) wherein R ³ represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ⁴ represents a linear, branched or cyclic alkyl group or an aryl group containing 2 to 8 carbon and R ⁵ represents an unbranched, branched or cyclic alkyl radical or an aryl radical

-19 radical or oxy-aryl radical having 2 to 8 carbon atoms, with a C 1 -C ₄ alkyl or phenyl radical being preferred, and [Z] denotes an unbranched polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups or alkoxylated, preferably ethoxylated or propoxylated derivatives of these residues. In this case too, it is preferred to prepare [Z] by reductive amination of sugars such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. Said N-alkoxy- or N-aryloxy-substituted compounds can then be prepared, for example, as described in International Patent Application WO-A-95/07 331 by converting fatty acid methyl esters in the presence of an alkoxide catalyst to the desired poly hydroxy fatty acid amides. A particularly preferred glucamide is melted just at 95-105 ° C. However, here too, as in the case of alkyl glycosides, the normal operating temperatures which are above the softening point but below the melting point are sufficient in the process according to the invention.

The preferred binder (s) content in the masterbatch is at least 2% (w / w) but less than 15% (w / w), especially less than 10% (w / w), and particularly preferably the binder (s) content is from 3 to 6% (w / w). always referring to the total weight of the masterbatch. The anhydrous swellable polymers are used in particular in amounts below 10% by weight, preferably in amounts of from 4 to 8% by weight, most preferably from 5 to 6% by weight.

In a preferred embodiment of the process according to the invention, the solids for the preparation of solid and free-flowing premixes are first mixed together in a conventional mixing and mixing system at room temperature to slightly elevated temperature, preferably below the melting or softening point of the binder. / or granulating device. The solids mentioned are those which, according to European patent EP-B-0 486 592, can serve as plasticizers and / or glidants. These include, in particular, anionic surfactants such as alkylbenzene sulfonate and / or (fatty) alkyl sulfate, but also polymers such as polymeric polycarboxylates. A more detailed description of possible anionic surfactants and polymers is given later elsewhere in the list of possible excipients. The glidant may additionally serve as a binder or binders or binder mixtures.

Advantageously, the binders are blended into the compositions as the last component. As mentioned above, the binders can be added as solids, i.e. at an operating temperature below their melting or softening point, or as a melt. However, it is preferable to admix under such conditions as to ensure a homogeneous distribution of the binder in the solid mixture as uniformly as possible. When using very fine binders, the admixing can be carried out at temperatures below 40 ° C, for example at binder temperatures between 15 and 30 ° C. However, it is preferred that the binder has a temperature at which it is already in the form of a melt, that is, a temperature higher than the softening temperature, more preferably the binder is in the fully molten state. Preferred melt temperatures are in the range of 60 to 150 ° C, more preferably the temperature range is from 80 to 120 ° C. During the mixing process at room temperature to slightly elevated temperature, but below the softening point or the melting point of the binder, solidification of the melt occurs almost immediately and the masterbatch according to the invention takes a solid and free-flowing form. In any case, the preferred mixing process will take until the melt solidifies and the masterbatch is in a solid and free-flowing form.

The joining of washing or cleaning compositions and / or raw materials with simultaneous or subsequent shaping can be carried out by conventional methods in which compaction forces are applied, i.e. by methods such as granulation, compression (compacting), for example compacting on rolls or extrusion, or tabletting, optionally with an additive. conventional particulate disintegrating or pelletizing agents. Pre-mixed mixtures such as spray-dried granules may be used in the masterbatch; the invention is not limited thereto. According to the method of the present invention, no spray-dried granules need be added, since very fine raw materials with dust fractions can also be processed without any difficulty by the method of the present invention without being pre-treated by agglomeration, for example in a spray drier.

The actual granulation, compacting, tabletting, pelletizing or extrusion processes are carried out according to the invention at operating temperatures which, at least in the compaction process, correspond at least to the softening point, if not the melting point of the binder. In one preferred embodiment of the invention, the processing temperature is significantly higher than the melting temperature, optionally above the temperature at which the binder is added as a melt. In the compaction process, it is particularly advantageous to work in such a manner

-21 a temperature which is not more than 20 ° C above the melting point or above the upper melting point of the binder. While it is technically possible to work at even higher temperatures, it has been shown that a temperature difference of 20 ° C from the melting point or the softening point of the binder is quite sufficient, and further raising the temperature does not bring any further advantages. For this reason, especially for energy reasons, it is advantageous to operate above, but as close as possible to the melting point or the upper temperature limit of the binder melting range. Said temperature regime has the further advantage that substances sensitive to higher temperatures, for example peroxide bleaching agents such as perborates and / or percarbonates, but also enzymes can be processed without significant losses of the active substance. The possibility of precisely controlling the temperature of the binders, especially at the critical compaction stage, i.e. between mixing / homogenizing the masterbatch and the molding, allows a very suitable and gentle guidance of the entire production process so that the masterbatch is only briefly exposed to higher temperatures. Said exposure time is preferably between 10 seconds and at most 5 minutes, more preferably the exposure time is at most 3 minutes.

In a process that is substantially water-free, not only peroxide bleaches can be processed without losing their efficacy, but also peroxide bleaches can be treated simultaneously with bleach activator (see below for detailed description) without worrying. decrease in activator activity.

In one preferred embodiment, the process of the invention is carried out by extrusion, as described, for example, in European patent EP-B-0 486 592 or in the international patent application WO-A-93/021 176. In this method, the solid masterbatch is extruded by pressure. The extruded head of material is cut to a predetermined size by means of a slicer. The homogeneous and solid masterbatch comprises a plasticizer and / or a glidant which causes the masterbatch to soften under extrusion or the effect of specific work and to be extrudable. Preferred plasticizers and / or glidants are surfactants and / or polymers which, within the scope of the present invention, with the exception of the aforementioned nonionic surfactants, are used in the masterbatch not in a liquid state and especially not in an aqueous environment but in a solid state.

Applicants explicitly refer to the aforementioned patents and patent applications for clarification of individual extrusion processes. In one preferred embodiment of the present invention, the masterbatch, preferably in a continuous manner, is fed to a planetary screw extruder (extruder) or to a twin or twin screw extruder with the same or counter-rotating worms whose housing and granulation head of the screw extruder be heated to the required temperature. Under the effect of shear stresses from the extruder screw, the premix is plasticized and compacted. It is preferred that achieves pressure of 25.10 ⁵ Pa (25 bar) at extremely high flows of material and depending on the equipment used and the pressure may be lower. The extruded material comes from the extruder head in the form of a thin bundle - column. Finally, the extrudate is crushed by means of a rotary knife divider, preferably into a spherical to cylindrical shape of granular grains. The diameter of the die head and the length of the material to be separated are adjusted to the required granulate dimensions. In this embodiment, it is possible to maintain the production of granules in such a way that substantially uniform, predetermined grain sizes are achieved, and in individual cases, the absolute grain sizes can be adapted to their intended use. Generally, particle diameters of up to 0.8 cm are preferred. Important embodiments envisage the production of individual granules having grain sizes in the millimeter area, for example in the range of 0.5 mm to 5 mm, more preferably in the range of about 0.8 mm to 3 mm. The ratio of length to diameter of the cut primary granules is, in one important embodiment, in the range of about 1: 1 to about 3: 1. It is further preferred that the plastic primary granulate is still guided for further shaping (shaping); in this case, the edges of the raw extrudate are rounded such that spherical or approximately spherical shapes of the extruded grains can finally be obtained. Optionally, a smaller amount of dry powder, for example zeolite powder, such as zeolite NaA powder, may also be used in this manufacturing step. Said shaping can be carried out using rounding machines available on the market. Care should be taken that only a limited amount of fine-grained fraction is produced in this production step. The drying described in the prior art in the preferred embodiments of the prior art is saved within the scope of the present invention, since the method of preparation according to the present invention is

The invention proceeds substantially free of water, i.e. without the addition of free, unbound water.

Optionally, extrusion / compression can also be carried out in low-pressure screw extruders, hololi or extruders.

In one very preferred embodiment of the present invention, the temperature mode in the transition region of the screw, between the pre-divider and the extruder head, is adjusted to achieve at least the binder melting point or upper limit of the binder melting temperature range; preferably, the temperature is higher. In this case, the time of effect of the high temperature on the material in the compression zone of the extrusion is preferably below 2 minutes and in particular in the range between 30 seconds and 1 minute.

The short residence times, made possible by the use of the water-free preparation process of the present invention, further allow the extrusion of compositions containing peroxide bleaching agents, optionally together with bleach activators, at higher temperatures without loss of bleaching performance.

In one very preferred embodiment of the present invention, the binder used has a melting point or melting temperature range up to 75 ° C; operating temperatures which are at most 10 ° C and in particular at most only 5 ° C higher than the melting point or the upper temperature limit of the binder melting region have proved to be very suitable operating temperatures.

In the above-mentioned operating conditions, the binder also functions as a glidant in addition to the above-mentioned effects and furthermore prevents or at least limits the accumulation of labels on the walls of the device and on the compaction parts. This is true not only for processing in screw extruders, but also for processing in, for example, continuously operating mixers / granulators or in production on roller presses.

The compacted material preferably has temperatures not exceeding 80 ° C upon exit from the production apparatus, more preferably between 35 and 75 ° C. It is very advantageous to consider the outlet temperatures of the material, especially in the extrusion process from 40 to 70 ° C, for example up to 60 ° C.

As in the extrusion process and in other processes, it is advantageous to direct the primary granulate (or compactate) produced to the next shaping manufacturing step, in particular for rounding, so that spherical or almost spherical (beaded) shapes can be achieved in the final product. grains.

It is an essential feature of a preferred embodiment of the present invention that the particle size distribution of the masterbatch may be substantially wider than said distribution in the final product produced according to the present invention. The masterbatch may comprise a significantly larger proportion of fine-grained material, even dusty or even coarse-grained, and it is advantageous that the masterbatch with a relatively broad particle size distribution and a relatively high proportion of fine grains can be converted into an end product having a relatively narrow particle size distribution. and only small proportions of fine grains.

Since the production method of the present invention essentially does not use water, i.e. with the exception of the water contained ("as impurities") in the solid materials used, it is already in the production process. minimized, even eliminated, the risk of gelatinisation of the tenside raw materials and, moreover, this method also represents, from an ecological point of view, a full-fledged process which not only saves energy by eliminating subsequent drying, but also reduces emissions that arise in particular with current drying methods.

In contrast to the compositions produced hitherto, it has been shown that the behavior of the detergents produced according to the invention when reconstituting in a washing bath depends in particular on the ability to dissolve the individual components; the more ingredients are present, the faster they will dissolve, the faster the final product will dissolve; the more slowly soluble the components, the slower the dissolution of the final product. Unwanted interactions during re-dissolution, such as gelling and the like, do not appear to play any role in the process of the present invention, nor in detergents or cleaning compositions with very high densities, for example greater than 750 to 800 g.dm &^lt; ^-3 &^gt;

The composition, mixture and treated raw materials produced by the above-described processes exhibit an increased dissolution rate in comparison with the prior art compositions, mixtures and treated raw materials, which may have the same

Thus, the final composition, but not prepared by the process of the invention, was therefore not produced under anhydrous conditions by melt.

According to the invention, the present invention further comprises a particulate detergent or cleaning composition which has been produced by the process of the invention and whose dissolution properties depend solely on the properties of the individual raw materials and mixtures used. Without wishing to be limited to this theory, the Applicants are of the opinion that the said exceptional dissolution properties are due to a honeycomb-like particle structure (grain), the honeycomb being filled with a solid.

In one preferred embodiment of the invention, the granular or extruded detergent composition comprises at least 80% by weight of the composition and / or treated raw materials prepared according to the invention. The granular or extruded composition preferably comprises at least 80% (by weight) of the base granulate or base extrudate prepared according to the invention. The remaining fractions can be prepared by any of the known methods and admixed. It is also advantageous if the remainder, which can be mixtures and / or treated raw materials, are also produced by the process according to the invention. In particular, this will allow the base granulate and the remaining fractions to be produced with approximately equal bulk, with approximately equal bulk density, particle size and particle size distribution.

In another aspect, the invention encompasses mixtures and treated raw materials produced according to the invention, for example, granules (extrudates) of excipients, granules (extrudates) of bleach activators, or enzyme granules (extrudates). In particular, the treated feedstocks have an exceptionally high dissolution rate in water, especially when the feedstock is used in very fine form or ground.

Particularly preferred are basic granules, blends and treated raw materials having a spherical or bead shape.

Unexpectedly, the products obtained by the process of the invention exhibit very high bulk weights. The bulk density is preferably higher than 700 g.dm &^lt; ^{3 &gt};, especially between 750 and 1000 g.dm &^lt; ³ &^gt;. If the extrudates are mixed with other ingredients having lower bulk densities, the bulk density of the final product is reduced but not in the mixing ratio as would normally be expected. It is believed that a composition having approximately spherical particle shapes, and in particular extrudates, has been

The 26 produced by the process of the present invention are closer to an ideal spherical shape with a smooth "greasy" surface than the compositions and extrudates produced by the known method, in particular using water. This results in a higher degree of space filling in the compositions of the present invention, resulting in higher bulk weights, although a component that has neither spherical shape nor so high bulk density is admixed.

The resulting particulate end products can either be used directly as laundry or cleaning agents, or can be subsequently processed and / or treated by conventional methods. Conventional post-treatment methods may include the application of a very fine detergent or cleaning component ("powdering"), whereby the bulk density can generally be further increased. Advantageous post-processing may also be by the method of the applications of German patents DE-A-19 524 287 and DE-A-19 547 457, wherein the dust or at least very fine particles (so-called fines) of the additive are adhered to the particulate product of the production according to this patent. The present invention, which serves as a grain and produces a composition comprising a so-called fines as an outer shell. Advantageously, this can again be achieved by melt-agglomeration, using the same binder as in the process of the invention. For the agglomeration of melt-containing fines into a base granulate produced according to the invention, reference is expressly made to the published applications of German patents DE-A19 524 287 and DE-A-19 547 457.

Generally, it is understood that the fine particulate products produced by the process of the present invention serve as mixtures to which other components, optionally also other mixtures, are admixed. Reference is made herein to the cited patent applications and patents, in particular to European patent EP-B-0 486 592 as well as German patent applications DE-A-19 519 139, DE-A-19 524 287 and DE-A- In addition to enzymes, bleach activators and antifoams, in particular, salts such as silicates (crystalline or amorphous), including metasilicates, carbonates, bicarbonates, sulphates, hydrogen sulphates, citrates and other polycarboxylates, but also organic acids such as citric acid (see below). Addition of the admixtures in granular form and with a particle size distribution which is suitably adjusted

The particle size distribution of the composition produced by the process of the present invention.

The following is a detailed description of possible additives to the composition of the invention and the ingredients used in the method of the invention.

Important additives to the composition of the invention and the ingredients used in the process of the invention are surfactants, in particular anionic surfactants, which should be used or may be present in the composition of the invention in an amount of at least 0.5% (w / w). These surfactants include, in particular, sulfonates and sulfates, but also soaps.

Suitable sulphonate surfactants are preferably C8-C13-alkylbenzenesulphonates, olefin sulphonates, i.e. mixtures of alkene and hydroxyalkane sulphonates, as well as disulphonates, which can be obtained, for example, from C12- to C18-monoolefins having a terminal or internal double bond with sulphonation with gaseous oxide followed by alkaline or acid hydrolysis of the sulfonated product.

Suitable are alkane sulfonates which are prepared from C12- to C18-alkanes, for example by sulfonation or sulfoxidation followed by hydrolysis or neutralization.

Also suitable are esters of α-sulfonated fatty acids (estersulfonates), for example α-sulfonated methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids, which are prepared by α-sulfonation of fatty acid methyl esters of vegetable or animal origin having from 8 to 20 carbon atoms in a fatty acid molecule. The sulfonation product is neutralized to a water-soluble mono salt. Preferably, they are α-sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids, and sulfonated products of unsaturated fatty acids may also be used, but to a limited extent, for example in an amount of no more than about 2 to 3% by weight . Highly preferred are α-sulfonated alkyl esters of fatty acids whose alkyl chain of the ester group contains no more than 4 carbon atoms, such as, for example, the methyl ester, the ethyl ester, the propyl ester and the butyl ester. extremely

Preferred is the use of methyl ester of α-sulfonated fatty acid (MES), but also of its saponified di-salt.

Other suitable anionic surfactants are the sulfated glycerol esters of fatty acids which are mono-, di- and tri-esters, as well as mixtures thereof, as obtained by sterilizing the monoglycerol with 1 to 3 moles of fatty acid, or by esterifying triglycerides with 0.3 to 2 moles. moles of glycerol.

As alkyl (en) sulfates are the alkali metal salts, especially the sodium salts of sulfuric acid half esters of a C ₂ - to CIE- fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearylated fatty alcohol, or with a C ₁₀ to C ₂ o-oxo alcohol and corresponding semi-esters of secondary alcohols having the indicated chain length. Further preferred are alkyl (en) sulphates with the above-mentioned carbon chain lengths containing a synthetic, petrochemical-based, unbranched alkyl moiety having a similar structure to the corresponding compounds based on fatty chemistry raw materials. C12- to _C18 -alkyl sulfates are of interest from the washing technique, _C12 -C15-alkyl sulfates are preferred, and C14-C15-alkyl sulfates are particularly preferred. Suitable anionic surfactants are also 2,3-alkyl sulfates which are prepared, for example, according to U.S. Pat. No. 3,234,258 or 5,075,041, and are commercially available under the designation DAN (R) from Shell Oil Company.

Also suitable are monoesters of ethoxylated sulfuric acid with from 1 to 6 moles of ethylene oxide, a branched or branched C ₇ to C ₂ fatty alcohol, such as 2-methyl branched C ₉ to C ₁₁ alcohols, with an average of 3.5 mol ethylene oxide (EO), or C ₂ - to C ₈ - fatty alcohols containing 1 to 4 EO. They are used in detergent compositions only in relatively small amounts, for example in an amount of from 1 to 5% by weight, as they exhibit high foaming power.

Preferred anionic surfactants are also salts of alkylsulfosuccinic acid, which are referred to as sulfosuccinates or sulfoesters of succinic acid and are monoesters or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols, and most preferably ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ to C ₁₈ fatty alcohol residues or mixtures thereof. More preferably, the sulfosuccinates contain a fatty alcohol moiety that is derived from ethoxylated fatty alcohols, which themselves are nonionic

-29 surfactants (see below). Particularly preferred are again sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homologous distribution. Alkyl (en) succinic acids, preferably having 8 to 18 carbon atoms in the alkyl (en) chain, or salts thereof, may also be used.

Suitable further anionic surfactants are amino acid derivatives of fatty acids; examples of said amino acids include N-methyltaurine (taurides) and / or N-methylglycine (sarcosides). Highly preferred are the sarcosides and / or sarcosinates and, in particular, the higher sarcosinates and, optionally, unsaturated fatty acids, such as oleyl sarcosinate.

Of the other anionic surfactants, in particular soaps may be used, preferably in amounts of from 0.2 to 5% by weight. Particularly suitable are soaps of saturated fatty acids such as salts of lauryl, myristic, plamitic, stearic, hydrogenated erucic and behenic acids, in particular from natural fatty acids, for example mixed soaps derived from coconut, palm kernel or tallow fatty acids. Along with the aforementioned soaps or as an additive to the soaps, the aforementioned alkenylsuccinic acid salts can also be used.

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

The compositions according to the invention contain, optionally in the process according to the invention, anionic surfactants preferably used in amounts of from 1 to 30% by weight and in particular in amounts of from 5 to 25% by weight.

In addition to anionic and cationic surfactants, in addition to zwitterionischen surfactants and amphoteric surfactants, nonionic surfactants are particularly preferred.

Suitable anionic surfactants are alkoxylated, preferably ethoxylated, in particular primary alcohols, preferably having 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 may be unbranched or branched in the 2-position by methoxy group, optionally unbranched and branched moiety may be present in the mixture in analogy to that described for oxoalcohols. Particularly preferred are unbranched alcohol ethoxylates

-30 residues of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, soybean, or oleyl alcohol, and with an average of 2 to 6 EO per mole of alcohol. Preferred ethoxylated alcohols include, for example, C 12 to C ₁₄ - alcohol having 3 EO or 4 EO, C ₉ - to C n alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C 12 to C ₈ - alcohols containing 3 EO , 5 EO or 7 EO and mixtures thereof, such as mixtures of C12 to C14 alcohol with 3 EO and C 12 to C ₈ - an alcohol with 7 EO. The ethoxylation steps indicated represent a statistical mean, which may be an integer or a decimal number for the individual products. Preferred alcohol ethoxylates have a narrow homolog distribution (NRE). In addition to the aforementioned nonionic surfactants, fatty alcohols with more than 12 EO may be used as described above. Examples of these are alcohols (tallow derived) of 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.

Nonionic surfactants also include, in particular, the above-mentioned alkyl glycosides having the general formula RO (G) _X and polyhydroxy fatty acid amides having the general formulas (I) and (II).

Another group of preferred nonionic surfactants which are used either alone 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 esters, preferably having 1 to 4 atoms carbon in the alkyl chain, especially a fatty acid methyl ester, such as disclosed in Japanese Patent Application JP 58/2 175 598, or may be conveniently prepared by the method described in International Patent Application WO-A-90/13 533. As nonionic surfactants are: preferably methyl esters of C ₁₂ - to C ₁₈ - fatty acids with on average 3 to 15 EO, preferably on average 5 to 12 EO, such as a binder, as mentioned earlier, are preferred in particular ethoxylated fatty acid methyl esters. The methyl ester C 12 to C ₈ - fatty acid having 10 to 12 EO may advantageously be used as a surfactant, and as a binder.

Suitable nonionic surfactants may also be those of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamino oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide and fatty acid alkanolamides. The preferred amount of these nonionic surfactants in the composition is not more than the amount of ethoxylated fatty alcohol, more preferably not more than half its content.

Other surfactants are the so-called gemin surfactants. In the following, the term "compound" will mean those compounds having two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated from each other by an intermediate, "spacer". Said intermediate is generally a carbon chain of a length such that the hydrophilic groups are spaced apart enough to act independently of one another. Surfactants of this kind are generally characterized by an extremely low critical micelle concentration and the ability to greatly reduce the surface tension of water. In exceptional cases, in addition to dimeric surfactants, trimeric surfactants are also understood as meaning.

Suitable gemin-surfactants are, for example, sulfated mixed hydroxyethers according to German patent application DE-A-4,321,022, or dimeric alcohol-bis- and trimeric alcohol-tris-ether sulfates according to German patent application DE-A19 503 061. closed end groups according to German patent application DE-A-19 513 391 are characterized in particular by bi- and trifunctional functions. Since the closed end-group surfactants have wetting properties and are low in foaming properties, they are particularly suitable for machine washing and cleaning applications.

However, gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides as described in International Patent Applications WO-A-95/19 953, WO-A-95/19 954 and WO-A-95/19 955 may also be used.

In addition to surfactants, the most important components of detergents and cleaning agents are, in particular, inorganic and organic auxiliaries.

It is preferred to use zeolite A and / or zeolite P as fine crystalline, synthetic and bound water containing zeolite raw materials. As zeolite P, for example, Zeolith MAP® (a commercial product of the Crosfield form) can be used. The zeolite is available for use as a spray-dried powder, but also as a non-dried, still wet-stabilized suspension. When zeolite is used in the form of a suspension, the suspension may contain a low proportion of nonionic surfactant additive as stabilizers, for example 1 to 3% by weight, based on the zeolite, ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide. groups, C ₂ to C14 fatty alcohols containing 4 to 5 ethylene oxide groups or ethoxylated

-32izotridekanoly. Suitable zeolites have a mean particle size of less than 10 microns (volume distribution; Coulter-Counter method) and are preferably comprised of 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

A suitable substitute or partial substitute for phosphates and zeolite are crystalline layered silicates having the general formula NaMSi _x O _{2x +} i.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. Preferred values for x are 2, 3, or 4. The layered silicates of this type are described, for example, in European patent application EP-A-0 164 514. Preferred layered silicates of the above formula are those in which M is sodium and x is 2 or 3. Even more preferably, either β- or sodium δ-silicates are Na ₂ Si ₂ O ₅ .y H ₂ O.

Preferred excipients also include amorphous silicates having a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, more preferably from 1: 2 to 1: 2.8, and most preferably from 1: 2 to 1: 2. 6, which are slowly soluble and have secondary scrubbing capabilities. The slower dissolution of the usual amorphous sodium silicates may be due to various influences, such as surface treatment, mixing, pressing / compacting, or stronger drying, in advance. In the context of the present invention, the term "amorphous" also means "X-ray-amorphous". This means that the silicates in X-ray diffraction analyzes do not give any sharp diffraction maxima, as is typical of crystalline substances; however, amorphous substances may have one or more diffraction maxima whose width is multiple degrees of diffraction angle. However, they may have very good properties as excipients if the silicate particles give blurred or even sharp diffraction maxima in electrodiffraction analyzes. This can be explained by the fact that the products exhibit structures in the microcrystalline region of 10 to several hundred nanometers; values up to a maximum of 50 nm are preferred, and even more preferably values up to a maximum of 20 nm. Said so-called x-ray amorphous silicates, which are more slowly soluble than conventional waterglass products, are described, for example, in German patent application DE-A4 400 024. Compacted / compacted amorphous silicates and dried X-ray silicates are highly preferred.

Of course, commonly known phosphates can also be used as excipients, unless such use is to be avoided for environmental reasons. Sodium salts of orthophosphoric, pyrophosphoric and especially tripolyphosphoric acid are particularly suitable. Their content should not exceed 25% by weight, preferably not more than 20% by weight, based on the total amount of the finished product. In several cases, in particular, tripolyphosphates, in small quantities, up to a maximum of 10% (by weight, based on the finished product) have been shown to show a synergistic improvement in secondary washing ability in combination with other excipients.

Suitable substitutes or partial substitutes for zeolites are layered silicates from natural sources and also synthetic layered silicates. Said layered silicates are known, for example, from the applications of the inventions DE-B-2,334,899, EP-A-0 026 529 and DE-A-3 526 405. Their use is not limited to a certain chemical composition or structural formula. Smectites, especially bentonites, are preferred.

Suitable layered silicates which belong to the group of water-swellable smectites are, for example, montmorillonite, hectorite or saponite. According to the above formulas, small amounts of iron are incorporated in the crystal structure of the layered silicates. Due to the ion exchange properties, the layered silicates may further comprise hydrogen ions, alkali metal ions, caustic earth metal ions, in particular Na ⁺ and Ca ²⁺ ions. The proportion of hydrate water is generally in the range of 8 to 20% (w / w) and is dependent on the source or the processing method. Useful layered silicates are known, for example, from U.S. Pat. Nos. 3,966,629, EP-A-0 026 529 and EP-A-0 028 432. Layer silicates which, after treatment with alkali, are free of calcium ions and are preferred for use. strong coloring iron ions.

Useful organic bases are, for example, in the form of sodium salts of polycarboxylic acids, such as citric, adipic, succinic, glutaric, tartaric, sugar, aminocarboxylic acids, nitrilotriacetic acid (NTA), and mixtures thereof, unless there is an objection to the use of said substances. in terms of ecology. Preferred salts are polycarboxylic acid salts such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, and mixtures thereof.

-34The acids themselves may also be used. In addition to their effect as adjuvants in the composition, the acids also have the acid component properties and thus serve to set lower or moderate pH values of the detergent or cleaning composition. Of this group, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of said acids are mentioned. When using acids, it is preferred that they are used in anhydrous form in the premixes of the present invention and are not subsequently admixed.

Other suitable organic excipients are dextrins, for example oligomers or optionally carbohydrate polymers, which can be obtained by hydrolysis of starches. The hydrolysis can be carried out in a conventional manner, for example by acid hydrolysis or by an enzyme-catalyzed process. Preferably, these will be hydrolytic products with average relative molecular weights in the range of 400 to 500,000. The polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40 is preferred, in particular from 2 to 30. DE is a conventional reduction rate not only maltodextrins with DE between 3 and 20 and dry glucose syrups with DE between 20 and 37, but also the so-called yellow and white dextrins with higher molecular weights in the range from 2000 to 30,000. British Patent Application 9,419,091 discloses a preferred dextrin. The oxidized derivatives of the aforementioned dextrins are their conversion products by the action of oxidizing agents capable of oxidizing at least one sugar group of the sugar ring to a carboxyl group. Said oxidized dextrins and processes for their preparation are known, for example, from the applications of the following patents EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A 0 542 496, as well as international patent applications WO -A-92 / 18,542, WO-A93 / 08,251, WO-A-94 / 28,030, WO-A-95/07303, WO-A-95 / 12,619 and WO-A95 / 20,608. a C ₆ carbohydrate oxidation product may be preferred.

Other suitable excipients are oxydisuccinates and other disuccinate derivatives, preferably ethylenediamine disuccinate. Particularly preferred in this connection are glycerol disuccinates and glycerol trisuccinates, as described, for example, in U.S. Pat. Nos. 4,524,009, 4,639,325, European Patent Application EP-A-0 150 930 and Japanese Patent Application JP 93/339 896. Suitable Dosage of these substances in zeolite and / or silicate formulations is 3 to 15% by weight.

Other useful organic excipients are, for example, acetylated hydroxy acids or their salts, which may also be in the form of lactones and which contain at least 4 carbon atoms, at least one hydroxyl group and at most two acid groups. Excipients of this kind are described, for example, in WO-A-95/200 029.

Suitable polymeric polycarboxylates are, for example, sodium salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular weight of from 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are, in particular, copolymers of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Particularly preferred are acrylic acid / maleic acid copolymers containing 50-90% acrylic acid and 50-10% (w / w) maleic acid. Their relative molecular weight (based on the free acids) is generally 5000 to 200,000, preferably 10,000 to 120,000, in particular 50,000 to 100,000.

The content of (co) polymeric polycarboxylates in the composition is within the conventional range and preferably is 1-10% (w / w).

Also particularly preferred are biodegradable polymers from more than two different monomer units, for example those containing, according to DE-A-4 300 772, acrylic acid and maleic acid, as well as vinyl alcohol or vinyl alcohol derivatives or DE-C as monomeric salts. -4,221,381 contain acrylic acid and 2-alkylalyl sulfonic acid as well as carbohydrate derivatives as monomeric salts.

Further preferred copolymers are described in German patent applications DE-A-4 303 320 and DE-A-4 417 734 and preferably have acrolein acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

Other suitable adjuvants are the oxidation products of polyglucosanes containing carboxyl groups and / or their water-soluble salts, such as disclosed in International Patent Application WO-A-93/08 521, or whose preparation is described, for example, in International Patent Application WO93 / Also suitable are oxidized oligosaccharides according to German patent application DE-A-19 600 018.

As other preferred excipients are also known aminodicarboxylic acids, their salts or precursors thereof. Highly preferred are polyaspartic acids, or salts or derivatives thereof, which have been disclosed in German Patent Application DE-A19 400 086 to exhibit a stabilizing whitening effect in addition to the properties of the additive.

Other suitable excipients are polyacetals which can be prepared by converting dialdehydes with polycarboxylic acids having 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European Patent Application EP-A-0 280 223. Preferred polyacetals are prepared from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde as well as mixtures thereof and from polyolecarboxylic acids such as gluconic acid and / or glucoheptonic acid.

The compositions may further comprise components which suitably affect the washability of oils and greases from fabrics. This effect is particularly evident in the multi-stained and laundered textile articles which have been washed once more with the detergent composition of the present invention comprising said oil and a grease-dissolving component. Preferred oils and grease-dissolving components are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxycellulose with a proportion of methoxy groups of from 15 to 30% (by weight) and hydroxyl groups of from 1 to 15% (by weight), based on the nonionic cellulose ether. As is known in the art, these components further include polymers of phthalic acid and / or terephthalic acid, or derivatives thereof, in particular polymers of ethylene terephthalate and / or polyethylene glycol terephthalate, or their anionic and / or nonionic modified derivatives. Of these, sulfonated derivatives of phthalic acid polymers and terephthalic acid polymers are particularly preferred.

Other suitable formulation components are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates, as well as the aforementioned slow-soluble silicates, or mixtures thereof; Preferred are alkali metal and amorphous silicates, especially sodium silicate with a molar ratio Na ₂ O: SiO ₂ 1: 1 to 1: 4.5, preferably 1: 2 to 1: 3.5. The sodium carbonate content of the composition is preferably up to 20% (w / w), more preferably between 5 and 15% (w / w). The sodium silicate content of the composition is, if any

The silicate will not use as an excipient, generally up to about 10% (w / w), preferably between 2 and 8% (w / w).

As described in International Patent Application WO-A-94/01222, alkali metal carbonates can be replaced by sulfur-free amino acids having 2 to 11 carbon atoms and optionally other carboxyl and / or amine groups, or salts thereof. It is possible within the scope of the invention for partial or complete replacement of the alkali metal carbonate with glycine or glycinate.

Other detergent ingredients include graying inhibitors, antifoams, bleaching agents and bleach activators, optical brighteners, enzymes, textile softeners, dyes and fragrances as well as neutral salts such as sulfates and chlorides in the form of their sodium or potassium salts.

Acid salts or only slightly basic salts may also be used to lower the pH of the detergent or cleaning compositions. Preferred acidic components are hydrogen sulphates and / or bicarbonates, or the abovementioned organic polycarboxylic acids, which can simultaneously be used as auxiliaries. It is very advantageous to use citric acid which is either additionally admixed (conventional production method) or dosed in the anhydrous solid state already in the masterbatch.

The bleaching agents to be released in an aqueous environment of H ₂ O _{2 l} of the compound are of particular interest as sodium perborate tetrahydrate and sodium perborate monohydrate. Other useful bleaching agents are, for example, sodium percarbonate, peroxopyrophosphate, peroxocitrate as well as H ₂ O ₂ releasing salts, or peracids such as peroxybenzoates, peroxophthalates, diperoxoazelaic acid, phthalimino peracid or diperoxodideacid. A preferred content of bleaching agents in the composition is 5 to 25% (w / w) and in particular 10 to 20% (w / w), preferably perborate monohydrate or percarbonate.

Bleach activators which may be used are compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids, preferably having 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those having O- and / or Nacyl groups having the above-mentioned number of carbon atoms and / or optionally

-38-substituted benzoyl groups. Preference is given to several acylated alkyleneamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycourils, in particular tetraacetylglycouril (TAGU), N-acylimides in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular N-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol acetate 2,5-dihydrofuran and known enol esters, such as acetylated sorbitol and mannitol, and mixtures (SORMAN) described in European patent application EP-A-0 525 239 and from DE-A-19 616 693 and DE-A-19.616 767 , acylated saccharide derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose, as well as acylated and optionally alkylated glucamine and gluconolactone, and / or or N-acylated lactams, such as Nbenzoyl caprolactam, which are known from International Patent Applications WO-A94 / 27 970, WO-A-94/28 102, WO-A-94/28 103, WO-A-95 / OO 626, WO-A-95/14 759 and WO-A-95/17 498. It is also advantageous to use known hydrophilic substituted acyl acetals from German patent application DE-A-19 616 769 and German patent application DE-A-19 616 770 as well as Acyllactams are described in WO-A-95 / 14,075. Known combinations of conventional bleach activators can also be used from DE-A-4,443,177. Said bleach activators are used in customary amounts, preferably in amounts of from 1 to 10% by weight, in particular from 2 to 8% by weight, based on the total weight of the composition.

When used in automatic washing machines, it may be advantageous to add foam inhibitors - antifoams to the detergents. Suitable antifoams are, for example, soaps of natural or synthetic origin, which contain a high proportion of C18 to C24 fatty acids. Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, in this case silanated, silicic acid, as well as paraffins, waxes, microcrystalline waxes, and mixtures thereof with silanated silicic acid or bistearylethylenediamide. Mixtures of different foam inhibitors are also preferably used, for example those containing silicones, paraffins or waxes. Particularly preferred are such foam inhibitors,

Which contain silicones and / or paraffins which are bound to a granulated, water-soluble carrier. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.

The polyphosphonic acid salts used are preferably neutral reacting sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate, diethylenetriaminepentamethylene phosphonate or ethylenediaminetetramethylene phosphonate in amounts of from 0.1 to 1.5% by weight.

Suitable enzymes are, in particular, those of the group of hydrolases, such as proteases, lipases or lipolytic enzymes, amylases, cellulases or mixtures thereof. Oxyreductases are also suitable.

Particularly suitable are enzymatic active compounds obtained from strains of bacteria or fungi such as Bacillus subtillis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens. Preferred are proteases of the subtilisin type, and in particular proteases obtained from the Bacillus lentus strain. Of particular interest here are mixtures of enzymes, for example mixtures of proteases and amylases, or proteases and lipases, or lipolytically acting enzymes, or proteases and cellulases, or, cellulases and lipases, or lipolytically acting enzymes, or proteases, amylases and lipases, or lipolytically acting enzymes. or proteases, lipases or lipolytically acting enzymes and cellulases, in particular mixtures containing proteases and / or lipases, optionally mixtures with lipolytically acting enzymes. Examples of lipolytic enzymes are known cutinases. In individual cases, peroxidases or oxidases may also be suitable. Suitable amylases include, in particular, α-amylases, iso-amylases, pullulanases and pectinases. Of the cellulases, cellobiohydrolase, endoglucanase and β-glucosidase, which are also known as cellobiases or mixtures of said enzymes, are preferred. Since different cellulase types differ from each other by CMCase and avicelase activity, the desired activity of the composition can be adjusted by targeted mixing of cellulases.

Said enzymes may be used adsorbed on carriers and / or incorporated into the hollow forms of the components of the compositions, thereby protecting them from premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules in the composition may, for example, be about 0.1 to 5% by weight, preferably 0.1 to 2% by weight.

In addition to phosphonates, the composition may contain other enzyme stabilizers. For example, 0.5 to 1% by weight of sodium formate may be used. Proteases that are stabilized with soluble calcium salts at a preferred calcium content of 1.2% based on the enzyme may also be used. In addition to calcium salts, magnesium salts can serve as enzyme stabilizers. Further preferred is the use of boron compounds, for example boric acid, boric oxide, borax and other alkali metal borates such as salts of ortho-trihydrogen boronic acid (H ₃ BO ₃ ), hydrogen boronic acid (HBO ₂ ) and dihydrogen tetra-boronic acid (H ₂ B ₄ O 7).

The role of the graying inhibitors in the wash liquor is to maintain loose dirt in the fiber suspension and thus prevent the dirt from being trapped again.

Suitable for this purpose are water-soluble colloids, in particular of organic origin, for example water-soluble salts of polymeric carboxylic acids, gelatin, gelatin, salts of ether-carboxylic acids or ether-sulfonic acids of starch or cellulose, or salts of acidic esters of sulfuric acid and cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Further, soluble starch preparations and other starch products such as starches, starch aldehydes and the like can be used. Polyvinylpyrrolidone is also useful. However, it is preferred to use cellulose ethers such as carboxymethylcellulose (Na-salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, as well as polyvinylpyrrolidone, for example in amounts of 0.1 to 5%. % by weight), always referring to the finished composition.

Detergents and cleaning agents may contain as optical brighteners diaminostilbenedisulfonic acid derivatives or alkali metal salts thereof. Suitable salts are, for example, 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid salts or similarly constructed compounds having, in place of the morpholine group, diethanolamine, methylamine, aniline or 2-methoxyethylamine. Substituted diphenylstyryl-type brighteners may also be present, for example, the alkaline salt 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 above brighteners may also be used.

EXAMPLES

Detergent or cleaning agent M1 and M2

Formulations M1 and M2 were prepared as follows.

In a batch mixer (20 dm ³ ) equipped with a knife crusher (Zerhacker), a solid premix was made from the basic ingredients, including the binder, which in this case was added in solid form. (In one preferred embodiment, the binder was injected into the premix by nozzles in the form of a sprayable melt; however, this did not significantly change the end product properties. The melt solidified shortly after introduction into the solids mixture. The mixture was then homogenized for a further 2 minutes and fed to a 2-screw extruder. The pelletizing head of the extruder was preheated to a temperature between 50 and 65 ° C, preferably to 62 ° C. The addition, in this case at a temperature of less than 45 ° C and a pressure of 100 bar (1 bar) of liquid nonionic surfactant, was carried out with the spray nozzles. The effect of shear forces, caused by screws through an extruder, the master batch plasticized and subsequently at a pressure of between 50.10 ⁵ and 100.10 ⁵ Pa (50 to 100 bar), preferably 78.10 ⁵ Pa (78 bar) extruded (extruded) orifice extrusion head of the extruder, thin bundles - columns with a diameter of 1.4 mm, which, after exiting the orifice, were cut into granules with approximately round granular shapes (length-to-diameter ratio of about 1, hot-cutting) by cutting with separating knives. The outgoing warm granulate was rounded on a conventional Marumerizer® rounding machine for one minute, in which case it was coated with a fine powder material.

The bulk density of the extrudate produced was 800 ± 50 g.dm &^lt; ³ &^gt;.

A homogeneous premix of 61% (by weight) of granulate 1, spray-dried (composition below), 6% (by weight) of C- sulphates, was used to prepare M1 according to the invention. _2- to C ₁₈ fatty alcohols (composition: 92.00% by weight of the active ingredient, 3.70% by weight of sodium sulfate, 2.8% by weight of other salts of raw materials and unsulfated fractions, as well as 1.5% by weight of water), 3 % by weight

-42kopolymérnej sodium salt of acrylic acid and maleic acid (in powder form), 20% sodium perborate monohydrate and 6% by weight of polyethylene glycol as a binder, which had a ratio of molecular weight of about 4 000 to flow the powder was sprayed C ^ - to C ₈ - fatty alcohol with an average of 7 EO in an amount of 4% by weight. The masterbatch was subsequently extruded. The extrudate exhibited a bulk density of 758 g.dm < ³ > in the following sieve analysis and an 8% L-test.

Sieve analysis M1:

sew 1.60 mm

1.25 mm 1.00 mm 0.80 mm below sieve 0.80 mm rest 6% (w / w) 76%

8%

4% overflow 6% (w / w)

To determine the undissolved residue, more precisely to determine the dissolution properties (L-test), 8 g of the test product were mixed in a 2,000 ml beaker with stirring (800 rpm, laboratory mixer with propeller) at a height of 1.5 cm centered above the bottom of the beaker) for 1.5 minutes at 30 ° C. The test was performed with water having a hardness of 160 mg equivalents in dm ³ (16 ° German). The wash bath was then poured through a 80 µm sieve. The beaker was rinsed with a very small amount of cold water and the rinsing water was also passed through said sieve. The determination was performed in duplicate. The sieve with residue was dried in an oven at 40 ± 2 ° C to a steady weight to determine the undissolved detergent residue. The residue was expressed as a percentage (w / w) as the mean of the two individual tests. As a rule, a further test was performed with a deviation of more than 20% from each result, but this was not necessary in these cases.

The tendency to gel when dissolving the composition in a water wash bath was tested with a towel and bowl test; a wash was used for this purpose

-43 dark plastic bowl (eg dark red); 5 dm ^{3 of} drinking water (16 ° German, 30 ° C) was poured into the bowl and M1 was added in an amount of 25 g. After 15 seconds, the composition was mixed by hand in the bowl. After another 15 seconds, one blue terry towel was placed in the wash bath and moved like a normal hand wash. After 30 seconds the walls of the bowl were wiped with a towel. After a further 30 seconds, the towel was slipped and visually assessed. The evaluation stated:

mark 1: flawless appearance, no observable residues mark 2: permissible, isolated residues that do not impair the characteristics mark 3: visible residues, at critical evaluation residues begin to deteriorate the product from mark 4: clearly distinguishable and degrading residues in increasing numbers and increasingly.

The wash solution was then separated by decantation and the residue was treated with 5-10 ml of water and again visually assessed. The evaluation stated:

mark 1: flawless appearance, no noticeable residues mark 2: permissible, individual residues, very finely dispersed, adding no water to gels mark 3: visible residues, at critical evaluation residues begin to degrade product from mark 4 above: clearly distinguishable and degrading residues in increasing numbers and increasingly, agglomerates to clusters, with the addition of water gelling.

M1 had both marks 1 and 2 in both the towel test and the bowl test.

For comparison, a detergent V1 was prepared which contained the same ingredients in the final product, but in which the copolymer was added not as a powder but as an approximately 30% aqueous solution. The excess water was then dried by fluidized bed drying. The bulk density of the extrudate was about 770 g.dm &^lt; -1 &^gt;. The L-test gave a value of 28%. In the towel test, V1 was graded 3 to 4, and in the bowl test, grade 4.

Detergent M2 has proven very suitable for washing colored textile products. For its preparation, they were mixed and extruded as described above: 65.71% (by weight) of granulate 2 (composition see below), spray dried, 11.83% (by weight) of an alkyl sulphate mixture produced in a fluidized bed (composition: 75%) C12- to _C18 -alkyl sulphate, 17% by weight sodium sulfate, 3% by weight sodium carbonate, 1% by weight water, residual salt from solutions, 2.96% by weight copolymer sodium salts acrylic acid and meleic acid (in powder form), 6,99% by weight of trisodium citrate dihydrate, 3,59% by weight of polyethylene glycol with molecular weights of 4 000 and 8,92% by weight of C ₁₂ to C ₁₈ fatty acids alcohol with an average of 7 EO.

The extrudate with a granularity, characterized by the sieve analysis results below, had a bulk density of 811 g.dm &^lt; ^{3 >} and a solubility test (L-test) of 2%. In the bowl test, scores of 1-2 were obtained.

I

Sieve analysis M2:

sew 1.60 mm

1.25 mm 1.00 mm 0.80 mm below sieve 0.80 mm remainder 2% (w / w) 90%

7%%

1% overflow

For comparison, a mixture of V2 having the same composition of the final product was prepared, but the copolymer was not added in powder form but added as an approximately 30% solution. Excess water was then removed by fluidized bed drying. The bulk density of the extrudate was clearly below 800 g.dm &^lt; ³ &^gt;, the results of the L-test gave a value greater than 20%. When the alkyl sulfate mixture was not coextruded but according to German patent application DE-A-19 519139

45 additionally admixed, then the bulk density of the extrudate was 780 g.dm &^lt; ^-3 &^gt;, the L-test result was 7% and the bowl test score was 1-2.

By treating extrudate M2 by adding 3 parts by weight of enzyme granulate, 4 parts by weight of granulated defoamer, 2.5 parts by weight of polymers (Repelotex®, manufactured by Rhône-Paulenc) and 0.5 parts by weight of silicic acid per 90 parts by weight of extrudate M2. (for additional treatment of particle surfaces) composition A2 was prepared having a bulk density of 820 g.dm &^lt; ^{-3 >} (increased bulk density!) and a value of 7% in the L-test and with unchanged scores from the bowl test. On the other hand, in the same treatment of 90 parts by weight of the comparative extrudate with the admixed alkyl sulphate mixture, the L-test value increased to 12% while the bulk density fell to 735 g.dm &^lt; ³ &^gt;.

The composition of the invention was also prepared by supplying 3-5% by weight of a nonionic surfactant to a spray dried mixture; the mixture was subsequently treated with a nonionic surfactant.

For example, the composition of the invention was also prepared using a mixed binder of polyethylene glycol having a molecular weight of 4000 and cetyl stearyl alcohol with an average of 20 EO in a weight ratio of 1: 2 to 5: 1.

The products of the invention were also prepared by the premix powder employed as the alkyl benzene sodium salt C ₉ - to C ₁₃ -alkylbenzénsulfónovej acid, comprising 85% (by weight) of alkyl benzene sulfonate, 4.5% (wt) of sodium carbonate, 3, 5% (w / w) sodium sulfate, 2% (w / w) sodium chloride and 4% (w / w) water and the unsulfated fraction. Depending on the individual recipes, the extrudates showed L-test result values of less than 15% or less than 10%. As comparative tests to the latter mixtures, tests were performed in which a concentrated aqueous alkylbenzenesulfonate paste was used in place of the alkylbenzene sulfonate powder and the water was then removed by drying; all these products showed values above 20% in the L-tests.

-46Composition of spray-dried granules

Granulate 1, spray-dried (data expressed in% by weight):

26.30% C8 to C13 alkylbenzenesulfonate 1.10% tallow fatty alcohol with an average of 5 EO

1:40% sodium soap of C 12 to C ₈ - fatty acid

9.40% sodium carbonate

4.00% sodium acrylic / maleic acid copolymers 39.50% zeolite A; on the anhydrous active substance)

2.80% amorphous sodium disilicate 13.60% water residue of salt from solutions.

Granulate 2, spray-dried (data expressed in% by weight):

12.07% C _g - to C 3 alkyl benzene sulfonate

3.00% Sodium soap C 12 to C ₈ -fatty acids

0.03% sodium hydroxide

4.15% sodium carbonate

0.80% phosphonate

0.80% polyvinylpyrrolidone

57.75% of zeolite A based on the anhydrous active ingredient

4.15 sodium salts of copolymers of acrylic acid and maleic acid

16.65% water residue: salts from solutions.

Other compositions M3-M10 of the present invention exhibited the following compositions and were prepared as described above.

-47Table 1 Composition of M3 to M6 (% by weight)

composition M3 M4 M5 M6 Granulate 1, spray dried 57 60 64 55 Sodium perborate monohydrate 20 23 - 25 Polyethylene glycol (4 000) 5 - - - Polyethylene glycol (2 000), unilaterally sealed with methyl end groups 7 Fatty acid methyl esters C ₆ / s-12 EO 6 C 12-18 fatty alcohol + 7 EO 6 6 7 7 C-12/18-alkyl sulphate (92% active ingredient, 3.70% sodium sulfate, 2.80%) % of other raw material salts and unsulfated fraction, 1.5% water) 7 5 8 6 Polyglycoside of fatty alcohols C-12/14 (78% active substance, 18% glass module with module 2,4, 5% water) 5 C 18-18 fatty alcohol ethoxylate + 80 EO 6 Trisodium citrate dihydrate - - 15 -

-48Table 2 Composition of mixtures M7 to M10 (% by weight)

composition M7 M8 M9 M10 Granulate 1, spray dried 72 51 54.5 52 Sodium perborate monohydrate - 20 20 20 Polyethylene glycol (4 000) 6 5 - Polyethylene glycol (2 000), unilaterally sealed with methyl end groups 6 7 C 12-18 fatty alcohol + 7 EO 7 8 7 - C12-14 fatty alcohol + 5 EO - - - 7 C 12 H -alkyl sulphate (92% active 3.70% sodium sulfate, 2.80 % of other raw material salts and unsulfated fraction, 1.5% water) 15 5 10 Polyglycoside of fatty alcohols C12 / 14 (78% active substance, 18% glass module with module 2,4, 5% water) 4 Trisodium citrate dihydrate 15 - - - Tetraacetylethylenediamine (95%) TAED, 2% carboxymethylcellulose, 2.75% salt, 0.25% water) 8.5

-49Miss test results for mixtures M3 to M10:

M3 1 to 2 M4 1 to 2 M5 1 M6 1 to 2 M7 1 M8 1 M9 1 to 2 M10 1 to 2.

PV <f * \

Claims (22)

Process for preparing particulate detergents or cleaning compositions, or mixtures or treated raw materials, having a bulk density of more than 600 g.dm ^{3 *} , by combining mixtures of detergents or cleaning ingredients and / or raw materials with simultaneous or subsequent shaping, characterized in that: that initially a solid particulate premix to which each raw material and / or composition that is at room temperature and a pressure of 10 ⁵ Pa (1 bar) used in the solid state and have a melting point or softening point below 45 ° C, the optionally containing up to 10% of nonionic surfactants which are liquid at temperatures below 45 ° C and at a pressure of 10 ⁵ Pa (1 bar) and are converted to granular material at temperatures of at least 45 ° C and optionally further processed or treated ; where the premix is - essentially anhydrous, - one or more anionic surfactants and at least one raw material or mixture are used in the masterbatch and at a pressure of 10 ⁵ Pa (1 bar) and temperatures below 45 ° C in the solid state but under melt-processing conditions wherein the melt acts polyfunctionally; it serves as a water-soluble binder, which, however, acts as a glidant in production and also serves as an adhesive for solid laundry or cleaning compositions or raw materials; in contrast, it disintegrates when the said composition is dissolved in a water wash. 2. A process according to claim 1, wherein the masterbatch has no total water content greater than 15% by weight, said water not being in the form of free water, and preferably having a non-bound water content. for zeolites and / or silicates not higher than 10% by weight and in particular lower than 7% by weight. The process according to claim 1 or 2, characterized in that the masterbatch in addition to the solid constituents further comprises up to 10% by weight of nonionic surfactants which are liquid at a pressure of 10 ⁵ Pa (1 bar) and temperatures below 45 ° C. Especially alkoxylated alcohols such as fatty alcohols or oxoalcohols having a carbon chain length of between 8 and 20 carbons and in particular having an average of 3 to 7 ethylene oxide units per mole of alcohol, with the addition of liquid nonionic surfactants and a disintegrating binder, shall be carried out separately. Method according to one of claims 1 to 3, characterized in that the melting point of the premixes of the individual substances used or the softening point of the premixes of the mixtures used is higher than 45 ° C, preferably at least 50 ° C. Method according to any one of claims 1 to 4, characterized in that mixtures and raw materials having at least 80% by weight, preferably at least 85% by weight and most preferably at least 85% by weight are used in the premix. ) a substantially higher softening or melting point than that achieved under the conditions of the production method. . Method according to one of Claims 1 to 5, characterized in that in the compaction work step several stages are carried out in the temperature range, for example 2 to 20 ° C above the melting point or above the softening point. Method according to any one of claims 1 to 6, characterized in that one or more binders are used which are almost completely dissolved at a concentration of 8 g of binder per 1 dm ^{3 of} water at 30 ° C within 90 seconds. Method according to one of Claims 1 to 7, characterized in that a binder is used which, at temperatures of not more than 130 ° C, preferably not more than 100 ° C and in particular up to 90 ° C, is completely in the molten state. Process according to one of Claims 1 to 6, characterized in that the solid components for preparing the solid and free-flowing premix are first at room temperature. Only at slightly elevated temperatures, which are preferably below the melting point or below the melting range of the binder, and in particular below 35 ° C, are introduced into a conventional mixer and / or granulation device. Method according to any one of claims 1 to 9, characterized in that a binder is added to the mixture as the last component, admixing is carried out under processing conditions such that the highest possible uniform, homogeneous distribution of the binder in the mixture of solids is achieved as solidifying melt, or as a powder. Method according to one of Claims 1 to 10, characterized in that the binder incorporation takes place at temperatures at which the binder is in the form of a melt, the preferred melt temperatures being at 60 to 150 ° C, in particular temperatures from 80-120 ° C. I '' ' Method according to any one of claims 1 to 11, characterized in that the mixing process is carried out until the melt solidifies and the premix is in a solid, free-flowing state. Method according to any one of claims 1 to 12, characterized in that a masterbatch is used in which the binder or binder content is at least 2% (w / w) but less than 15% (w / w), preferably less than 2% (w / w). 10% by weight and most preferably 3 to 6% by weight, in each case based on the weight of the masterbatch. Method according to one of Claims 1 to 13, characterized in that the processing temperature in the actual granulation, compression, tabletting, pelletizing or extrusion process is set above the melting point or the temperature of the binder (s) as however, it is preferred that the processing temperature is not more than 20 ° C higher than the melting point or the lower temperature of the binder melting temperature range. -5315. Method according to any one of claims 1 to 14, characterized in that the binder has a melting point or a melting temperature range of at most 150 ° C, preferably at most 100 ° C and most preferably up to 75 ° C, and the processing temperature is 10 ° C and preferably at most 5 ° C above the melting point or above the upper limit of the binder melting temperature range. Method according to one of Claims 1 to 15, characterized in that the duration of the application of the temperature between the mixing / homogenization of the masterbatch and the shaping, i.e. in the compaction region, is between 10 seconds and at most 5 minutes, preferably at most 3 minutes. . Method according to one of Claims 1 to 16, characterized in that the preparation is carried out by extrusion, whereby the premix is compacted, plasticized, extruded in the form of fine bundles through the orifice in the extruder head and finally crushed by means of a rotary cutter, preferably the spherical (bead shape) to cylindrical shape of the granulate grains and the temperature regime in the transition region of the extrusion worms, the pre-separator and the orifice die are set to at least reach the temperature of the upper melting range of the binder, preferably higher. Process according to claim 18, characterized in that the duration of the application of the temperature in the compression zone of the extrusion is at most 2 minutes and preferably in the range between 30 seconds and 1 minute. Method according to one of Claims 1 to 18, characterized in that the compacted mass has a temperature of not more than 80 ° C, preferably between 35 and 75 ° C and most preferably between 40 and 70 ° C just after leaving the production plant. , for example up to 60 ° C. Method according to any one of claims 1 to 19, characterized in that a masterbatch having a relatively broad particle size distribution and a relatively Converts a high proportion of fine grains to an end product with a relatively narrow particle size distribution and relatively small proportion of fine grains. Particulate washing or cleaning composition, composition or treated raw material having a bulk density above 600 g.dm ^-3 obtained according to any one of claims 1 to 20, wherein a solid masterbatch is first prepared from the mixtures and / or raw materials, the individual raw materials of which and / or mixtures which are solid at room temperature and 10 ⁵ Pa (1 bar) and have a melting point or softening point of not less than 45 ° C, optionally containing up to 10% by weight of nonionic surfactants which: are liquid at temperatures below 45 ° C and at a pressure of 10 ⁵ Pa (1 bar) and, under the influence of compaction forces at temperatures of at least 45 ° C, the premix is converted into a granular material which may optionally be subsequently treated or treated, the masterbatch is substantially anhydrous, characterized in that one or more anionic surfactants are used, as at least one raw material or one mixture, which is optionally added to the masterbatch; anionic surfactant or anionic surfactant The C 'surfactants are in solid form at a pressure of 10 Pa (1 bar) and temperatures below 45 ° C, but are in the melt state under processing conditions, the melt serving as a polyfunctional, water-soluble binder which performs the function of producing the composition. glidant and for the ingredients of the compositions or raw materials of the solid laundry detergent or cleaning agent also performs a sticky function, but disintegrates when the composition is dissolved in the aqueous laundry bath; The particulate (particulate) detergent or cleaning composition also has a honeycomb-like structure wherein the honeycombs are filled with a solid. A granular or extruded detergent composition according to claim 21, characterized in that it comprises at least 80% (by weight) of the mixtures and / or treated raw materials according to the invention and in particular contains at least 80% (by weight) of the basic granulate or base extrudate prepared according to this It is very advantageous if the other components are also mixtures or treated raw materials which have been prepared according to any one of claims 1 to 20. -5523. Composition according to claims 21 or 22, characterized in that the grains are coated on the surface with a powdered or at least fine-grained component (the so-called fine fraction) which has adhered to the surface during melt-agglomeration. Molded detergent, in particular a tablet, prepared according to any one of claims 1 to 20, wherein a solid premix is first prepared from the mixtures and / or the raw materials, the individual raw materials and / or mixtures being at room temperature and 10 ⁵ Pa (1). (bar) in the solid state and have a melting point or softening point of not less than 45 ° C, and optionally said premix contains up to 10% (by weight) of nonionic surfactants which are at a pressure of 10 ⁵ Pa (1 bar) and below ° C liquid, and under the influence of compaction forces, the masterbatch at temperatures of at least 45 ° C is converted to a granular material which is further processed or treated, said masterbatch being substantially anhydrous, characterized in that the molded detergent comprises one or more more anionic surfactants, I at least one raw material or mixture which is optionally added to the masterbatch; said anionic surfactant or anionic surfactants at a pressure of 10 ⁵ Pa (1 bar) and a temperature below 45 ° C in a solid form, but the process conditions are known in the melt, wherein the melt serves as a polyfunctional, water-soluble binder, in the manufacture of said composition fulfills the function of a glidant and, for the ingredients of the composition or raw materials of the solid detergent or cleaning composition, also performs a sticky function, but disintegrating in dissolving said composition in the aqueous washing bath may contain one or more particulate disintegrants in the washing bath. ¹