EP1257628B1 - Agglomerates containing layered minerals and nonionic surfactants - Google Patents

Abstract

The invention relates to agglomerates containing layered silicate, with non-ionic tensides, for use as a detergent additive. The agglomerates contain at least one natural or synthetic layered silicate chosen from the group of clays containing montmorillonite, especially betonite, and attapulgite, hectorite and/or beidellite, the quantity thereof being more than 10 wt. % in relation to the total quantity of support materials; at least one precipitated silicic acid, the quantity thereof being at least 12 wt. %, and at least one non-ionic tenside, the quantity thereof being more than 50 wt. %. No compaction or extrusion takes place during the production of the agglomerates.

Description

The invention relates to layer silicate-containing agglomerates nonionic surfactants, a process for their preparation and their use as detergent additive.

Nonionic surfactants are increasingly being used in powder detergents used. The reasons are first in their good Washing properties even at low temperatures. This is possible This is in line with the trend towards lower washing temperatures in European Countries and those already used for a long time low washing temperatures in America and Asia. Farther become the washing properties of nonionic surfactants not or only slightly influenced by a high water hardness. Also have nonionic surfactants to anionic Surfactants better cleaning properties for fatty Dirt as well as for synthetic fiber fabrics on.

Due to its liquid to waxy consistency that is Penetration of nonionic surfactants in larger quantities in powdered detergents, however, with some difficulty connected. This is how the use of nonionic surfactants leads in washing powders produced by a spraying process Be easy to gluing even during spray drying of the nozzles and to a swelling of the powder the evaporation of volatile contaminants in the nonionic surfactants.

In the prior art, therefore, the nonionic surfactants usually applied to the powder only after spray drying. However, here it allows the absorption capacity of not obtained from the spray-drying process, larger Apply or incorporate amounts of nonionic surfactants.

Even with powders that are not made by spray drying may be desirable, the content of nonionic Surfactants continue to increase. However, in this case too the absorption capacity of the powder for other surfactants limited.

The prior art already contains many detergent compositions known solid support systems for nonionic Containing surfactants. Often these systems are in their absorption capacity limited to nonionic surfactants. Farther are made of many known in the art carrier systems for nonionic surfactants, the latter prematurely during the Storage released. This effect is called "bleeding" called the agglomerates. After all, many are well known Agglomerates especially at high loadings with nonionic Surfactants sticky and therefore not free-flowing.

JP 0009087699 AA describes a granular nonionic A detergent composition containing a nonionic Surfactant, a clay mineral, such as montmorillonite, an oil-absorbing Carrier, such as amorphous silica, and a silicone. It may contain further additives, such as sodium silicate as a builder organic polyacrylate salt, also as builder, an optical one Brightener, an enzyme, a bleach and an extender present be. The ingredients are kneaded and extruded and then crushed. So it does not find a simple one Agglomeration instead.

JP 0011310791 describes a granular, nonionic Detergent composition containing a nonionic surfactant, a clay mineral and an oil-absorbing carrier. The Ingredients are mixed, kneaded, extruded and then crushed. A simple agglomeration process is not described.

US-A-4,861,510 describes porous detergent granules, containing sodium sulfate and synthetic phyllosilicates. The granules are prepared by spray drying, wherein a porous granulate is formed, which acts on liquid surfactants can be. The liquid absorption capacity is between 2 and 50 wt .-%, preferably up to 35 wt .-%. According to the invention, the surfactant content is over 50%, and the Agglomerates are not produced by spray drying.

DE-A-38 35 918 (= EP-A-0 362 881 = US 5,354,493) describes a process for the preparation of surfactant-containing Granules containing zeolites and bentonites as support materials can contain. After this procedure is in the Mixing step (a) the nonionic surfactant with water, optionally a part, but less than 50 wt .-% of the total amount the water-soluble or water-insoluble solids may contain, mixed until formation of a gel phase, whereupon, in the step (b), the remaining main amount the solids are added and the mixture until formation is processed mechanically by granules. The weight ratio of nonionic surfactant and water in the Gel phase to total existing solids is 25:75 to 65:35. A net content of nonionic surfactant, based on the finished granules, the publication is not to remove. Tenside contents are calculated from the examples (based on anhydrous alcohol ethoxylate) from 10 to 20.5 Wt .-%. The surfactant content is therefore well below 50 wt .-%. There the surfactant uptake capacity of zeolite A is only 26% by weight, it is not possible on the basis of zeolite as sole carrier material granules with surfactant contents of produce more than 50%. This is not possible with Carrier mixtures of bentonites and zeolites, as bentonite granules absorb only a maximum of about 40 wt .-% surfactants can.

EP-A-0 690 123 describes a process for the preparation a powdered detergent, wherein (1) a builder (soda, Zeolite, STPP, trisodium nitrilotriacetate, citrates or Sulfates or mixtures thereof) with a nonionic surfactant (2) a barrier material (amorphous silicates / precipitated silicas) is added and (3) a further processing done with the builder to the final granules. The total content of surfactant is 5 to 50 wt .-%, is therefore below the upper limit of the invention. Farther the products of the invention are only in maximum made two steps. In addition, the inventive Agglomerates containing montmorillonite-containing phyllosilicates.

The object of the invention was therefore agglomerates with a high content to provide nonionic surfactants. not are sticky, do not "bleed" and release more quickly allow the nonionic surfactants in the wash liquor. Furthermore, in the release of nonionic Surfactants often observed to reduce gel effect as possible become. The resulting gel phases have a high Viscosity, which prevents rapid dissolution of the surfactants and may cause sticking of the particles upon dissolution cause.

This object is achieved by the layer silicate according to the invention Agglomerates according to claim 1.

a) mindestens ein natürliches oder synthetisches Schichtsilicat, ausgewählt aus der Gruppe der montmorillonithaltigen Tone, insbesondere Bentonit, sowie Attapulgit, Hectorit und/oder Beidellit (Komponente a), in einer Menge von mehr als 10 Gew.-%

b) mindestens eine gefällte Kieselsäure, in einer Menge von mindestens 12 Gew.-% (Komponente b),
jeweils bezogen auf die Gesamtmenge an Trägermaterialien,

c) mindestens ein nichtionisches Tensid, in einer Menge von > 50 Gew.-% (Komponente c) bezogen auf das gesamte Agglomerat,

wobei bei der Herstellung des Agglomerats keine Kompaktierung oder Extrusion erfolgt. Contain the agglomerates of the invention

a) at least one natural or synthetic layered silicate selected from the group of montmorillonite-containing clays, in particular bentonite, as well as attapulgite, hectorite and / or beidellite (component a), in an amount of more than 10% by weight

b) at least one precipitated silica, in an amount of at least 12% by weight (component b),
in each case based on the total amount of support materials,

c) at least one nonionic surfactant, in an amount of> 50% by weight (component c) based on the total agglomerate,

wherein during the production of the agglomerate no compaction or extrusion takes place.

Thus, it was surprisingly found that the inventive Agglomerates with the above composition very can absorb high levels of nonionic surfactants without that they become sticky or "bleed".

The agglomerates according to the invention can be particularly advantageous Washing powders are admixed, the above-mentioned Gelation effect on the one hand only on the agglomerates remains limited and not the entire detergent composition recorded, and on the other hand, surprisingly low fails.

It was unexpectedly found that at a salary of at least 12% by weight of precipitated silica, preferably from at least 15 to at least 20% by weight precipitated silica, a synergistic effect with the mentioned layer silicates occurs and a very high incorporation of nonionic surfactants is made possible without causing stickiness or "bleeding" of the Agglomerates leads.

Furthermore, in the case of the agglomerates according to the invention, the rapid Dissolution of agglomerate particles and rapid release ensures the non-ionic surfactants in the wash liquor, while avoiding incrustations on the laundry can be.

It was found to be natural or synthetic Phyllosilicates the montmorillonite-containing silicates, such as bentonite, as well as attapulgite, hectorite and / or beidellite in particular provide advantageous results.

Thus, according to a preferred embodiment, natural or synthetic bentonites (preferably Na bentonite), attapulgites, Beidellite and / or hectorite used. Especially Bentonite and hectorite also show a positive Effect on the washing performance or a fabric softening Effect.

In addition to natural layer silicates can according to the invention also synthetic phyllosilicates are used, for example synthetic hectorite.

It was found that a previous activation, in particular an alkaline activation of the phyllosilicates, positive for the properties of the agglomerates according to the invention effect. According to a particularly preferred embodiment is for example activated bentonite, in particular soda-activated bentonite used.

As mentioned above, it shows in a content of precipitated Silica of at least 12 wt .-% based on the Total amount of carrier materials (components a, b and possibly d according to claim 1 or 7) in combination with the natural or synthetic layered silicates, surprisingly synergistic effect. Therefore, the amount of precipitated Silica in the agglomerates according to the invention adjusted that, on the one hand, they are at least 12% by weight, preferably at least 14% by weight, and in particular at least 16 wt .-%, based on the total amount of Support materials.

It is believed, without the invention being based on this theoretical Mechanism of action would be limited in that According to the invention agglomerates, the layered silicate used in the manner of a "house of cards" or scaffolding a porous structure forms for receiving the nonionic surfactant, wherein the Structure stabilized by the highly porous precipitated silica and this with the three-dimensional layer silicate structure interacts. The agglomerates according to the invention Therefore, have a particularly high and relatively stable Porosity on. It is also believed that the precipitated silica a (partial) delamination of the layered silicate causes.

A compaction or extrusion is likely a more parallel alignment of the layered silicate platelets, which negatively affects the porosity of the agglomerates and their surfactant receptivity affects.

To this "stabilized house of cards structure", which for recording high amounts of surfactant is particularly suitable not to affect or even destroy, become the invention Agglomerates therefore neither compacted nor extruded. there the expert is familiar with what under compaction and Extrusion is to be understood, according to the invention such Energy inputs should be avoided, which is a significant Change the porosity and density of the agglomerates cause would. So is at too high energy inputs or the impact high shear or compression forces, in particular in (roll) compaction or extrusion, the above described stabilized house structure Bentonite platelets and silica particles impaired. Under Compaction is also a (compacting) kneading here Understood.

Because, however, apart from the above-described unexpected Effect, no positive influence of precipitated silicas on the washing properties is known, and precipitated silicas On the other hand, are also quite expensive, it is according to the invention preferred that the amount of precipitated used Silica not more than 40% by weight, preferably not more than 30 Wt .-%, based on the total agglomerates. Surprisingly can be despite the relatively small Amount of precipitated silica in the agglomerates very high Achieve absorption rates for nonionic surfactants, wherein the agglomerates according to the invention have a fast solubility exhibit. Furthermore, the agglomerates according to the invention show surprisingly with the same surfactant content as agglomerates According to the prior art, a significantly lower stickiness.

The agglomerates according to the invention are advantageously prepared in the usual sizes for detergent additives particle sizes, those skilled in the art are familiar.

In contrast, in a compaction or extrusion the particles first a premix, for example by Kneading in cylindrical rollers, or by kneading in one Extruder, carried out, followed by coarse material as Cake or extruded through a die extrudate obtained becomes. This material must be in a subsequent step are crushed, which in particular in accordance with the invention aspired high surfactant content and increased tackiness of the compacted or extruded material problematic as well as energy and cost intensive.

In the agglomerates according to the invention, it is possible to use all conventional precipitated silicas known to the person skilled in the art. Generally, starting material for the recovery of silicic acids by wet route are alkali silicate solutions, preferably soda water glass, from which amorphous silicic acid is precipitated by the addition of acid. After filtration, washing and drying, the precipitated product consists of 86 to 88% SiO ₂ and 10 to 12% water which is physically bound both in the molecular structure and on the surface, as well as residues of the salt formed during the reaction and small amounts of metal oxide , By varying the most important precipitation parameters, such as precipitation temperature, pH, electrolyte concentration and precipitation duration, it is possible to produce silicas with different surface properties. Silicas can be produced in the range of specific surface areas of about 25 to 700 m ² / g.

The silicic acid suspension obtained in the precipitation is dissolved in Filter presses transferred, wherein the solids content of the filter cake between about 15 and 20%. The drying takes place according to different procedures, which is common Connect grinding and visual steps.

Both hydrophilic and hydrophobic silicas can be used be used, with hydrophobic silicic acids simultaneously can serve as a defoamer.

The silicas used in the present invention preferably have an average particle diameter from about 1 to 100 microns. In most cases will be Precipitated silicas with a high specific surface area and high adsorptive capacity, by the oil number or Dibutylphthalateahl (DBP number) according to DIN 53601 characterized is preferred.

All agglomerates can be prepared by a person skilled in the art use common nonionic surfactants. These include, without being limited to the group of alcohol ethoxylates or fatty alcohol polyethylene glycol ethers, the alkylpolyglycosides, the fatty alcohol polyglycol ether methyl ester, fatty acid methyl ester ethoxylates, the sorbitan ester or mixtures it. Preferred are fatty alcohol polyethylene glycol ethers, Alkyl polyglycosides, fatty acid methyl ester ethoxylates and Fettalkoholpolyglycolethermethylester. Especially preferred are fatty alcohol polyethylene glycol ethers, fatty alcohol polyglycol ether methyl esters or mixtures of both. Using of fatty acid methyl ester ethoxylates, the inventive Dissolve agglomerates surprisingly quickly.

For the fatty alcohol polyethylene glycol ethers, those are preferred which are common in detergent applications, i. the Ethoxylation degrees between 1 and 12 and alkyl chain radicals having 10 to 17 carbon units. Fettalkoholpolyethylenglycolether with a few ethoxylate units preferably in mixtures with higher ethoxylated fatty alcohol polyethylene glycol ethers used. The individual case preferred nonionic surfactants are of the specific ones Requirements for the detergent depending and can each be determined by the skilled person by means of routine experiments.

In addition to the surfactants, the agglomerates can be added in the The prior art contains known additives. Especially in agglomerates with alcohol ethoxylate or fatty alcohol polyethylene glycol ether can the agglomerates of the invention additives known in the art are added, such as e.g. Alcohols such as ethanol or glycerol, polyethylene glycols or hydrotropes such as Na cumene sulphonate. For the polyethylene glycols In particular those are used which are low molecular weight Have masses, in particular 200 to 6000 g / mol. These are usually made prior to agglomeration with the surfactant mixed and in amounts of 0.1 to 30%, based on the Amount of surfactant used.

On the preferred method for producing the inventive Agglomerates will be discussed in more detail below.

According to a preferred embodiment, the inventive Agglomerates at least 52 wt .-%, in particular at least 55% by weight, more preferably at least 58% % By weight of nonionic surfactants, based on the total agglomerate.

Preferably, the ratio of layered silicate to precipitated Silica, based on wt .-% in the inventive Agglomerates, between 2: 1 and 1: 2. After a special preferred embodiment are the layered silicate and the precipitated silica in about the same amounts, based on wt .-%, before.

According to a particularly preferred embodiment of the invention the agglomerates contain 10 to 15% by weight Bentonite, 5 to 15 wt .-% zeolite and 10 to 30 % By weight of precipitated silica, based on the total agglomerate.

Although the agglomerates according to the invention, as mentioned above, additionally contain additives known in the art may consist of a preferred embodiment the agglomerates consist essentially of nonionic surfactant, Phyllosilicate and precipitated silica, leaving one intimate contact between these components ensured is. Preferably, the above components make at least 85 wt .-%, in particular at least 90 wt .-%, and especially preferably 95 wt .-% of the agglomerates.

According to another embodiment of the present invention it was surprisingly found that the additional Inclusion of at least one zeolite in the agglomerates, preferably in the amount between 0.5 and 60 wt .-%, and in particular between 5 and 30% by weight, based on the carrier material, leads to particularly positive results. It is known, that it is not readily possible agglomerates by agglomeration of zeolite with nonionic surfactant too obtained because of the fineness of the zeolites only heavy agglomerates with usual particle size in more satisfactory Make yield.

It has now surprisingly been found that by the targeted Combination of zeolite with a layered silicate according to Component (a) of claim 1, a precipitated silica according to component (b) of claim 1, and a nonionic A surfactant according to component (c) of claim 1, a material achieved better yield of agglomerates in the desired size can be. It is believed without the invention is limited to this assumption that the used Layered silicate acts as a kind of binder and by the Interaction of the components a particularly high absorption capacity for nonionic surfactants is possible, without that this leads to stickiness of the resulting agglomerates or "bleeding" leads. Also, zeolite seems to some extent the function of the precipitated silica in the above take over the described "stabilized house structure" to be able to.

a) mindestens ein natürliches oder synthetisches Schichtsilicat, ausgewählt aus der Gruppe der montmorillonithaltigen Tone, insbesondere Bentonit, sowie Attapulgit, Hectorit und/ oder Beidellit, in einer Menge von mehr als 10 Gew.-% (Komponente a);

b) mindestens eine gefällte Kieselsäure in einer Menge von mindestens 12 Gew.-% (Komponente b);
jeweils bezogen auf die Gesamtmenge an Trägermaterialien,

c) mindestens ein nichtionisches Tensid in einer Menge von größer als 50 Gew.-% (Komponente c), bezogen auf das Gesamtagglomerat;

d) gegebenenfalls ein Zeolith, vorzugsweise in einer Menge von 0,5 Gew.-% bis 30 Gew.-%, bezogen auf die Gesamtmenge an Trägermaterialien;
ohne Kompaktierung oder Extrusion intensiv vermischt und agglomeriert werden.

According to the invention, all commercially available zeolites can be used for the agglomerates, for example Wessalith P®, Wessalith 2000® from Degussa, Doucil A24® and Doucil A4® from Crosfield, Eijsden, the Netherlands. The layer silicate-containing agglomerates can be prepared according to the invention by a process, wherein

a) at least one natural or synthetic layered silicate selected from the group of montmorillonite-containing clays, in particular bentonite, as well as attapulgite, hectorite and / or beidellite, in an amount of more than 10 wt .-% (component a);

b) at least one precipitated silica in an amount of at least 12% by weight (component b);
in each case based on the total amount of support materials,

c) at least one nonionic surfactant in an amount of greater than 50 wt .-% (component c), based on the total agglomerate;

d) optionally a zeolite, preferably in an amount of 0.5 wt .-% to 30 wt .-%, based on the total amount of support materials;
Intensively mixed and agglomerated without compaction or extrusion.

According to a preferred embodiment becomes intensive Mixing generates a mechanical fluidized bed. Can do this in general, the known in the art intensive mixer in batch or continuous processes be used. Agglomeration becomes batchwise Batch mixers from Eirich, Hartheim, Loedige mixer (e.g., Loedige FKM mixer, Paderborn) or Drais (Drais Turbomix, Mannheim) in question. at continuous process control can typically be mixer von Loedige, Paderborn (e.g., Loedige CB mixer), Drais, Mannheim (e.g., Drais CoriMix), of Ballestra, Milan, Italy (e.g., Ballestra Cetemix) or from Schugi-Leylistad, The Netherlands (e.g., Schugi Flexomix).

If a continuous process is used, two can also be used Mixers are combined with each other, such. a song CB and a Loedige KM mixer, whereby in the second mixer also a coating with an inorganic powder take place can.

The production of the agglomerates is preferably carried out in one Intensive mixer by mixing the above-mentioned support materials with the surfactant. In many cases it is preferred the support materials (component a, b, and optionally d) intensive mixing in advance. The surfactant or the Surfactant mixture, which is optionally provided with other additives is, can be added in the pure state or mixed with water become. Preference is given to water contents between 0 and set about 50%. Particular preference is given to water contents between 0 and about 20%. The use of pure surfactants agglomeration has the advantage that the resulting Agglomerates do not need to be dried. This also applies to surfactant-water mixtures which have water contents, those of the finished washing powder or Waschpulverformlinge correspond.

According to a particularly preferred embodiment takes place in a coating of the agglomerate particles to a second mixer, whereby the structure of the particles is obtained remains.

According to the invention, the coating of the agglomerate particles Zeolite, bentonite, talc or titanium dioxide powder. If the agglomerates according to the invention already contain zeolite are, the coating can also be omitted, if one given sufficient degree of whiteness of Agglomeratteilchen and a further reduction of stickiness is not required.

Preferably, no according to the present invention Crushing of the agglomerate particles.

Another aspect of the present invention is concerned layered mineral agglomerates with nonionic surfactants, which are obtainable by the above method.

According to the invention, the agglomerates are used as additives to detergents used. It is particularly advantageous that due to the very high content of nonionic surfactants only added quite small amounts of the detergent composition Need to become. This is also the aforementioned gel effect limited to the added agglomerates and due the composition of the agglomerates according to the invention quite low. The added agglomerates meet both the function of providing a sufficient salary on nonionic surfactants as well as the increase of Soft grip of the wash.

Another aspect of the present invention relates to Detergent or a detergent additive, the or the Contains agglomerates according to the invention.

According to a preferred embodiment of the invention the agglomerates are used in detergents which are in Tablet form present.

The invention will be described below by way of examples closer purifies, which serve only for illustration and the invention should not be restricted in any way.

Examples Introduction to the examples: Implementation of agglomerations

For the preparation of the agglomerates discussed in the following examples Unless otherwise stated, an Eirich Intensive Mixer was used R02E used. This was the low setting (Level 1) for the rotational speed of the plate as well as the maximum speed of rotation for the Swirler chosen. The agglomeration parameters were, if not stated otherwise, in the following each chosen so that more than 50% of the agglomerates in a particle size range from 0.2 to 1.2 mm. The mean particle size can be like known in the art by routine choice the manufacturing parameters are modified. The agglomerates were indicated, with inorganic powders such. Coated or zeolite coated. These were the following Method used: In a first variant was the material is transferred into a plastic bag, the inorganic one Powder was added and shaken for about 2 minutes. In another variant, the coating (the coating) performed in Eirichmischer. This was after the agglomeration added the inorganic powder for coating and then the agglomerate / powder mixture again for 2 minutes mixed. The other results were comparable.

Measurements of the dissolution behavior of the nonionic surfactants in the agglomerates

To determine the dissolution behavior of the surfactants as a function the time was the measurement of the surface tension of the solution the agglomerates used. The measurement of the surface tension as a function of time, the bubble pressure method was used with an online tensiometer, SITA-Online F10. to Recording of the measured curves was performed with a bubble frequency of 1 Hz worked. The measurements were standardized samples used of particle sizes between 0.2 and 1.2 mm. It samples of 1 g were used, distilled in 200 ml Add water and stir with a length of 1.5 cm was stirred at a frequency of 150 revolutions. The Surface tension can be used as a measure of this measurement Surfactant release serve. As a comparison, this was the following most widely used surfactant Genapol OA 070 in one concentration of 0.5 g / l used. Such a solution showed under the same measuring conditions a surface tension of 30-32 mN / m.

Determination of bulk density:

The bulk density (bulk density) was in the following Examples determined by adding 100 g of the agglomerates in a 1,000 ml can filled and shaken for about 30 seconds.

The measuring cylinder is weighed empty to 10 mg. On it is the Powder funnels with tripod and clamp over the opening of the cylinder attached. After starting the stopwatch of the Measuring cylinder within 15 seconds with the agglomerates filled. With the spatula is continuously poured filling, so that the measuring cylinder is always filled slightly overhanging is. After 2 minutes, the supernatant is removed by spatula, being careful that no pressing forces compact the material in the cylinder. The filled measuring cylinder is brushed and weighed.

Bulk density is expressed in g / l. General allow the bulk densities obtained of more than 600 g / l, in particular of more than 650 g / l, also a use of the invention Agglomerates in common compact detergents.

Example 1: Agglomerates of nonionic surfactants and mixtures of the precipitated silica Sipernat 50 and the bentonite EX0255

For this purpose, the corresponding powders were placed in the Eirich mixer and agglomerated by slow addition of the surfactant. As component a) was an alkaline activated bentonite from Süd-Chemie (EX0255), as component b) the precipitated silica Sipernat 50, available from Degussa, Frankfurt, and as component c) the nonionic surfactant Imbentin-C / 135/070 the company Kolb used. As a comparative example, the pure bentonite and the pure precipitated silica were agglomerated with the nonionic surfactant. In all cases, so much surfactant was added that free-flowing agglomerates were obtained. The surfactant content of the agglomerates produced is listed in the following table. To increase the whiteness these can be coated with 10% Wessalith P. Agglomerates of nonionic surfactants and mixtures of sipernate 50 and bentonite as solid carriers Share of EX 0255 in% Amount used EX 0255 [g] Amount used Sipernat 50 [g] Addition to imbentin C135 / 070 [g] Surfactant content of agglomerates [%] 100 800 - 676 45, 8 98 784 16 719 47 95 760 40 746 48 90 720 80 806 50.2 88 704 96 910 53.2 85 680 120 945 54.2 75 300 100 588 59.5 66.66 300 150 697 60.8 50 200 200 761 65.5 0
(Comparison, pure Sipernat 50) - 400 1090 74

The above results are graphic in Figure 1 played.

The straight line shown in Figure 1 shows for comparison the course, which one with an ideal mixing behavior of the Support materials with respect to the binding capacity for nonionic Surfactants would be expected. As shown in Table 1 and Figure 1, the content of the agglomerates increases to nonionic Surfactants at levels above about 12% precipitated silica, based on the total amount of support materials, significantly disproportionately too, if one part of the bentonite replaced by the precipitated silica.

For the above agglomerates, the speed became the surfactant release by measuring the interfacial tension as a function of the stirring time on the basis of the above-described Method determined.

It was found that in the mixtures according to Table 1 by the addition of the precipitated silica to the bentonite the surfactant release was improved. This effect was at the Silica contents according to the invention from about 12 wt .-% based on the support materials particularly significant, resulting by a significant lowering of the interfacial tension showed.

Example 2: Agglomerates of nonionic surfactants and mixtures of sipernate 22 and EX 0255 as solid carriers

Analogously to Example 1 above, mixtures of Sipernat 22 (from Degussa, Frankfurt) with bentonite EX 0255 from Süd-Chemie AG (sodium bentonite with high swelling capacity) were investigated. The resulting agglomerates were coated for further investigations with 10% Wessalith P (zeolite). The results obtained are shown in Table 2 below. Agglomerates of mixtures of EX 0255 and Sipernat 22 with the nonionic surfactant Genapol OA 070 Share of EX 0255 in% Amount used EX 0255 [g] Amount used Sipernat 22 [g] Addition to Genapol OA 070 [g] Surfactant content of agglomerates [%] 100 800 - 645 44.6 98 784 16 655 45 95 760 40 677 46 90 720 80 730 48 88 704 96 878 52.3 85 680 120 910 53.2 75 450 150 750 55.5 66.66 400 200 823 58 50 250 250 780 61 0
(Comparison, pure Sipernat 22) - so 62

The results from Table 2 are shown in the figure below 2 graphically reproduced.

As in Example 1, when using more than about 12 wt .-% precipitated silica a disproportionate increase the Tensidaufnahmefähigkeit. Exactly the investigation showed the surfactant release from those given in Table 2 Agglomerates comparable results as in Example 1 specified.

The above data also show that replacement half of the bentonite through the precipitated silica agglomerates with only about one percent lower surfactant content produce compared to pure precipitated silica to let.

The good agglomeration of these systems was also documented in the size distribution of the agglomerates. So could at a Backing material made of 50% Sipernat 22 and 50% EX 0255 after the Coating can be obtained with zeolite agglomerates, of which over 80% in a size range between 0.2 and 1.2 mm was. The fine fraction (agglomerates with sizes less than 0.2 mm) was in this system after optimization of the manufacturing parameters below 5%. The bulk density of these agglomerates was 650 g / l.

Example 3: Agglomerates of mixtures of Laundrosil DGA with different precipitated silicas

Analogous agglomerates could also be made with blends of Laundrosil DGA, a soda-activated bentonite available from Süd-Chemie AG, and other precipitated silicas. Also in these cases the agglomerates were coated with 10% Wessalith P. The following Table 3 lists the composition and bulk density of the agglomerates screened to sizes of 0.2-1.2 mm: Agglomerates of mixtures of Laundrosil DGA and various precipitated silicas and the nonionic surfactant Genapol OA 070 bentonite silica relationship surfactant Bulk weight after coating with 10% Wessalith P Laundrosil DGA Sipernat 22 1: 1 59% 650 g / l Laundrosil DGA Sipernat 22 S (Degussa) 1: 1 59% 720 g / l Laundrosil DGA Neosyl GP (Crosfield) 1: 1 58% 670 g / l

As can be seen from the table, can also by the Use of further precipitated silicas in the inventive Agglomerates free-flowing granules with very high contents be prepared on nonionic surfactants. The like The surfactant release test given in Example 1 above a very rapid release of the nonionic surfactants from the invention given in Table 3 above Agglomerates.

Example 4 Comparison of the agglomeration according to the invention in the intensive mixer with an extrusion or compaction

To the advantages of the manufacturing method according to the invention to document by agglomeration in an intensive mixer, this was compared to a compaction or Extrusion of the prior art examined.

The agglomeration was carried out with the Eirich R02E mixer discussed above carried out. 200 g of Sipernat 22 were used for this purpose with 200 g Laundrosil DGA presented in the Eirich mixer and after intense Mixing, the powder was agglomerated with Genapol OA 070. This agglomerates containing 59% Genapol OA 070 received. These can be optional with 10% Wessalith P (zeolite) are coated by the appropriate Amount of zeolite is added to the agglomerates and the Mixture is mixed again. The process can be optimized in this way be that maximum 20% of agglomerates greater than 2 mm and a maximum of 20% of the agglomerates are less than 0.5 mm.

Granulating press / extrusion

After the intensive mixing as described above the above composition in an Eirich R15 mixer and the addition of 10% zeolite A was for extrusion a granulating press type Kahl 38/604 K of the company Amandus Kahl, Hamburg, used.

A throughput of 2 t / h was tested. It turned out that the material used is too dry for extrusion was not extruded at room temperature or by the Nozzles of the granulating press could be pressed. this could be bypassed by an addition of water, which is however adversely affects the product properties, either subsequent drying is required or added Water additionally be transported with the product which increases the transport costs of the final product. With some effort, only granules could be obtained the one cylindrical shape with a length of 2 mm and a Diameter of 2 to 3 mm.

The comminution required before addition to a washing powder could not after pressing on the extruder be carried out because the knives stuck and the plant had to be cleaned in very short intervals. The few obtained granules also showed a slower surfactant release as the agglomerates produced according to the invention on.

compacting

The same material was used for the compaction, also used for the extrusion described above has been. It became a compactor of the company Sahut Conreur S.A. (Raismes-France) used with cylinders of a length of 600 mm and a diameter of 145 mm. The compactor was operated at 8 rpm and pressures of 2.5 - 5 t / cm driven. The distance between the two cylinders was 2 mm. The power consumption of the compactor was 26 kW. It worked with a throughput of 2.7 t / h.

It was found that the nonionic surfactant partially was pressed out of the raw material. This resulted in a Gluing the rollers. The resulting end product left For this reason, it is very difficult to crush and sieve and showed a considerable stickiness.

In summary, it was found that the invention Agglomerates vs. extruded or compacted Materials advantageous properties with respect to surfactant uptake, low tack and fast surfactant release showed. In addition, particle sizes could be achieved with high yields obtained from about 0.4 to 2 mm particle diameter, as they are common in the detergent industry. moreover this is for the production of the agglomerates according to the invention used procedures less time and cost intensive.

It also showed that the high pressure at the compaction and extrusion a part of the surfactant again was squeezed out of the structure, causing the beneficial Properties of agglomerates are lost again.

To prevent this, would require additional powder components be added, which in turn, however, the content of nonionic surfactants would be reduced and components introduced that would not have a positive impact on the washing properties to have.

The method according to the invention is thus much more efficient, cheaper and comes with much less machine use than when extruding or compacting the case is, especially in the latter manufacturing processes in general, a subsequent comminution the extruded or compacted products required is.

Example 5: Investigation of the storage stability at 40 ° C over 3 days

In order to investigate the subsequent "bleeding" of the agglomerates, the storage stability was examined as follows:

A sample of Example 2 with a carrier material based on Sipernat 22 and EX0255 in the ratio 1: 1, which to increase Whiteness grade has been coated with 10% Wessalith P. was a 3-day storage test at 40 ° C in a drying oven subjected to the Heraeus brand. After the camp test a sieve analysis was performed in 0.2 mm increments. To the The comparison became part of the corresponding agglomerates of Sieben analysis subjected without storing at 40 ° C. Like in shown below, the agglomerates are under such storage conditions stable. A clumping could not be proved since the sieve analyzes are stored at room temperature and the samples stored at 40 ° C within the Measuring error and small deviations caused by the sampling is identical.

Example 6: Agglomerates with a fatty acid methyl ester ethoxylate

In this example, it was investigated whether the production of Agglomerates with similar high surfactant content also using of fatty acid methyl ester ethoxylate is possible. For this 400 g of a mixture of Laundrosil DGA and Sipernat 22 in the ratio 1: 1 in an Eirich mixer presented with the nonionic surfactant Genagen 24 MEE 080 (Clariant, Frankfurt) by slow addition of the surfactant agglomerated. It could obtain agglomerates with a surfactant content of 58% become. These showed after coating with 10% Wessalith P and a screening on particle sizes of 0.2 - 1.2 mm a bulk density of 700 g / l. Also these agglomerates show in the test shown above (measurement of the surface tension as a function of stirring time with 1 g of granules) a rapid release of the nonionic surfactant. Already after 70 sec stirring time, surface tension values of 30 - achieved 35 mN / m.

Example 7: Agglomerates with other bentonites or other layer minerals / Influence of the degree of activation of the bentonite

To the influence of a previous activation of the used Bentonite was used instead of in the above Examples 1 and 2 used bentonite EX0255 of corresponding unactivated bentonite EX0276 used. The Preparation of the agglomerates was as described in Example 1 carried out, wherein the respective bentonite in the ratio of 1: 1, based on wt .-%, with the precipitated silica sipernate 22 was used. It turned out that when used of the non-activated bentonite EX0276 a surfactant content of 54%, while using the corresponding Activated bentonite EX0255 a significantly higher Tenside content of 61% was reached. This proves the positive Influence of activation of the phyllosilicate used.

Example 8: Agglomerates using hectorite instead of bentonite

Agglomerates were prepared as described in Example 1, instead of bentonite EX0255 the hectorite Optigel SH, available from Süd-Chemie AG has been. Again, it was found that from a content of about 12 wt .-% precipitated silica a disproportionate increase the surfactant uptake was observed. It could at a ratio of hectorite: precipitated silica logo CNRS logo INIST 1: 1, a surfactant content of 58% can be achieved.

Example 9: Agglomerates of nonionic surfactants and mixtures of zeolite, bentonite and precipitated silica

Using Laundrosil DGA (Süd-Chemie AG) as a layered mineral component, Wessalith P (Degussa) as a zeolite component, and Sipernat 22 (Degussa) as a precipitated silica, agglomerates were prepared according to Example 1 which had the above components in the proportions shown in Table 4 below contained. Agglomerates with ternary carrier mixtures of phyllosilicate, precipitated silica and zeolite Layered mineral component Zeolite component Silica component Ratio of the individual components Surfactant content of agglomerates [%] Laundrosil DGA Wessalith P (Degussa) Sipernat 22 1: 1: 2 57 Laundrosil DGA Wessalith P (Degussa) Sipernat 22 2: 1: 2 53.3

Surprisingly, it was found that compared to Example 7 (or Example 3) by replacing a portion of the precipitated silica by zeolite the maximum content of nonionic Surfactant is reduced only slightly (by 2%), although the pure zeolite (Wessalith P) only a Tensidaufnahmevermögen has about 30%. Obviously, the zeolite can be used here Precipitated silicic acid functional in the stabilized "house of cards structure" replace the agglomerates according to the invention.

Claims (20)

1. Agglomerates containing layered silicate with non-ionic surfactants as a detergent additive, containing

   a) at least one natural or synthetic layered silicate, chosen from the group of clays containing montmorillonite, in particular bentonite, and also attapulgite, hectorite and/or beidellite in a quantity of more than 10 % by weight (component a),

   b) at least one precipitated silicic acid, in a quantity of at least 12 % by weight (component b), in each case in relation to the total quantity of support materials,

   c) at least one non-ionic surfactant, in a quantity of > 50 % by weight (component c) in relation to the total agglomerate, wherein no compacting or extrusion takes place during the production of the agglomerate.
2. Agglomerates according to Claim 1, characterised in that they contain at least 52 % by weight, in particular at least 55 % by weight, of non-ionic surfactant.
3. Agglomerates according to Claim 1 or 2, characterised in that they contain up to 75 % by weight, and in particular up to 80 % by weight, of non-ionic surfactant.
4. Agglomerates according to any one of the preceding Claims, characterised in that they have a content of at least 15 % by weight, in particular at least 20 % by weight, of precipitated silicic acid in relation to the total quantity of support materials.
5. Agglomerates according to any one of the preceding Claims, characterised in that the ratio of layered silicate to precipitated silicic acid, in relation to percent by weight, is between 1:20 and 20:1, preferably between 2:1 and 1:2, in particular at approximately 1:1.
6. Agglomerates according to any one of the preceding Claims, characterised in that the components a) to c) constitute at least 85 % by weight, preferably at least 90 % by weight, and especially preferably at least 95 % by weight of the agglomerates.
7. Agglomerates according to any one of Claims 1 to 5, characterised in that additionally at least one zeolite (component d) is contained preferably in a quantity of between 0.5 and 60 % by weight, in particular between 5 and 30 % by weight, in relation to the support materials.
8. Agglomerates according to any one of the preceding Claims, characterised in that 10 to 15 % of bentonite, 5 to 15 % by weight of zeolite and 10 to 30 % by weight of precipitated silicic acid are contained in relation to the total agglomerate.
9. Agglomerates according to Claim 6 or 7, characterised in that the components a) to d) constitute at least 85 % by weight, preferably at least 90 % by weight, and especially preferably at least 95 % by weight of the agglomerates.
10. A method of producing agglomerates containing layered silicate with non-ionic surfactant, wherein

    a) at least one natural or synthetic layered silicate, chosen from the group of clays containing montmorillonite, in particular bentonite, and also attapulgite, hectorite and/or beidellite in a quantity of more than 10 % by weight (component a),

    b) at least one precipitated silicic acid, in a quantity of at least 12 % by weight (component b), in each case in relation to the total quantity of support materials,

    c) at least one non-ionic surfactant, in a quantity of > 50 % by weight (component c) in relation to the total agglomerate;

    d) optionally at least one zeolite, preferably in a quantity of from 0.5 % by weight to 60 % by weight, in relation to the total quantity of support materials, are intensively mixed and agglomerated without compacting or extrusion.
11. A method according to Claim 10, characterised in that more than 60 %, in particular more than 80 % of the particles have a particle diameter of between 0.1 and 3 mm, in particular between 0.2 and 2 mm, especially preferably between 0.4 and 1.4 mm.
12. A method according to Claim 10 or 11, characterised in that the intensive mixing and agglomeration takes place in a mechanically produced fluidised bed.
13. A method according to any one of Claims 10 to 12, characterised in that the apparatus for carrying out the intensive mixing is a continuously or discontinuously operated intensive mixer.
14. A method according to any one of Claims 10 to 13, characterised in that a coating of the agglomerate particles is effected in a second mixer, the structure of the particles being maintained.
15. A method according to any one of Claims 10 to 14, characterised in that zeolite, bentonite, talcum or titanium dioxide powder are used for the coating.
16. Agglomerates containing layered mineral with non-ionic surfactants, which can be obtained in accordance with the method according to any one of Claims 10 to 15.
17. Use of the agglomerates containing layered mineral with non-ionic surfactants according to any one of Claims 1 to 9 in a detergent.
18. Use according to Claim 17, wherein the agglomerates containing layered mineral are used in the detergent in a quantity of 0.5 to 60 % by weight, in particular 1 to 40 % by weight, and especially preferably 5 to 25 % by weight.
19. Use according to either one of Claims 17 and 18, characterised in that the detergent is present in a tablet form.
20. A detergent or detergent additive, containing the agglomerates according to any one of Claims 1 to 19.

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