EP0648259B1 - Solid detergent composition with improved washing-in behaviour - Google Patents

Abstract

A powder of granular active washing compsn., is prepd. by mixing (a) a pre-prepd. washing powder or granulate with bulk wt. above 500 g/l, with (b) a liq. or solid, hydrophobic and/or water-insol. component, not a zeolite, in ratio by wt. of (a):(b) of 20-2000:1. Pref. the compsn. has bulk wt. 700-1200 g/l (800-1000 g/l), and is prepd. by spray-drying, opt. followed by compacting or mixing with other non-spray-dryable components. It may be prepd. by pressing a uniform pre-mix, opt. contg. a plasticiser, through orifices of 0.5-5 mm, followed by comminution of the extrudate in a cutting machine and rounding off in a unit, opt. using a mixt. with other washing components. The agent is pref. a paraffin, inert siloxane, fatty acid or salt, long-chain alcohol (opt. alkoxylated or sulphated), Si02, and/or inorganic anionic and/or cationic laminar cpd., esp. hydrophobised Si02, laminar silicate and/or hydrotalcite. Treatment may be in a machine for rounding off, pref. a spheroniser.

Description

The invention relates to a method for the treatment of wash-active solid Preparations with high bulk density, in powder or granule form are present with liquid or solid, hydrophobic or slightly water-soluble Fabrics, and the products they produce, in their induction behavior Products improved in household washing machines.

In general, washing-active preparations include washing, rinsing and cleaning agents understood, as well as their surfactant-containing precursors or premixes. Especially when such preparations have higher amounts contain nonionic surfactants, they tend to add water to the fact that during the dissolving or dispersing process a forms gel-like phase, which can lead to sticking of the powder grains. Under unfavorable conditions, as in some household washing machines with special design features, it can in the case of Detergents come to deposits of lumpy residue, which then are not available for the actual use of the product. This behavior often has a particularly disruptive effect on solid powdery materials Agents with high bulk density, which are usually none or contain little inorganic filler salts which increase the dissolution rate.

It is the concept of the following described invention, the dissolution or Disintegration behavior of active washing preparations with high Bulk weights through a special treatment of the surface of the particles to optimize so that under the conditions of flushing a Detergent in a household washing machine the individual washing powder particles separated faster by the inflowing water flow when they can clump together.

To improve the induction behavior of detergents, the patent literature already described a number of proposals. So in German patent application DE 38 18 829 a detergent intermediate or Detergent ingredient described, the dissolving behavior produced from it Universal detergent improved. The procedure described there suggests in the cation exchanger (builder), for example made of zeolite NaA, together with a defined soap, consists of polycarboxylic acids and use nonionic surfactants and the average grain size and that Determine the bulk density in a certain range. Furthermore there is the suggestion that the non-ionic surfactants with a water or not to mix poorly soluble compound containing hydrophobic residues. A mixture of, for example, is used as such a hydrophobic compound Tallow fatty acid partial glyceride and tallow fatty acid amide of hydroxylethylenediamine suggested. Although according to the teaching of this application Having a detergent made with good detergent behavior is a clear one The disadvantage is that the teaching described there is specific to the recipe is. It therefore does not allow others to come from different considerations out cheap formulations of wash-active preparations without essential Intervention in the formulation structure through a post-treatment step to improve.

This also applies to detergent additives with improved wash-in behavior, which are described in the German patent application DE 38 22 479 will. The subject of this published specification is granular detergent additives, consisting of a granular, porous, water-soluble or dispersible carrier material and water-soluble adsorbed thereon or water-dispersible nonionic surfactants in which the adsorbed nonionic surfactant in a homogeneous mixture with a Hydrophobic substance having polar groups is present, the weight ratio from nonionic surfactant to hydrophobic substance 99: 1 to 60:40. The hydrophobic substance preferably consists of Fatty acids with 12 to 22 carbon atoms.

The unpublished German patent application DE 41 23 195 describes a process for the preparation of detergent preparations in powder or granular form by treating a prefabricated powder or Granules with a liquid, reactive polysiloxane component in certain Weight ratios. This will speed up the dissolution of the active detergent preparation and this measure reduces their washability improved.

European patent application EP 0 360 330 A2 describes the improvement of the detergent behavior of powder detergents by spraying with an intimate mixture of C _8-22 fatty acid and liquid nonionic surfactant. That the density of spray-dried detergents containing 4 to 20% by weight of anionic surfactant, 2 to 20% by weight of nonionic surfactant, 20 to 50% by weight of builder and 3 to 25% by weight of washing alkalis, by treating with at least half of the can increase the total amount of nonionic surfactant contained in the agent in a mixer is known from European patent application EP 0 337 330. Spray-dried detergents are known from European patent application EP 0 337 523 A1 which, in addition to anionic and / or nonionic surfactants to improve the residue behavior, contain an additive which is insoluble in such surfactants and water, for example a paraffin, and which has a melting point in the range from 30 to 70 ° C and a contact angle to water of at least 75 °.

In particular in the production of detergents with high bulk density is the last Process step the powdering of the powder product, preferably produced by granulation with finely divided zeolite, in particular zeolite Na-A, not unusual, as for example proposed in international patent application WO 91/02047. This measure serves in essential to avoid sticking of the not yet completely dry or warmed, thus containing certain ingredients in a liquid and therefore sticky state Powder products right after production. Has the induction behavior of the finished products this powdering has no influence.

Against the background of this prior art, it is the object of the invention to be wash-active Preparations with a high bulk density as part of a post-treatment step and to be modified largely independently of their respective composition so that the The tendency to clump when water is added decreases.

Another object of the invention is to provide high detergents Bulk weight and improved washing-in behavior in washing machines. In addition, it is one The object of the invention to provide detergent precursors which can be easily washed in and which are have such detergents made up.

The invention thus relates to a method for producing a wash-active Preparation in powder or granule form with high bulk density and improved induction behavior, characterized in that a prefabricated detergent powder or Granules with a bulk density of more than 500 g / l with mixing with a liquid or solid, hydrophobic and / or water-insoluble component, which is not a zeolite, in contact brings, the weight ratio of prefabricated powder to liquid or solid, hydrophobic and / or water-insoluble treatment agent between 20: 1 and 2000: 1 adjusted and the treatment agent from the group comprising inert siloxanes, fatty acid salts, Alcohols with 10 to 22 carbon atoms, which can also be sulfated, silicas. inorganic anionic layered compounds, such as layered silicates, inorganic cationic Layer compounds, such as hydrotalcites, and mixtures thereof are selected.

The method according to the invention can be carried out with comparatively little technical effort carry out. The respective wash-active preparation, which is in your The induction behavior should be improved. So for example a detergent, a Intermediate detergent or a detergent or cleaning agent or other solid surfactant-containing preparations, which are in powder or granule form.

The largely water-insoluble inorganic solids under the suitable treatment agents are used in the form of commercially available fine-particle powder. It is largely irrelevant whether these materials exist as crystalline substances or amorphous. The above Silicas, layered silicates and hydrotalcites can in particular also be hydrophobic Form are used. It must be surprising that such inorganic materials are suitable are to improve the washing-in behavior of the detergent preparations according to the invention, while the desired effect with the same use of finely divided zeolite is not or at least does not occur to a sufficient extent. As a further advantage of the invention The process is to be evaluated that some of the treatment agents which can be used according to the invention, especially siloxanes, additional benefits in detergents, especially foam regulators Effect.

Inert siloxanes in the context of the invention are liquid organopolysiloxanes, in particular alkyl and aryl polysiloxanes, their copolymers and block polymers with polyalkylene oxides and their acylation products with long-chain fatty acids. They can be present as such or, if desired, in mixtures with other compounds customary as defoaming agents, which include, in particular, paraffins, long-chain fatty acid esters and finely divided silica, which can also be silanized or otherwise hydrophobized. The paraffins in question are generally a complex mixture of substances without a sharp melting point. For characterization, one usually determines its melting range by differential thermal analysis (DTA), as described in "The Analyst" 87 (1962), 420, and / or its solidification point. This is the temperature at which the wax changes from the liquid to the solid state by slow cooling. Paraffins which are completely liquid at room temperature, that is to say those having a solidification point below 25 ° C., and paraffins which are solid at room temperature can be used. For example, the paraffin wax mixtures known from European patent application EP 309 931 can be used, for example from 26% by weight to 49% by weight of microcrystalline paraffin wax with a solidification point of 62 ° C to 90 ° C, 20% by weight to 49%. -% hard paraffin with a solidification point from 42 ° C to 56 ° C and 2 wt .-% to 25 wt .-% soft paraffin with a solidification point from 35 ° C to 40 ° C. Paraffins or paraffin mixtures which solidify in the range from 30 ° C. to 90 ° C. are preferably used. It should be noted that even paraffin wax mixtures that appear solid at room temperature can contain different proportions of liquid paraffin. Particularly preferred paraffin wax mixtures at 30 ° C have a liquid fraction of less than 10% by weight, in particular from 2% by weight to 5% by weight, at 40 ° C a liquid fraction of less than 30% by weight, preferably of 5 % By weight to 25% by weight and in particular from 5% by weight to 15% by weight, at 60 ° C. a liquid fraction of 30% by weight to 60% by weight, in particular 40% by weight % to 55% by weight, at 80 ° C a liquid content of 80% by weight to 100% by weight, and at 90 ° C a liquid content of 100% by weight. The temperature at which a liquid content of 100% by weight of the paraffin wax is reached is still below 85 ° C. in particularly preferred paraffin wax mixtures, in particular at 75 ° C. to 82 ° C. In a preferred embodiment of the process according to the invention, organopolysiloxanes containing silica, in particular dimethylpolysiloxanes, are used. The content of finely divided silica, if present, is preferably from 5% by weight to 10% by weight, based on organopolysiloxane. If liquid organopolysiloxanes are to be used, their viscosity at room temperature is preferably 15,000 mPa.s to 38,000 mPa.s. It can be measured using conventional methods, for example a Brookfield viscometer model RVT using spindle No. 5 at 10 revolutions per minute. It is also possible to use finely divided solid or solid organopolysiloxanes. The solid formulations possible in this connection include the Silkones on organic porous carrier material with protective coating described in the international patent application WO 93/01269, the similarly composed, glycerin-containing foam regulation granules of the international patent application WO 92/13056 and in particular those from the European patent application EP 496 510 known fine-particle foam regulators based on silicone starch.

The fatty acid salts which can be used as treatment agents according to the invention are preferably selected from those of the saturated or mono- to polyunsaturated C ₈ -C ₂₂ -carboxylic acids. In particular, these include pelargonic, capric acid, lauric acid, lauroleic, myristic, Myristoleinsäure acid, palmitic acid, stearic acid, Petroselin acid petroselaidic, oleic acid, elaidic acid, linoleic acid, Linolaidinsäure, linolenic acid, eleostearic acid, arachidonic acid, Gadoleinsäure, arachidonic acid, behenic acid, erucic acid, Brassidic acid and clupanodonic acid. Among these, the C ₁₆ to C ₂₀ carboxylic acids are preferred. The fatty acid salts include those with a mono-, di- or trivalent countercation, in particular the sodium, potassium, lithium, magnesium, calcium and aluminum salts. Among them, calcium stearate is particularly preferred.

The long-chain alcohols in the sense of the invention are derived from the linear or branched chain primary or secondary alcohols with 10 to 22 carbon atoms selected. Are preferred the descendants of the above-mentioned fatty acids, so-called fatty alcohols, though also their branched-chain analogs, so-called oxo alcohols, are suitable. The alcohols can also be sulfated.

To the in Possible sulfation products in particular include primary alkyl sulfates with preferably linear alkyl radicals having 10 to 20 carbon atoms, the an alkali, ammonium or alkyl or hydroxyalkyl substituted Have ammonium ion as a counter cation. They are particularly suitable Derivatives of the linear alcohols with in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols. Useful Accordingly, the sulfation products of primary fatty alcohols in particular with linear dodecyl, tetradecyl, hexadecyl or octadecyl radicals and their mixtures. Particularly preferred alkyl sulfates contain a tallow alkyl radical, that is, mixtures with essentially hexadecyl and octadecyl radicals. The alkyl sulfates can in a known manner by reaction of the corresponding alcohol component with a conventional sulfating reagent, especially sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali, ammonium or alkyl or hydroxyalkyl substituted Ammonium bases are made.

In the case of silicas, a distinction is made between precipitated silicas, which come from aqueous Silicate solution are deposited, and pyrogenic, through a combustion process silicas usually obtained from silicon halides, the latter in particular because of their little or no presence Water content is often referred to as silicon dioxide. Preferably finely divided fumed silicas are used in the context of the invention, such as commercially available, for example, under the name Aerosil® are.

Silica gel as well as inorganic anionic or cationic layer compounds can be used as such or in previously hydrophobicized form will. These are usually treated with organohalosilanes received products understood, as in the case of hydrophobized Silicic acid, for example, in the US patents US 3 207 698 or US 3 388 073. Also by fixing of organopolysiloxanes, for example polydimethylsiloxane, to fine particles Silicon dioxide, such as from the US patent Known from US 3,235,509, hydrophobized silicas can be obtained will. Another example is with dimethyldichlorosilane or trimethylchlorosilane implemented fumed silica called. The water repellent of the anroganic substances mentioned necessary amounts of silane or siloxane are extremely small, they are usually not more than about 5% by weight of the amount of substance to be hydrophobized.

Contacting the detergent preparation with the treatment agent is expediently carried out with mixing. The mixing ratios lie for the ratio of active washing preparation to treatment agent preferably between 25: 1 and 1000: 1, in particular between 100: 1 and 500: 1. The treatment according to the invention can be carried out in conventional granulators, universal mixers or rounding devices, for example spheronizers, and can be done by powdering the pre-made wash-active Preparation with a solid treatment agent, which is appropriate for this is in the form of a fine powder, or by spraying a liquid Treatment agents are made. The treatment agent is preferred applied to the detergent preparation in such quantities, that the weight ratio of surfactant contained in this to treatment agent from 10: 1 to 200: 1, in particular 30: 1 to 120: 1, being particularly in the case of containing a relatively large amount of nonionic surfactant Preparations are more at the treatment-richer end of the said Range ratio of preferably 10: 1 to 50: 1 (Surfactant to treatment agent) is selected.

It is an advantage of the method according to the invention that it is not can only be applied to the finished detergent preparations, but if these preparations consist of several types of powder, from which only one powder type can be improved in its induction behavior must also target these partial powder quantities.

If intended, a compacted heavy powder, which before the treatment according to the invention with an unusable according to the invention Substance, for example zeolite Na-A, has been powdered in its To improve washability, this can also be done by a mixture of material not usable according to the invention with inventive usable treatment agent applies simultaneously and so saves one processing step. In a preferred embodiment The method according to the invention therefore becomes more washable improving washing-active preparation brought into contact with a mixture, the finely divided zeolite Na-A in detergent quality and an inventive suitable, especially solid treatment agent in proportions from 99: 1 to 25:75, preferably 95: 5 to 20:80 and in particular Contains 80:20 to 50:50. Are preferred in this context Mixtures of zeolite with pyrogenic silica and / or fatty acid calcium salts. This procedure can be used, for example WO 91/02047 known advantage of drying by the application of zeolite the washability improvement according to the invention without additional effort couple.

The method according to the invention shows particularly clear effects active detergent preparations in powder or granule form, which has a bulk density have between 700 and 1200 g per liter. After a special one Embodiment of the method according to the invention is therefore based on corresponding active detergent preparations with such a liter weight from 700 g / l to 1200 g / l, in particular 800 g / l to 1000 g / l. The emerging Products with improved induction behavior also show Bulk weights in the areas mentioned. However, as Another advantage of the invention is that in addition to improving the Induction behavior by the method according to the invention also an increase the bulk density of the detergent preparation can take place.

In the case of those suitable according to the invention as starting materials active detergent preparations can be by granulation processes, for example by wet granulation and subsequent drying, in particular Fluid bed drying, trade manufactured agents. However, it is possible also the use of spray-dried, possibly post-compacted Means. Of course, pressed washing-active preparations, produced by, for example, compacting or pelleting, be modified according to the invention.

A preferred starting product is, for example, spray drying and subsequent post-compression of the detergent pre-product, mixed with other non-spray-dry detergent ingredients results in a detergent. The manufacture of such, especially more suitable as starting products for the process according to the invention wash-active preparations with increased density is in the patent literature described.

A particularly preferred prefabricated wash-active preparation as a starting material for the method according to the invention is one according to the method product produced by international patent application WO 91/02047. It is a by extrusion of a homogeneous premix, optionally with the addition of a plasticizer can take place via hole shapes, which preferably have an opening width from 0.5 mm to 5 mm, then crushing the Extrudate by means of a cutting device and subsequent treatment in detergent or preliminary detergent product produced by a rounder, that also in admixture with other detergent components in the invention Procedure can be used.

Treatment with the liquid or solid, hydrophobic and / or water-insoluble In this case, the component is preferably carried out in the rounding device, than which a Spheronizer is preferably used.

Washing-active preparations are obtained by the process according to the invention in powder or granule form, which on their surface and in particular the externally accessible parts of its surface the hydrophobic and / or contain water-insoluble component.

An additional advantage of the invention is that the dissolution rate the preparation treated according to the invention is not significant changes, although their inductability is significantly improved.

Although practically any washing-active preparations in powder or granule form can be improved in their macroscopic dissolving or dispersing behavior by delaying the dissolving behavior of the individual grain and the method thus makes it possible to create improved cleaning agents, detergents or other surfactant-containing preparations, the invention relates to their preferred embodiment containing a granular solid detergent or cleaning agent 5 to 40% by weight Anionic surfactant, 1 to 20% by weight nonionic surfactant, 10 to 65% by weight Builder, up to 35% by weight, preferably 5% by weight to 15% by weight of alkali component, up to 15% by weight, preferably 3% by weight to 7% by weight of cobuilder, up to 40% by weight, preferably 10% by weight to 30% by weight of bleach, up to 15% by weight, preferably 1% by weight to 10% by weight of bleach activator, up to 20% by weight, preferably 2% by weight to 10% by weight alkali silicate, 0.1 to 10% by weight at least one substance from the group of foam inhibitors, foam boosters, fabric softeners, graying inhibitors, optical brighteners, dyes, adjusting agents, fillers, and 1 to 20% by weight Water, produced by the process according to the invention and containing on the grain surface the liquid or solid, hydrophobic and / or water-insoluble component in an amount of 1 part by weight to 25 to 1200, in particular 100 to 1000 parts by weight of the composition.

Solid agents modified according to the invention based on the following composition are particularly preferred: 5 to 35% by weight anionic surfactant from the group of alkylbenzenesulfonates, fatty alcohol sulfates, fatty alcohol ether sulfates, olefin sulfonates and / or fatty acid alkyl ester sulfates, 1 to 15% by weight nonionic surfactant from the group of alkyl polyethylene glycol ethers, nonylphenol polyethylene glycol ethers and / or alkyl polyglycosides, 20 to 50% by weight Zeolite NaA, up to 20% by weight, preferably 5% by weight to 15% by weight of alkali carbonate, up to 10% by weight, preferably 3% by weight to 7% by weight of polycarboxylic acid, 13 to 25% by weight Bleach, 1 to 10% by weight Bleach activator, up to 6% by weight, preferably 2% by weight to 5% by weight alkali silicate, 0.1 to 3.5% by weight Foam inhibitor and 1 to 3% by weight one or more substances from the group of textile softeners, graying inhibitors, enzymes, optical brighteners, dyes, fragrances, formulation aids or adjusting agents.

The method according to the invention can also be used successfully if if not the ready-formulated detergent, but only the surfactants containing portion is treated. So you can, for example, by Spray drying manufactured detergent precursors, so-called compounds, use as such or directly after a compression step. Such Pre-products usually contain all of the recipe components Detergents that are insensitive to heat. You are therefore free from, for example Bleaches or enzymes, but contain builders and die Proportions of surfactant.

Corresponding detergent precursors can, for example, up to 40 wt .-% Contain 85% by weight of anionic surfactant and 15% by weight to 60% by weight of alkali carbonate or, for example, from 20% by weight to 50% by weight of zeolite, 5% by weight to 15% by weight of layered silicate and / or alkali silicate and up to 35% by weight, in particular 15 wt .-% to 25 wt .-% nonionic surfactant.

In a further preferred embodiment of the method according to the invention are treated with high-surfactant detergent preparations. At These are products that meet the framework recipes listed mentioned ingredients can contain, at least 12% by weight, preferably at least 20% by weight and in particular 40% by weight up to 85% by weight of anionic surfactant is contained. In addition, non-ionic Surfactant be present, preferably in amounts of 1 wt .-% to 40 wt .-% and especially in amounts such that the weight ratio of anionic surfactant to nonionic surfactant is 10: 1 to 1: 3. Such high surfactant wash-active preparations are preferably with the treatment agent in mixing ratios (ratio of washing-active preparation to treatment agents) from 20: 1 to 1500: 1, in particular from 100: 1 to 1000: 1 treated.

Regarding the individual components of the above-mentioned washing active The following applies in particular to preparations:

Anionic surfactants are generally sulfonate or sulfate type surfactants. The surfactants containing sulfate groups include, in particular, alkyl sulfates and the corresponding sulfation products of alkoxylated, especially ethoxylated alcohols. Surfactants containing sulfonate groups are in particular alkylbenzenesulfonates, α-sulfofatty acid ester salts and α-sulfo fatty acid disalts. The anionic surfactants are usually in Form of their alkali salts, especially their sodium salts.

Addition products of 2 to 20 are preferred as nonionic surfactants 3 to 15 moles of ethylene oxide to 1 mole of a compound with essentially 10 to 20 carbon atoms from the group of alcohols and alkylphenols usable. The addition products from 7 are particularly important up to 15 moles of ethylene oxide to primary alcohols, such as coconut or tallow fatty alcohols, on oleyl alcohol, on oxo alcohols, or on secondary Alcohols with 8 to 18, preferably 12 to 18, carbon atoms, as well as mono- or dialkylphenols with 6 to 14 carbon atoms in the alkyl radicals. Besides these However, water-soluble nonionic surfactants are not either not completely water-soluble polyglycol ethers with 2 to 6 ethylene glycol ether residues of interest in the molecule, especially when they are together used with water-soluble nonionic or anionic surfactants will. Other suitable nonionic surfactants are alkyl glycosides or alkyl polyglycosides, the alkyl group of 8 to 18, preferably Has 10 to 16 carbon atoms.

In addition to alkali carbonates, builder substances are generally, in particular Understand sodium carbonate, synthetic zeolites and polycarboxylic acids. Fine-crystalline, synthetic water-containing zeolites are preferred of the type NaA, which have a calcium binding capacity (according to the information in the German patent DE 22 24 837) in the range from 100 to 200 mg CaO / g exhibit. Their particle size is usually in the range from 1 to 10 µm.

Suitable (co) polymeric polycarboxylic acids are polyacrylates, polymethacrylates and especially copolymers of acrylic acid with maleic acid, preferably those from 50% to 90% acrylic acid and 10% to 50% maleic acid. The molecular weight of the homopolymers is generally between 1000 and 100,000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on free acid. A particularly preferred one Acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000. The acids mentioned are usually in the form of their water-soluble Salts, especially the sodium salts, are used.

Suitable, albeit less preferred, compounds of this class are Copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ether, in which the proportion of acid is at least 50%. Polyacetal carboxylic acids, as described, for example, in US Pat U.S. Patents 4,144,226 and 4,146,495 and described by Polymerization of esters of glycolic acid, introduction of stable terminal End groups and saponification to the sodium or potassium salts can be obtained. Also suitable are polymeric acids which are obtained by polymerizing Acrolein and disproportionation of the polymer according to Canizzaro using strong Alkalis can be obtained. They are essentially made up of acrylic acid units and vinyl alcohol units or acrolein units.

Suitable alkali components are alkali silicates, in particular sodium silicates of the composition Na ₂ O: SiO ₂ = 1: 1 to 1: 3.5, preferably 1: 2 to 1: 3.35. Alkali carbonates and hydroxides, in particular the sodium compounds, are also suitable as alkali components.

The detergents according to the invention can contain phosphonic acids as cobuilders, for example aminoalkanephosphonic acids. As aminoalkanephosphonic acids come preferably ethylenediamine tetramethylene phosphonate (EDTMP), Diethylenetrimain pentamethylene phosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of neutral reactions Sodium salts, for example as the hexasodium salt from EDTMP or used as the hepta and octa sodium salt of DTPMP. Your share in the Agents, calculated on free acid, is preferably up to 1% by weight, in particular 0.1 to 0.5% by weight. Another suitable phosphonic acid is the 1-hydroxyethane-1,1-diphosphonic acid or the disodium salt or the Tetrasodium salt of this acid.

The detergents according to the invention furthermore preferably contain bleaches. Among the compounds used as bleaching agents in water, H ₂ O ₂ compounds, the sodium perborate tetrahydrate have (NaBO ₂ .H ₂ O ₂ • 3 H ₂ O) and the monohydrate (NaBO ₂ .H ₂ O ₂₎ are particularly important. However, other borates which produce H ₂ O _{2 can also} be used, for example the perborax Na ₂ B ₄ O ₇ .4H ₂ O ₂ . These compounds can be partially or completely replaced by other active oxygen carriers, in particular by peroxy hydrates, such as peroxycarbonates (Na ₂ CO ₃ .1.5 H ₂ O ₂ ), peroxypyrophosphates, citrate perhydrates, urea - H ₂ O ₂ - or melamine H ₂ O ₂ -Compounds and replaced by peracidic salts or peracids such as perbenzoates, peroxyphthalates, diperazelaic acid or diperdodecanedioic acid.

In order to achieve an improved bleaching effect when washing at temperatures below 80 ° C., in particular in the range from 40 to 60 ° C., bleach activators can be incorporated into the preparations. Examples of these are N-acyl or O-acyl compounds which form organic peracids with H ₂ O ₂ , preferably N, N'-tetraacylated diamines, such as N, N, N ', N'-tetraacetyl-ethylenediamine, and also carboxylic anhydrides, such as benzoic anhydride and phthalic anhydride and esters of polyols such as glucose pentaacetate.

The detergents can in particular be used as optical brighteners for cotton Derivatives of diaminostilbenedisulfonic acid or their alkali metal salts contain. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid or similarly constructed Compounds that have a diethanolamino group instead of the morpholino group, a methylamino group or a 2-methoxyethylamino group carry. Brighteners for polyamide fibers are those of the 1,3-diaryl-2-pyrazoline type in question, for example 1- (p-sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline. Brighteners of the substituted type can also be used 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl can be used. Mixtures of the aforementioned brighteners can also be used.

Enzymes come from the class of proteases, lipases, amylases, Cellulases and their mixture in question. Bacterial strains are particularly suitable or mushrooms such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus derived enzymatic agents. The enzymes can be adsorbed on carriers and / or embedded in coating substance to protect them against premature decomposition.

Suitable foam inhibitors are organopolysiloxanes and their mixtures with microfine, optionally silanized silica, paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica. Bis-acylamides derived from C _12-20 fatty acids and C _2-6 diamines or from C _12-20 alkyl amines and C _2-6 dicarboxylic acids can also be used. Mixtures of various foam additives are also advantageously used, for example those made from silicones and paraffins or waxes or from bis-acylamides and paraffins or waxes. The foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.

Layered silicates from the class are suitable as textile softening additives the bentonites and smectites, for example those according to DE 23 34 899 or EP 026 529. Synthetic, finely divided sheet silicates are also suitable with smectite-like crystal phase, as characterized in more detail in DE 35 26 405. The layered silicate content can be, for example, up to 5% by weight 20% by weight.

Examples Examples 1 to 4

As described in Examples 1 to 5 of WO 91/2047, a granular agent S1 with a bulk density of 813 g / l and the composition given below was produced. In contrast to the process there, strands with a diameter of 1.4 mm were extruded in the kneader-extruder / granulation, a continuously operated fluidized-bed dryer was used for drying the granules, and the final granulate was sieved using a sieve with a mesh size of 2 mm.

Composition of the active washing preparation S1 : 24% by weight surfactant (Mixture of 21% by weight anionic surfactant and 3% by weight nonionic surfactant), 21% by weight Zeolite Na-A, 18% by weight Sodium perborate monohydrate, 13% by weight Sodium, 6% by weight Polycarboxylate (Sokalan ^(R) CP 5, manufacturer BASF), 3% by weight Sodium silicate, Balance to 100 wt .-% water, optical brightener, defoamer, soap.

In a spheronizer (Spheronizer ^(R) RM 400, manufacturer Schlüter Fa., Neustadt) was submitted to S1 and 0.6 wt .-% calcium stearate (B1 treating agent), 0.4 wt .-% of amorphous silica (Aerosil ^(R) 200 , Manufacturer Degussa; treatment agent B2 ) or 0.3% by weight of hydrophobicized silica (Aerosil ^(R) R 972, manufacturer Degussa; treatment agent B3 ), each based on the amount of S1 , applied (mixing time 45 seconds). 0.3% by weight of melted paraffin (melting range 51-53 ° C., manufacturer Merck; treatment agent B4 ) was applied to the preparation S1 in a rotor granulator (GPC6-3, manufacturer Glatt, Binzen) via a nozzle head. Means M1 to M4 were thus obtained with the bulk weights (g / l) given in Table 1.

To determine the induction behavior, conditions were simulated that correspond to an induction device of a household washing machine operated under critical conditions. In each case 100 g of product were introduced into the test device (Zanussi induction channel). After a rest period of 1 minute, 10 liters of tap water were fed in within 80 seconds. The amount of the remaining residue (in grams) is given in Table 1 (column wash-in test). In addition, the dissolution rate was examined in a further test, the time being measured within which 90% by weight of the composition were in a stirred vessel (5 g of the composition to be examined in 500 g of water at 20 ° C., concentration measurement via conductivity) had solved. The values determined (in minutes: seconds) are also listed in Table 1. medium Bulk density Wash-in test Dissolution rate S1 813 16.3 2:57 M1 856 7.6 2:49 M2 778 1.0 3:02 M3 843 6.5 3:05 M4 740 0.1 3:03

It can be seen that the dissolution rates of the agents M1 to M4 modified according to the invention do not differ significantly from those of the untreated starting material S1 , but that the values for the flushability are very effectively improved by the treatment according to the invention.

Example 5

A wash-active preparation S2 of the same composition as mentioned above for S1, although the powdering with zeolite had been dispensed with in the production process according to WO 91/2047, with a bulk density of 783 g / l was mixed with 3 in a mixer (Atika mixer) % By weight of a mixture of zeolite Na-A and silica (Aerosil ^(R) 200; weight ratio 80:20; treatment agent B5 ), based on the amount of S2 , treated. The resulting agent M5 did not differ significantly in its dissolution behavior from the starting material S2 . For comparison, an agent V1 was prepared by treating S2 with 3% by weight of zeolite Na-A. To test the flushing behavior, a 5 ° inclined channel with a hemispherical cross-section, into which 40 g of the product to be tested had been added, was flowed through with water from a shower head (3 liters of cold tap water per minute). The amount of water required to completely rinse was measured if less than 1 minute (corresponding to 3 l) was required for this. Otherwise, the residue remaining after 1 minute was weighed out and the value reduced by 30% to take into account the amount of water absorbed. The value R of the induction resistance (in arbitrary units) was additionally determined from the amount of water required for induction (in 0.1 liters) and possibly the residue (in grams) determined. The larger this value R, the worse the flushing behavior of the sample examined. The values given in table 2 are mean values from 2 determinations in each case. Induction resistance medium Induction resistance R S2 24.5 V1 22.2 M5 4.0

It can be seen that the application of zeolite only improves the flushing behavior insignificantly ( V1 compared to S2 ), while the simultaneous treatment with pyrogenic silica dramatically improves the flushability ( M5 ).

Examples 6 and 7

The wash-active preparation S2 from Example 5 was in a rounding device (Spheronizer ^(R) RM 400, manufacturer Schlüter, Neustadt) as described in Examples 1 to 4 with 1.0 wt .-% calcium stearate (treatment agent B5 ) or 3 wt .-% of a mixture of calcium stearate and zeolite Na-A (weight ratio 1: 2; treatment agent B6 ), each based on the amount of S2 , treated (resulting agents M5 and M6 ). The dissolution rate was not significantly affected by this treatment. To check the washability improvement, 80 g each of the agents to be tested were placed in the wash-in chamber of household washing machines (machine I: Elektrolux ^(R) Eco 3; machine II: Miele Novotronic ^(R) W 717; machine III: source Privileg ^(R) 200) (wet chamber), flushed in at a water pressure of 0.5 bar (amount of water drawn in machine I: 12.7 l; in machine II: 13.1 l; in machine III: 11.7 l), then the remaining wet residue balanced and deducted 30% each as water contained in this. The residue values given in Table 3 (in grams) resulted as the mean values from 10 measurements with the associated fluctuation ranges as bracketed values. medium Bulk density [g / l] Residue in machine I. II III S2 783 10.7 (1.4) 22.9 (3.6) 14.5 (3.3) M5 746 1.0 (0.2) 0 (-) 0.7 (0.1) M6 756 1.7 (0.3) 0 (-) 1.0 (0.3)

Claims (13)

1. A process for the production of a powder-form or granular washing-active formulation with high bulk density and improved dispensing behaviour, characterized in that a prepared washing-active powder or granules with a bulk density above 500 g/l is/are contacted while mixing with a liquid or solid, hydrophobic and/or water-insoluble component which is not a zeolite, the ratio by weight of prepared powder to liquid or solid, hydrophobic and/or water-insoluble treatment agent being adjusted to between 20:1 and 2000:1 and the treatment agent being selected from the group consisting of inert siloxanes, fatty acid salts, alcohols containing 10 to 22 carbon atoms, which may even be sulfated, silicas, inorganic anionic layer compounds, inorganic cationic layer compounds and mixtures thereof.
2. A process as claimed in claim 1, characterized in that hydrophobicized silica, hydrophobicized layer silicate, hydrophobicized hydrotalcite or a mixture thereof is used as the treatment agent.
3. A process as claimed in claim 1 or 2, characterized in that the ratio by weight of prepared powder to treatment agent is between 25:1 and 1000:1 and more particularly between 100:1 and 500:1.
4. A process as claimed in any of claims 1 to 3, characterized in that the treatment agent, more particularly in solid form, is used in admixture with fine-particle zeolite NaA, the ratio by weight of zeolite to treatment agent being 99:1 to 25:75 and more particularly 95:5 to 20:80.
5. A process as claimed in any of claims 1 to 4, characterized in that a detergent with a bulk density of 700 g/l to 1200 g/l and more particularly 800 g/l to 1000 g/l is used as the prepared washing-active powder or granules.
6. A process as claimed in any of claims 1 to 5, characterized in that a detergent compound produced by spray drying and optionally post-compaction or a mixture thereof with other detergent ingredients, more particularly non-spray-dryable detergent ingredients, is used as the prepared washing-active formulation.
7. A process as claimed in any of claims 1 to 6, characterized in that a detergent or detergent compound produced by extrusion of a homogeneous compound, optionally in the presence of a plasticizer, through multiple-bore dies preferably having a bore diameter of 0.5 mm to 5 mm to form strands, size reduction of the extrudate by a cutting unit and subsequent treatment in a rounding unit, or a mixture thereof with other detergent ingredients, is used as the prepared washing-active formulation.
8. A process as claimed in claim 7, characterized in that the treatment with the liquid or solid hydrophobic and/or water-insoluble component is carried out in the rounding unit which is preferably a spheronizer.
9. A process as claimed in any of claims 1 to 8, characterized in that the ratio by weight of surfactant in the washing-active formulation to treatment agent is 10:1 to 200:1 and more particularly 30:1 to 120:1.
10. A granular solid detergent containing 5 to 40% by weight of anionic surfactant, 1 to 20% by weight of nonionic surfactant, 10 to 65% by weight of builder, up to 35% by weight and preferably 5% by weight to 15% by weight of an alkali component, up to 15% by weight and preferably 3% by weight to 7% by weight of cobuilder, up to 40% by weight and preferably 10% by weight to 30% by weight of bleaching agent, up to 15% by weight and preferably 1% by weight to 10% by weight of bleach activator, up to 20% by weight and preferably 2% by weight to 10% by weight of alkali metal silicate, 0.1 to 10% by weight of at least one substance from the group of foam inhibitors, foam boosters, fabric softeners, redeposition inhibitors, optical brighteners, dyes, fillers and 1 to 20% by weight of water, produced by the process claimed in any of claims 1 to 9, characterized in that it contains the liquid or solid, hydrophobic and/or water-insoluble component on the particle surface in a quantity of 1 part by weight to 25 to 1,200 and more particularly 100 to 1,000 parts by weight of granulated detergent.
11. A detergent as claimed in claim 10, characterized in that it contains 5 to 35% by weight of anionic surfactant selected from the group of alkyl benzenesulfonates, fatty alcohol sulfates, fatty alcohol ether sulfates, olefin sulfonates and/or fatty acid alkyl ester sulfates, 1 to15%byweight of nonionic surfactant from the group of alkyl polyethylene glycol ethers, nonylphenol polyethylene glycol ethers and/or alkyl polyglycosides, 20 to 50% by weight of zeolite NaA. up to 20% by weight and preferably 5% by weight to 15% by weight of alkali metal carbonate, up to 10% by weight and preferably 3% by weight to 7% by weight of polycarboxylic acid, 13 to 25% by weight of bleaching agent, 1 to 10% by weight of bleach activator, up to 6% by weight and preferably 2% by weight to 5% by weight of alkali metal silicate, 0.1 to 3.5% by weight of foam inhibitor and 1 to 3% by weight of one or more substances from the group of fabric softeners, redeposition inhibitors, enzymes, optical brighteners, dyes, fragrances, formulation aids or fillers.
12. A washing-active formulation containing at least 12% by weight and preferably at least 20% by weight and more particularly 40% by weight to 85% by weight of anionic surfactant and optionally nonionic surfactant in a quantity of 1% by weight to 40% by weight and more particularly in such quantities that the ratio by weight of anionic surfactant to nonionic surfactant is 10:1 to 1:3, produced by the process claimed in any of claims 1 to 9, characterized in that it contains the liquid or solid, hydrophobic and/or water-insoluble component on the particle surface in a quantity of 1 part by weight to 100 to 1,000 parts by weight of detergent compound.
13. A formulation as claimed in any of claims 10 to 12, characterized in that it has a bulk density of 700 g/l to 1,200 g/l and more particularly in the range from 800 g/l to 1,000 g/l.