ES2232608T3 - AGLOMERATES CONTAINING STRATIFIED SILICATES WITH NON-IONIC TENSIOACTIVE AGENTS. - 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

Agglomerates containing silicates stratified with non-ionic surfactants.

The invention relates to agglomerates containing silicates stratified with non-ionic surfactants, at a procedure for its production, as well as its use as detergent additive.

Nonionic surfactants are used increasingly in detergents in powder form. The reasons for this they are first of all in their good properties of washing, even at low temperatures. This is accompanied by the tendency to lower wash temperatures in countries European, and for the low washing temperatures, already used for a long time in America and Asia. In addition, the properties washing agents that have non-ionic surfactants do not they influence, or they are only slightly influenced by a high hardness of the Water. Also, nonionic surfactants have some cleaning properties for a dirt that contains grease as well as for fabrics based on synthetic fibers, which are better in comparison with those of anionic surfactants.

Because of its consistency from liquid to waxy, the penetration of non-ionic surfactants into high amounts in powdered detergents is linked However with some difficulties. Thus, the employment of agents nonionic surfactants in washing powders, which are produced by an atomization process, already during drying by atomization, easily leads to a sticking of the nozzles and to a swelling of the dust by evaporation of impurities easily volatile in non-ionic surfactants.

In the state of the art, the agents non-ionic surfactants are applied on the powders, therefore in most cases, only after drying by atomization. However, here the absorption capacity of powders obtained from the spray drying process, does not allow to apply or incorporate large quantities of agents nonionic surfactants.

Also in the case of powders, which are not produced by spray drying, it may be desirable to increase even plus the content of non-ionic surfactants. Also in In this case, however, the absorption capacity of the powder for other additional surfactants.

In the state of the art many are already known detergent compositions, containing solid systems of support for non-ionic surfactants. Often these systems are limited in terms of their absorption capacity for nonionic surfactants. In addition, from many support systems, known in the state of the art, for non-ionic surfactants, the latter are released prematurely during storage. This effect is designated as "exudation" (of the English bleeding) of the agglomerates. Finally, many known agglomerates, especially in the case of high degrees of charge with non-ionic surfactants, they are sticky and therefore unable to run.

Japanese patent document JP 0009087699 AA describes a granular composition of non-ionic detergent, which contains a nonionic surfactant, a clay mineral, such as montmorillonite, an oil absorbent support, such as a amorphous silicic acid, and a silicone. Others may be present additives, such as a sodium silicate as an improving agent for detergency, an organic polyacrylate salt, also as an agent detergency builder, an optical lightening agent, an enzyme, a bleaching agent and a spreading agent. The ingredients are They knead and extrude, and then crumble. For that reason, not No simple agglomeration takes place.

JP 0011310791 describes a granular composition of non-ionic detergent, which contains an agent non-ionic surfactant, a clay mineral and an absorbent support of oils The ingredients are mixed, kneaded, extruded and then then crumble. A simple procedure is not described of agglomeration.

U.S. Patent Document US-A-4,861,510 describes granules Porous detergents, containing sodium sulfate and silicates synthetic stratified The granules are produced by spray drying, resulting in a porous granulate, which It can be loaded with liquid surfactants. The capacity of reception (absorption) of liquids is between 2 and 50% in weight, preferably up to 35% by weight. According to the invention, the content of surfactant is above 50%, and the agglomerates are not produced by desiccation by atomization.

The German patent application document DE-A-38.35.918 (= document of European patent application EP-A-0.362.881 = US document 5,354,493) describes a process for the production of granules containing surfactants, which can contain zeolites and bentonites as support materials. From according to this procedure, in the mixing stage (a) the nonionic surfactant is mixed with water, which eventually may contain a part, but less than 50% by weight of the amount total of water soluble or insoluble solid materials in water, until the formation of a gel phase, after which in step (b) is added to the mixture the remaining principal amount of solid materials, and the mixture is mechanically processed until the formation of granules. The agent weight ratio non-ionic surfactant and water in the gel phase, to the materials solids present in total, is from 25:75 to 65:35. It can not detach from that publication a net content of an agent nonionic surfactant, referred to the finished granules. Starting of the examples, surfactant agent contents are calculated (referring to an ethoxylated anhydrous alcohol compound) of 10 a 20.5% by weight. The content of surfactant is located by therefore well below 50% by weight. Since the ability to reception of the surfactant, which has zeolite A, is only 26% by weight, it is not possible to produce, based on Zeolite as the sole support material, granulated with some Surfactant content of more than 50%. This is also not possible in the case of support mixtures based on bentonites and zeolites, since bentonite granules can receive maximum only about 40% by weight of agent surfactant

The document EP-A-0.690.123 describes a procedure for the production of a detergent in powder form, wherein (1) a detergency builder (carbonate of sodium, a zeolite, STPP, nitrile-triacetate trisodium, citrates or sulfates or mixtures thereof) agglomerates with a non-ionic surfactant, (2) a barrier material is added (amorphous silicates / precipitation silicic acids), and (3) are carries out further treatment together with the improving agent of detergency to form the final granulate. Total content of surfactant is 5 to 50% by weight, and therefore is located below the upper limit value according to the invention. In addition, the products according to the invention are produced only in At most two stages. Otherwise, the conglomerates conforming to invention have to contain stratified silicates with a certain Montmorillonite content.

It was therefore mission of the invention to put disposal agglomerated with a high content of agents non-ionic surfactants, which are not sticky, do not "exude" and make possible a faster release of agents non-ionic surfactants in the wash treatment bath. In addition, the effect of gelation, which can often be observe when the release of the surfactants is not ionic, should be decreased as much as possible. The gel phases, which result in this case, have a high viscosity, which prevents a rapid dissolution of surfactants, and may cause a glue of the particles when dissolving.

The problem posed by this mission is solved by agglomerates containing stratified silicates, according to the invention according to claim 1.

The agglomerates according to the invention they contain

to)

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

b)

by at least one precipitated silicic acid, in an amount of at least minus 12% by weight (component b),

in each case referred to the quantity total materials of support,

C)

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

not making any compaction or extrusion when producing the agglomerate.

Thus, it was surprisingly found that agglomerates according to the invention with the preceding composition, they can receive very high amounts of non-surfactants ionic, without them becoming sticky or "exuding".

The agglomerates according to the invention can be add in a particularly advantageous way to washing powders, remaining the gel formation effect, previously mentioned, on the one hand, limited only to agglomerates and not covering the total detergent composition, and resulting, by another part, also surprisingly small.

In this context, it was shown in a way unexpected that in the case of a content of at least 12% in weight of a precipitated silicic acid, preferably at least minus 15 to at least 20% by weight of a silicic acid precipitated, a synergistic effect appears with the silicates stratified above, and a very high incorporation of nonionic surfactants, without this leads to a stickiness or an "exudation" of the agglomerates

In addition, in the case of compliant agglomerates The invention quickly guarantees the dissolution of the particles of these agglomerates, as well as the rapid release of agents surfactants inside the wash treatment bath, being able to also avoid inlays on washed clothes.

It was found, finally, that as silicates natural or synthetic laminates, provide results especially advantageous silicates containing Montmorillonite, such as a bentonite, as well as an attapulgite, hectorite and / or beidellite.

Therefore, according to one way preferred embodiment, natural bentonites are used or synthetic (preferably a bentonite with Na), attapulgites, Beidellitas and / or hectoritas. In particular, in the cases of a bentonite and a hectorite additionally shows a more effect positive on washing performance or a softening effect of the tissues.

Together with natural stratified silicates, it they can also use stratified silicates according to the invention synthetic, for example a synthetic hectorite.

It was found that a preliminary activation, in particularly an activation under alkaline conditions of the silicates stratified, has a positive impact on the properties of agglomerates according to the invention. According to a way of especially preferred embodiment, for example a activated bentonite, in particular an activated bentonite with sodium carbonate

As mentioned above, in the case of a precipitated silicic acid content of at minus 12% by weight, based on the total amount of materials support (components a, b and possibly d according to the claims 1 and respectively 7), in combination with the natural or synthetic stratified silicates, shown surprisingly a synergistic effect. Therefore, the amount of silicic acid precipitated in the agglomerates according to the invention it is adjusted so that it is at least 12% in weight, preferably at least 14% by weight, and in particular at least 16% by weight, based on the total amount of support materials

It is assumed, without the invention being restricted to this theoretical mechanism of effect, that in the agglomerates according to the invention the stratified silicate used forms, by way of a "house of cards" or a scaffold, a porous structure for reception of the non-ionic surfactant, the structure being stabilized by the very porous precipitated silicic acid and this cooperating with the three-dimensional structure of the stratified silicate. The agglomerates according to the invention therefore have a particularly high and relatively stable porosity. In addition, it is assumed that precipitated silicic acid produces a (partial) de-stratification of the stratified silicate
slap

By means of a compaction or extrusion it is carried out probably a rather parallel orientation of the inserts of the stratified silicate, which has a negative impact on the porosity of the agglomerates and their ability to receive surfactants.

In order not to harm or even destroy this "stabilized structure of house of cards" which is especially suitable for receiving high amounts of surfactants, the agglomerates according to the invention are not therefore neither compacted nor extruded. In this case it turns out familiar to an expert in the specialty what is to be understood by compaction and extrusion, should be avoided according to the invention energy contributions such that they could produce a considerable modification of the porosity and density of agglomerates Thus, in the case of energy contributions too high, or in the case of the performance of high forces of shear or compression, as in particular in cases from compaction (with rollers) or extrusion, it results damaged the stabilized structure of house of cards that described above, based on bentonite inserts and silicic acid particles. By a compaction is understood in this context also a "compactor" kneading.

Since, however, leaving aside the Unexpected effect described above, no influence is known positive of the precipitated silicic acids on the properties washing, and precipitated silicic acids, on the other hand, are also very expensive, it is preferred according to the invention that the amount used precipitated silicic acid not above 40% by weight, and preferably not above 30% by weight, based on total agglomerates. So surprising, despite the relatively small amount of a silicic acid precipitated in the agglomerates, can be achieved very high absorption rates for non-surfactants ionic, presenting the agglomerates according to the invention a rapid solubility. In addition, the agglomerates according to the invention show surprisingly, with equal content of surfactants that the agglomerates according to the state of the art, a manifestly smaller stickiness.

The agglomerates according to the invention are produced advantageously in the particle sizes that are usual for detergent additives, which are familiar in this sector for a Expert in the specialty.

Unlike this, in the case of a compaction or extrusion of the particles must be carried out first a preliminary mixing, for example by kneading in cylindrical rollers, or by kneading in an extruder, obtaining then a thick material in the form of a cake or a material Extruded pressed through a nozzle. This material must be shredded at a subsequent stage, which in particular in the cases of the high content of intended surfactants according to the invention and the increased stickiness of the material compacted or extruded, it is problematic as well as of great Energy consumption and high costs.

In the agglomerates according to the invention can be use all precipitated silicic acids that are common and known to an expert in the field. In terms general, they constitute a starting material for obtaining wet silicic acids silicate solutions of alkali metals, preferably a soluble glass of sodium, to from which an amorphous silicic acid is precipitated by the addition of an acid. After filtration, washing and drying, the precipitated product consists of 86 to 88% SiO2 and 10 to 12% water, which is physically fixed both in the molecular association as well as near the surface as well as of remains of the salt that has resulted during the reaction, and of small impurities of metal oxides. By variation of the most important precipitation parameters, such as temperature Precipitation, pH value, electrolyte concentration and the duration of precipitation, acids can be produced silicic with different surface properties. Can be produce silicic acids in the range of surfaces specific of about 25 to 700 m2 / g.

The suspension of silicic acid, which has been obtained when the precipitation is carried out, it is transferred to presses of filtration, the solid material content of the filter cake between about 15 and 20%. Desiccation is performs according to different procedures, which follow frequently grinding and sorting stages.

You can use silicic acids both hydrophilic as well as hydrophobic, being able to silicic acids Hydrophobes serve at the same time as antifoaming agents.

The silicic acids used in the case of present invention, preferably have an average diameter of particles of about 1 to 100 µm. In most of the cases, precipitated silicic acids with a high specific surface area and high adsorption capacity, which is characterized by the oil index or the phthalate index of dibutyl (DBP index) in accordance with DIN 53601.

For the production of agglomerates, you can employ all nonionic surfactants that are familiar to an expert in the specialty. These include, without stay limited to him, the group of ethoxylated compounds of alcohols or of the (alcohol fatty) poly (ethylene glycol) ethers, of the alkyl polyglycosides, of the (alcohol fatty) poly (glycol) methyl esters-esters, of ethoxylated compounds of fatty acid methyl esters, of sorbitan esters, or mixtures thereof. They are preferred in this context the (fatty alcohol) poly (ethylene glycol) ethers, alkyl polyglycosides, ethoxylated compounds of fatty acid methyl esters and (alcohol fatty) poly (glycol) ethers-methyl esters. They are Especially preferred (alcohol fatty) -poly (ethylene glycol) ethers, the (alcohol fatty) poly (glycol) ethers-methyl esters, or mixtures from both. In the case of the use of ethoxylated compounds of fatty acid methyl esters, agglomerates conforming to invention can be dissolved in a surprisingly fast way.

Within the (alcohol fatty) poly (ethylene glycol) ethers are preferred which they are usual in detergent applications, that is, those that have degrees of ethoxylation between 1 and 12 as well as alkyl chain radicals with 10 to 17 carbon units. The (fatty alcohol) -poli (ethylene glycol) -ethers with few ethoxy units are used in this case, so preferred, in mixtures with (alcohol fatty) -poly (ethylene glycol) ethers that have a higher degree of ethoxylation. Nonionic surfactants, preferred in an individual case, are dependent on the requirements specific established for the detergent, and can be determined in each case by an expert in the specialty with the help of trials routine

Together with the surfactants, the agglomerates may contain additional additives known in the state of the art In particular in the case of agglomerates with a ethoxylated alcohol compound or with an (alcohol fatty) poly (ethylene glycol) ether, can be added to agglomerates according to the invention additives known in the state of the technique, such as eg alcohols such as ethanol or glycerol, poly (ethylene glycols), or hydrotropic agents, such as cumene sulphonate of Na In the case of poly- (ethylene glycols) are used in particular those that have low molecular masses, in particular from 200 to 6,000 g / mol. These will mix, as a rule before agglomeration, with the agent surfactant, and are used in amounts of 0.1 to 30%, referred to the amount of surfactant.

It goes on to give even more details about the preferred procedures for the production of agglomerates according to the invention.

According to a preferred form of embodiment, the agglomerates according to the invention therefore contain minus 52% by weight, in particular at least 55% by weight, so especially preferred at least 58% by weight of agents nonionic surfactants, referred to the total agglomerate.

Preferably, the silicate ratio stratified to precipitated silicic acid, based on% by weight in the agglomerates according to the invention, it is located between 2: 1 and 1: 2 According to an especially preferred form of embodiment, stratified silicate and silicic acid precipitate are presented in approximately the same amounts, referred to% by weight.

According to a compliant embodiment to the invention, especially preferred, the agglomerates contain 10 at 15% by weight of a bentonite, from 5 to 15% by weight of a zeolite and from 10 to 30% by weight of a precipitated silicic acid, based on total chipboard.

Even when the agglomerates according to the invention, as previously mentioned, they may contain additionally additives known in the state of the art, of according to a preferred embodiment the agglomerates they consist essentially of a non-ionic surfactant, of a stratified silicate and a precipitated silicic acid, so It ensures intimate contact between these components. So preferred, the preceding components constitute at least one 85% by weight, in particular at least 90% by weight, and so 95% by weight of the agglomerates is especially preferred.

According to another embodiment of the present invention, it was found in a surprising way that the additional reception of at least one zeolite in the agglomerates, preferably in an amount between 0.5 and 60% in weight, and in particular between 5 and 30% by weight, referred to the material of support, leads to especially positive results. Is known that it is not possible to obtain agglomerates by agglomerating a zeolite with a non-surfactant ionic, because of the fine particle character of the zeolites can occur only with difficulty agglomerates having a usual particle size, in a yield satisfactory.

He found himself finally, in a surprising way, that by the planned combination of a zeolite with a stratified silicate according to component (a) of the claim 1, with a precipitated silicic acid according to component (b) of claim 1, and with an agent nonionic surfactant according to component (c) of the claim 1, essentially performance can be achieved better of agglomerates that have the desired size. It is assumed, without that the invention be limited to this assumption, that the silicate Stratified used acts as a kind of binding agent and through the reciprocal cooperation of the components it is done especially high absorption capacity for agents possible non-ionic surfactants, without this leading to even tackiness of the agglomerates obtained or the "exudation". Too it seems that zeolite can take over to some extent the function of the silicic acid precipitated in the "structure stabilized house of cards "described before

According to the invention, they can be used for agglomerated all the usual zeolites in commerce, e.g. Wessalith P®, Wessalith 2000® by Degussa, Doucil A24® and Doucil A4® from the Crosfield entity, Eijsden, The Netherlands. The agglomerates that contain stratified silicates can be produced according to invention according to a procedure, in which they are mixed intensively

to)

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

b)

by at least one silicic acid precipitated in an amount of at least minus 12% by weight (component b);

in each case referred to the total amount of materials from support,

C)

by at least one nonionic surfactant in one in an amount greater than 50% (component c), referred to the total agglomerate;

d)

eventually a zeolite, so preferred in an amount of 0.5% to 30% by weight, based on the total amount of support materials;

without compaction or extrusion, and it agglomerate.

According to a preferred form of embodiment, for intensive mixing a layer is produced turbulent mechanics. For this they can be used in terms general intensive mixers known in the state of the technique according to procedures by (discontinuous) or continuous loads. If the agglomeration is carried out by charges, they come into question for this, mixers by loads of the entity Eirich, Hartheim, Loedige mixers (eg Loedige FKM, Paderborn mixers) or Drais (Drais Turbomix, Mannheim). In the case of an embodiment Continuous process, mixers can typically be used Loedige, Paderborn (eg Loedige-CB mixers), from Drais, Mannheim (eg Drais CoriMix), from Ballestra, Milan, Italy (eg Ballestra Cetemix), or of Schugi-Leylistad, The Netherlands (eg Schugi Flexomix)

If a continuous process is used, they can be combine two mixers with one another, such as a Loedige CB mixer and Loedige KM mixer, can be carried out in the second mixer also a powder coating inorganic.

The production of the agglomerates is carried out, of preferably, in an intensive mixer by mixing the Support materials described above with the surfactant. In many cases it is preferred to mix intensively in advance the support materials (components a, b, and eventually d). He surfactant, or the mixture of surfactants, which optionally it is provided with other additives, it can be added in the pure state or mixed with water. They fit preferentially in such case water contents between 0 and approximately 50% Especially preferred are contents of water between 0 and about 20%. The use of the pure surfactants for agglomeration have in this case the advantage that the resulting agglomerates do not have to be dried This is also valid for agent mixtures surfactants and water, which have water contents that correspond to those of the finished washing powder, or of the bodies molded of washing powders.

According to an embodiment especially preferred, a second mixer is made coating (of the English coating) of the particles of the agglomerate, keeping the structure of the particles.

According to the invention, for coating the agglomerate particles, a zeolite, a bentonite, are used, a talcum powder or a titanium dioxide powder. In the event that the agglomerates according to the invention already have a certain content of zeolite, the coating can also be dispensed with, provided when a sufficient degree of whiteness of the agglomerate particles and a decrease is not necessary Additional stickiness.

Preferably, in accordance with the present invention does not effect any shredding of the particles of the agglomerate.

A further aspect of the present invention is refers to agglomerates with non-ionic surfactants. that contain stratified minerals, which are obtainable from according to the previous procedure.

According to the invention, the agglomerates are used as detergent additives. In this case it is especially advantageous. the fact that, through the very high content of agents nonionic surfactants, only amounts have to be added Very small detergent composition. With that, also the aforementioned gelation effect on the Agglomerates added is limited and very small because of the composition according to the invention of the agglomerates. Agglomerates added in this case fulfill the function of both setting provision of a sufficient content of non-surfactants Ionic as well as increasing the soft touch of clothing washed

A further aspect of the present invention concerns a detergent or a detergent additive, which contains
the agglomerate (s) according to the invention.

According to a preferred embodiment according to the invention, the agglomerates can be used in detergents, which come in the form of tablets.

The invention is explained below with greater detail with the help of Examples., which serve only for illustration and should not limit in any way to invention.

Examples Introduction to the Examples Agglomeration realization

For the production of the conglomerates debated in the following Examples, if not indicated otherwise differently, an intensive Eirich R02E mixer is used. At In this case, the low setting (step 1) was chosen for the plate rotation speed, as well as the maximum speed of rotation for the cyclone The agglomeration parameters are they chose, when not indicated otherwise, hereinafter respectively in such a way that more than 50% of the agglomerates they were presented in a range of particle sizes of 0.2 - 1.2 mm The average particle size can be modified, as it is known according to the state of the art, by means of a Routine choice of production parameters. The agglomerates, if this is indicated, they were coated with powders inorganic such as talcum powder or zeolites. For this I know they used the following procedures: In a first variant, the material was transferred to a plastic bag, the powder inorganic was added to this and stirred thoroughly during approximately 2 minutes In an additional variant, the operation Coating was carried out in the Eirich mixer. For this, the powder was added after agglomeration. inorganic to coat it, and then the mixture of the chipboard and the powder was mixed again for 2 minutes. The others Results were comparable.

Measurements of agent dissolution behavior nonionic surfactants in the agglomerates

For the determination of the behavior of dissolution of the surfactants as a function of time, made use of the surface tension measurement of the solution of the agglomerates. The measurement of surface tension as a function of time was carried out according to the pressure method of bubbles with an online tensiometer, SITA-Online F10 To record the measurement curves, we worked with a 1 Hz bubble frequency. Measurements were used standardized samples with particle sizes included between 0.2 and 1.2 mm. 1 g samples were used, added to 200 ml of distilled water and stirred with a stirring fish that had a 1.5 cm length with a frequency of 150 revolutions. The surface tension can serve in the case of this measurement as measure for the release of the surfactant. As a comparison, Genapol OA 070 surfactant, hereinafter used in In most cases, it was used in a concentration of 0.5 g / l A solution of this type presented in the same conditions measuring a surface tension of 30-32 mN / m.

Bulk Density Determination

Bulk density (bulk weight) is determined, in the following Examples, by introducing 100 g of the agglomerated in a boat with a capacity of 1,000 ml, and stirring for about 30 seconds.

The graduated measuring cylinder is weighed in empty state of 10 mg. After this, the funnel for dust, With a tripod and a clamp, it is fixed over the opening of the cylinder. After having started the stopwatch, the cylinder measuring graduate is filled with the agglomerates in the course 15 seconds With a spatula it is subsequently loaded so constant a filling material, so that the cylinder of Measurement is always filled in a slightly outstanding way. After 2 minutes the material is removed with a spatula outstanding, having to pay attention that there are no forces of compression that compress the material in the cylinder. The cylinder Full measuring graduate is emptied with a brush and weighed.

The apparent density is indicated in g / l. In general terms, the apparent densities obtained, of more than 600 g / l, in particular more than 650 g / l, also allow a use of agglomerates according to the invention in detergents compact streams.

Example 1 Agglomerates based on non-ionic surfactants and mixtures Sipernat 50 precipitation silicic acid and EX bentonite 0255

For this, the corresponding powders are previously arranged in the Eirich mixer and agglomerated by Slow addition of surfactant.

As component a) a bentonite was used activated in alkaline conditions of the entity Süd-Chemie (EX 0255), as component b) was used Sipernat 50 precipitation silicic acid, obtainable from the Degussa entity, Frankfurt, and as component c) the agent was employed non-ionic surfactant Imbentin-C / 135/070 of the Kolb entity. As a comparative example, also pure bentonite as well as pure precipitation silicic acid they agglomerated with the nonionic surfactant. In all cases, so much was added amount of a surfactant that were obtained agglomerates still capable of shifting. The content of surfactant of the agglomerates produced are listed in the following Table. To increase the degree of whiteness these can be coated with 10% of Wessalith P.

TABLE 1 Agglomerates based on non-surfactants ionic and mixtures of Sipernat 50 and bentonite as supports solids

one

The preceding results are reproduced graphically in Figure 1.

The line drawn in Figure 1 shows how comparison the evolution that would have been expected in the case of ideal mixing behavior of support materials as regards the agglutination capacity for agents nonionic surfactants. As can be seen in Table 1 and in Figure 1, the content of the agglomerates in terms of agents non-ionic surfactants in the case of contents from approximately 12% precipitation silicic acid, referred to the total amount of support materials increases manifestly above the proportional reason, when a part of the Bentonite is replaced by precipitation silicic acid.

For the previous agglomerates, the release rate of the surfactant by measuring surface tension depending on the duration of the stirring, with the help of the method described above.

It was revealed that in the case of mixtures according to Table 1 the release of surfactant by adding silicic acid precipitated the bentonite. This effect was especially significant in the case of silicic acid contents according to the invention from about 12% by weight, referred to the support materials, which was shown by a considerable decrease in interfacial tension.

Example 2 Agglomerates based on non-ionic surfactants and mixtures of Sipernat 22 and EX 0255 as solid supports

In a manner analogous to that of Example 1 above, mixtures of Sipernat 22 (from the entity were investigated Degussa, Frankfurt) with the entity's bentonite EX 0255 Süd-Chemie AG (sodium bentonite with a high swelling capacity). The resulting agglomerates are coated with 10% of Wessalith P (zeolite) for further investigations. The results obtained are indicated in The following Table 2.

TABLE 2 Agglomerates based on mixtures of EX 0255 and Sipernat 22 with the non-ionic surfactant Genapol OA 070

2

The results in Table 2 are reproduced. graphically in the following Figure 2.

As in Example 1, in the case of used more than about 12% by weight of silicic acid precipitate showed an increase above the reason proportional, of the reception capacity of surfactant. Exactly the same, agent release investigation surfactant from the agglomerates indicated in Table 2 showed comparable results, as indicated in Table 1

The preceding data also show that by replacement of half of the bentonite with the silicic acid of precipitation, agglomerates with a content can occur of surfactant that is only minor in about somewhat percent, compared to precipitation silicic acid pure.

The good agglomeration of these systems is also documented in the distribution of sizes of the agglomerates. Thus, in the case of a support material based on 50% Sipernat 22 and 50% EX 0255, after coating with zeolite, some agglomerates could be obtained, of which more than one 80% was located in a range of sizes between 0.2 and 1.2 mm. The thin portion (agglomerates with sizes smaller than 0.2 mm) was located below 5% in this system, after having Optimized production parameters. The bulk weight of these agglomerates was located at 650 g / l.

Example 3 Agglomerates based on mixtures of Laundrosil DGA with different precipitated silicic acids

Similar agglomerates could be produced also with mixtures of Laundrosil DGA, of a bentonite activated with sodium carbonate, obtainable from the entity Süd-Chemie AG, and other silicic acids precipitates Also in these cases, the agglomerates were coated with 10% of Wessalith P. In the following Table 3 they are listed the composition and bulk weight of the agglomerates, which had been sieving at sizes of 0.2 - 1.2 mm.

TABLE 3 Agglomerates based on mixtures of Laundrosil DGA and different precipitation silicic acids as well as the agent non-ionic surfactant Genapol OA 070

3

As can be seen from the Table, also through the use of other silicic acids precipitated in the agglomerates according to the invention can produce about granules capable of bleed, with very high contents of nonionic surfactants. The agent release assay surfactant, indicated as above in Example 1, gave as a result a very rapid release of agents nonionic surfactants from agglomerates conforming to invention, indicated in the preceding Table 3.

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

In order to document the advantages of the process according to the invention of production by agglomeration in an intensive mixer, this was investigated in comparison with a compaction or extrusion, according to the state of the art

The agglomeration was carried out with the mixer Eirich R02E explained above. 200 g of Sipernat 22 were arranged previously for this, together with 200 g of Laundrosil DGA, in the Eirich mixer and, after intensive mixing, the powder it was agglomerated with Genapol OA 070. In this case, about agglomerates with a content of 59% Genapol OA 070. These are can optionally be coated with 10% Wessalith P (zeolite), adding to the agglomerates the corresponding amount of a zeolite and then mixing the mixture. The process can be done. optimize in such a way that a maximum of 20% of the agglomerates is greater than 2 mm and a maximum of 20% of the agglomerates is less than 0.5 mm

Granulation / extrusion press

After intensive mixing, led to out as described above, of the composition above in an Eirich R15 mixer and the addition of 10% of a zeolite A, a granulation press of the type Kahl 38/604 K of the entity Amandus Kahl, Hamburg.

A flow rate of 2 t / h was tested. In that case, it was revealed that the material used was too dry for an extrusion, and at room temperature it is not could extrude or compress through the press nozzles of granulation. This could be avoided by adding water, which however has a disadvantageous impact on the product properties, since either a subsequent drying, or the added water must be transported additionally with the product, thereby increasing the costs of Transportation of the final product. With some effort they could obtain only a few granules, which had a cylindrical shape with a length of 2 mm and a diameter of 2 to 3 mm.

The crushing, necessary before the addition to a washing powder, could not be carried out after pressing in the extruder, since the blades were sticking and the installation It had to be cleaned at very short intervals. The few particles of obtained granules also presented a release of the surfactant, which was slower than that of the agglomerates produced according to the invention.

Compaction

The same material was used for compaction, which had also been used for extrusion previously described. A compactor of the entity Sahut Conreur S.A. was used. (Raismes-France), which was equipped with cylinders which had a length of 600 mm and a diameter of 145 mm. He compactor was operated with 8 revolutions per minute and at about pressures of 2.5 - 5 t / cm. The distance between the two cylinders was 2 mm The power absorbed by the compactor was 26 kW. Be He worked with a flow rate of 2.7 t / h.

In that case it was shown that the surfactant non-ionic was partially extracted under pressure from the material raw. This led to a sticking of the rollers. The product resulting end, for this reason, could be crumbled and separated by screened only with many difficulties and manifested a considerable stickiness.

In summary it was revealed that the agglomerates produced according to the invention manifested some advantageous properties compared to extruded materials or compacted when it comes to receiving the agent surfactant, small stickiness and rapid release of surfactant In addition, they were obtained with high yields particle sizes with diameters of particles of approximately 0.4 to 2 mm, as usual in the detergent industry. In addition, the procedure used to the production of the agglomerates according to the invention consumes less Time and costs

It was also revealed that through the use of high pressure when compacting and extrusion, a part of the surfactant was extracted back to pressure from the structure, which again loses the advantageous properties of agglomerates.

In order to avoid this, they had to add additional components in the form of powders, so without However, the content of agents would be reduced again nonionic surfactants and certain components would be introduced, which they have no positive influence on the properties of washed.

The process according to the invention is essentially more efficient, cheaper and content with a job of machines essentially smaller than what happens in the case of a extrusion or compaction, since in the case of production procedures mentioned last are it usually still needs a subsequent shredding of Extruded or compacted products.

Example 5 Investigation of storage stability at 40 ° C for 3 days

In order to investigate the subsequent "exudation" of agglomerates, stability in Storage was investigated as follows:

A sample from Example 2 with a support material that was based on Sipernat 22 and EX 0255 in the 1: 1 ratio, which had been coated with 10% of Wessalith P with the In order to increase the degree of whiteness, it was subjected to a test of storage for 3 days at 40 ° C in a drying oven Heraeus brand. After the storage test, it was carried Perform a granulometric analysis on a sieve with 0.2 mm steps. As a comparison, a part of the corresponding agglomerates are subjected to a granulometric analysis, without storing them at 40 ° C. Such As shown below, the agglomerates are stable in Such storage conditions. Could not verify any agglutination, since the granulometric analyzes of the samples stored at room temperature and samples stored at 40 ° C they are identical, within the measurement error and with small deviations conditioned by the sampling.

Example 6 Agglomerated with an ethoxylated methyl ester compound of fatty acid

In this Example we investigated whether the production of agglomerates with a similarly high agent content surfactant is also possible through the use of a compound ethoxylated fatty acid methyl ester. For this, I know they previously had 400 g of a mixture of Laundrosil DGA and Sipernat 22 in the 1: 1 ratio in an Eirich mixer along with the non-ionic surfactant Genagen 24 MEE 080 (Clariant, Frankfurt) by slow addition of the surfactant. They could obtain agglomerates with a surfactant content of 58% These, after a coating with 10% Wessalith P and a sieving separation at particle sizes of 0.2 - 1.2 mm, had a bulk weight of 700 g / l. Also these agglomerates show, in the test shown above (measurement of surface tension depending on the duration of the stirring with 1 g of a granulate), a rapid release of the surfactant nonionic Already after an agitation duration of 70 seconds (s) surface tension values of 30-35 are achieved mN / m.

Example 7 Agglomerated with other different bentonites or other minerals stratified / influence of the degree of activation of the bentonite

In order to investigate the influence of a preliminary activation of the bentonite used, instead of the EX 0255 bentonite used in the preceding Examples 1 and 2, is used the corresponding bentonite EX 0276 not activated. The agglomerate production was carried out as has described in Example 1, the respective bentonite being used in the 1: 1 ratio, based on% by weight, with silicic acid of Sipernat precipitation 22. It was revealed that in the case of the use of the non-activated bentonite EX 0276, had reached a surfactant content of 54%, on the contrary of which, in the case of using the corresponding EX bentonite Activated 0255 a surfactant content was reached manifestly higher, 61%. This demonstrates the positive influence. of an activation of the stratified silicate used.

Example 8 Agglomerates obtained through the use of a hectorite in instead of a bentonite

Agglomerates were produced as described in Example 1, using instead of bentonite EX 0255 the hectorite Optigel SH, obtainable from the entity Süd-Chemie AG. Also in this case he got manifest that from an acid content of 12% by weight precipitated silicic could see an increase greater than proportional to the reception capacity of the surfactant. In the case of a ratio of hectorite to precipitated silicic acid = 1: 1, a surfactant content of 58%

Example 9 Agglomerates based on non-ionic surfactants and mixtures of zeolite, bentonite and precipitated silicic acid

Mediating use of Laundrosil DGA (Süd-Chemie AG) as a mineral component stratified, of Wessalith P (Degussa) as a zeolitic component, and of Sipernat 22 (Degussa) as precipitated silicic acid, it produced according to Example 1 agglomerates, which they contained the preceding components in the relationships indicated in The following Table 4.

TABLE 4 Agglomerates with ternary base support mixtures of a stratified silicate, a precipitated silicic acid and a zeolite

4

Surprisingly, it was found that, in comparison with Example 7 (or Example 3), by replacement of a part of the silicic acid precipitated by a zeolite is decreased only insignificantly (by 2%) the maximum agent content non-ionic surfactant, although pure zeolite (Wessalith P) it had only a capacity to receive the surfactant of about 30%. Manifestly, in this case the zeolite can functionally replace the silicic acid precipitated in the "stabilized structure of house of cards" of the agglomerates according to the invention.

Claims (20)

1. Agglomerates containing silicates stratified with non-ionic surfactants as an additive to detergents, which contain

to)

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

b)

by at least one precipitated silicic acid, in an amount of at least minus 12% by weight (component b),

in each case referred to the total amount of materials from support,

C)

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

not making any compaction or extrusion when producing the agglomerates 2. Agglomerates according to claim 1, characterized in that they contain at least 52% by weight of a non-ionic surfactant. 3. Agglomerates according to claim 1 or 2, characterized in that they contain up to 75% by weight, and in particular up to 80% by weight, of a non-ionic surfactant. 4. Agglomerates according to one of the preceding claims, characterized in that they have a content of at least 15% by weight, in particular at least 20% by weight, of a precipitated silicic acid, based on the total amount of materials of support. 5. Agglomerates according to one of the preceding claims, characterized in that the ratio of the layered silicate to the precipitated silicic acid, referred to as many percent by weight, is between 1:20 and 20: 1, preferably between 2: 1 and 1: 2, particularly in about 1: 1. 6. Agglomerates according to one of the preceding claims, characterized in that the components a) to c) constitute at least 85% by weight, preferably at least 90% by weight, and especially preferably at least one 95% by weight of the agglomerates. 7. Agglomerates according to one of claims 1 to 5, characterized in that at least one zeolite (component d) is additionally contained, preferably in an amount between 0.5 and 60% by weight, in particular between 5 and 30% by weight, based on support materials. 8. Agglomerates according to one of the preceding claims, characterized in that they contain 10 to 15% by weight of a bentonite, 5 to 15% by weight of a zeolite and 10 to 30% by weight of precipitated silicic acid, referred to the total agglomerate. 9. Agglomerates according to claim 6 or 7, characterized in that the components a) to d) constitute at least 85% by weight, preferably at least 90% by weight, and especially preferably minus 95% by weight of the agglomerates. 10. Procedure for the production of agglomerates containing stratified silicates, with an agent nonionic surfactant, in which they are intensively mixed

to)

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

b)

by at least one precipitated silicic acid, in an amount of at least minus 12% by weight (component b);

in each case referred to the quantity total materials of support,

C)

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

d)

eventually at least one zeolite, preferably in an amount of 0.5% by weight up to 60% in weight, referred to the total amount of support materials, without compaction or extrusion, and agglomerate.

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Method according to claim 10, characterized in that more than 60%, in particular more than 80%, of the particles have particle diameters between 0.1 and 3 mm, in particular between 0.2 and 2 mm, especially preferably between 0.4 and 1.4 mm. 12. Method according to claim 10 or 11, characterized in that intensive mixing and agglomeration are carried out in a mechanically produced fluidized layer. 13. Method according to one of claims 10 to 12, characterized in that in the case of the intensive mixing device it is an intensive mixer that is operated in a continuous or discontinuous mode. 14. Method according to one of claims 10 to 13, characterized in that a coating of the agglomerate particles is carried out in a second mixer, the particle structure being preserved. 15. Method according to one of claims 10 to 14, characterized in that a zeolite, a bentonite, a talcum powder or a titanium dioxide powder is used for coating. 16. Agglomerates containing minerals stratified with non-ionic surfactants, obtainable from according to the method according to one of claims 10 to fifteen. 17. Use of agglomerates containing stratified minerals, with non-ionic surfactants of according to one of claims 1 to 9 in a detergent. 18. Use according to claim 17, in which agglomerates containing stratified minerals they are used in the detergent in an amount of 0.5 to 60% by weight, in particular from 1 to 40% by weight, and especially preferably from 5 to 25% by weight. 19. Use according to one of claims 17 and 18, characterized in that the detergent is in the form of tablets. 20. Detergent or detergent additive, which contains the agglomerates according to one of the claims 1 to 9