EP1234870A2 - Solid detergent additives, their preparation and use - Google Patents

Abstract

Providing a detergent additive comprises a core of an antifoaming agent and a shell of an anionic surfactant. Detergent additive comprises a core of an antifoaming agent and a shell of an anionic surfactant or a mixture containing an alkali salt of a 1-22C carboxylic acid and/or a nonionic or zwitterionic surfactant(s).

Description

The invention relates to the field of detergents, in particular new coated ones Defoamer compositions for use in high-foaming detergents high anionic surfactant content.

State of the art

A typical feature of anionic surfactants is to develop foam. In many This is used in hand dishwashing detergents or hair shampoos, for example Effect expressly desired by the consumer and equated with performance.

In the area of household and industrial detergents, however, there is foam development largely undesirable, as too much foam development quickly becomes one Foaming the machine can result. Since on anionic surfactants as a component of However, because of their special performance profile, recipes are usually not dispensed with detergent formulations are often provided with defoamers.

Such defoamers are said to reduce the amount of foam generated during the washing process Limit acceptable levels without, however, detergent performance reduce or increase the price. From the prior art are one for this purpose Many known compounds, of which only the soaps at this point Paraffins and the silicones should be called.

So far, suitable defoamers have been produced either by drying the corresponding aqueous emulsions or dispersions or by direct spraying the defoamer component on a support. Known processes such as Fluid bed drying or fluid bed granulation, spray mixing process and conventional countercurrent drying used in the spray tower. In this process, in general also additives, such as sodium sulfate or zeolite as a carrier incorporated. Particular attention has been paid to this in the recent past directed the production of granules. Auxiliaries and defoamer components are with this approach - viewed macroscopically - in such granules in distributed substantially homogeneously, although it turns out under the microscope that a such granules can also have heterogeneous areas, for example zones in where the defoamer is concentrated. This has a problematic effect Compositions, however, from that they are not optimally incorporated into granules or Have the tablet form processed.

The previously known defoamers contain problems Detergents also feature that the defoamers themselves within the detergent migrate and bake if stored for long periods or when stored under pressure of the compositions can lead. In addition, it has been shown that the The effectiveness of defoamers usually increases with the storage time of Compositions containing defoamers based on those described above Phenomena subsides.

Attempts have also been made on the prior art to Detack surface-sticky granules by dusting them with inorganic salts. The problem with such methods is that the abrasion resistance such pollinated granules leaves something to be desired.

Another problem found in many defoamer formulations is evident then, such defoamer formulations in detergent preparations in Tablet form should be incorporated. Through the in the manufacture of the tablets applied high pressures, the defoamers are often distributed in the tablet in such a way that the effectiveness of the defoamers decreases significantly. However, this either leads to high-foaming formulations, which are undesirable for various reasons, or the amount of defoamer must be increased accordingly.

Conventional defoamers had to be improved in their effect, especially when it comes to detergents, preferably those in Tablet form, also effective to defoam if it contains a high proportion contain particularly high-foaming anionic surfactants.

The object of the invention was therefore to solve the problems mentioned above remedy.

The object on which the invention is based is achieved by detergent additives, as described in the text below.

description the invention

The invention relates to detergent additives in solid form feature that they consist of a defoaming compound as the core and one of them enveloping layer, wherein the enveloping layer at least one anionic Surfactant or, if at least one anionic surfactant, an alkali salt of an organic Carboxylic acid containing 1 to 22 carbon atoms is contained, a mixture of two or more anionic surfactants, or at least one nonionic surfactant or at least one contains zwitterionic surfactant.

Surprisingly, it was found that the inventive Detergent additives, which are coated defoamers, in Contrary to non-coated comparative products from the retail trade even in the Are capable of foaming detergents throughout the duration of the To regulate the washing process reliably when the detergent has a particularly high level Share of anionic surfactants or anionic surfactants with a particularly pronounced Foaming power included. It is not distracting if part of the coating due to the manufacturing process it gets into the defoamer grain. The coating of the Defoamer grain also does not have to be complete, it is sufficient if the Wrapping ensures that the migration of water and surfactants, in particular non-ionic surfactants, in the grain and thus the deactivation of the defoamer is prevented.

defoamers

The detergent additives according to the invention contain the defoaming agents Compounds - based on the total active substance and, if appropriate, carrier - preferably in total amounts from 75 to 99% by weight, preferably from 80 to 95 and in particular from 85 to 90% by weight. The defoamers can be waxy Act connections and / or silicone connections. An embodiment of the According to the present invention, only defoamer are used as defoamers Defoamer compounds included. Such connections are called "waxy" understood that have a melting point at atmospheric pressure above 25 ° C (room temperature), preferably have above 50 ° C and in particular above 70 ° C. The possibly Wax-like defoamer substances contained according to the invention are in water practically insoluble, i.e. at 20 ° C they have a solubility of less than 0.1 in 100 g of water % By weight. In principle, all wax-like known from the prior art Defoamer substances are included. Suitable waxy compounds are for example bisamides, fatty alcohols, fatty acids, carboxylic acid esters of one and polyhydric alcohols and paraffin waxes or mixtures thereof. alternative can of course also use the silicone compounds known for this purpose become.

Suitable paraffin waxes generally represent 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 paraffin 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., cannot be used according to the invention. For example, the paraffin wax mixtures known from EP 0309931 A1 of, for example, 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% by weight hard paraffin can be used with a solidification point of 42 ° C to 56 ° C and 2 wt .-% to 25 wt .-% soft paraffin with a solidification point of 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.

In the case of the paraffin waxes which can be used according to the invention, this liquid fraction is so as low as possible and preferably completely absent. So point particularly preferred Paraffin wax mixtures at 30 ° C, a liquid content of less than 10 wt .-%, in particular from 2% by weight to 5% by weight, at 40 ° C a liquid fraction of less than 30% by weight, preferably from 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 fraction of 80% by weight to 100% by weight, and a liquid content of 100% by weight at 90 ° C. The temperature at which a Liquid content of 100% by weight of the paraffin wax is achieved is particularly preferred Paraffin wax mixtures still below 85 ° C, especially at 75 ° C to 82 ° C. Both Paraffin waxes can be petrolatum, microcrystalline waxes or hydrogenated or act partially hydrogenated paraffin waxes.

Suitable bisamides as defoamers are those that differ from saturated fatty acids 12 to 22, preferably 14 to 18 carbon atoms and alkylene diamines with 2 to 7 carbon atoms derived. Suitable fatty acids are lauric, myristic, stearic, arachine and Beenic acid and its mixtures, such as those from natural fats respectively hardened oils such as tallow or hydrogenated palm oil are available. Suitable diamines are, for example, ethylenediamine, 1,3-propylenediamine, tetramethylenediamine, Pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluyiendiamine. Preferred diamines are ethylenediamine and hexamethylenediamine. Particularly preferred Bisamides are bismyristoyiethylenediamine, bispalmitoyiethylenediamine, Bisstearoyiethylenediamine and their mixtures and the corresponding derivatives of Hexamethylenediamine.

Suitable carboxylic acid esters as defoamers are derived from carboxylic acids with 12 to 28 carbon atoms. In particular, these are esters of behenic acid, stearic acid, hydroxystearic acid, oleic acid, palmitic acid, myristic acid and / or lauric acid. The alcohol part of the carboxylic acid ester contains a mono- or polyhydric alcohol with 1 to 28 carbon atoms in the hydrocarbon chain. Examples of suitable alcohols are behenyl alcohol, arachidyl alcohol, coconut alcohol, 12-hydroxystearyl alcohol, oleyl alcohol and lauryl alcohol as well as ethylene glycol, glycerin, polyvinyl alcohol, sucrose, erythritol, pentaerythritol, sorbitan and / or sorbitol. Preferred esters are those of ethylene glycol, glycerol and sorbitan, the acid part of the ester being selected in particular from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid. Eligible esters of polyhydric alcohols are, for example, xylitol monopalmitate, pentarythritol monostearate, glycerol monostearate, ethylene glycol monostearate and sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan dilaurate, sorbitan dististearate, sorbitan dandghenoate and mixed sorbitan dibehenate, and sorbitan dandebehenate, and sorbitan dandebehenate as well as mixed sorbitan dandebehenate and sorbitan dandebiolate. Glycerol esters which can be used are the mono-, di- or triesters of glycerol and the carboxylic acids mentioned, the mono- or diesters being preferred. Glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobehenate and glycerol distearate are examples of this. Examples of suitable natural esters as defoamers are beeswax, which mainly consists of the esters CH ₃ (CH ₂ ) ₂₄ COO (CH ₂ ) ₂₇ CH ₃ and CH ₃ (CH ₂ ) ₂₆ COO (CH ₂ ) ₂₅ CH ₃ , and carnauba wax , which is a mixture of carnauba acid alkyl esters, often in combination with small amounts of free carnauba acid, other long-chain acids, high-molecular alcohols and hydrocarbons.

Suitable carboxylic acids as a further defoamer compound are, in particular, behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid and lauric acid and mixtures thereof, as can be obtained from natural fats or optionally hardened oils, such as tallow or hydrogenated palm oil. Saturated fatty acids with 12 to 22, in particular 18 to 22, carbon atoms are preferred.

Suitable fatty alcohols as a further defoamer compound are the hydrogenated products of the fatty acids described. Dialkyl ethers may also be present as defoamers. The ethers can be constructed asymmetrically or symmetrically, ie contain two identical or different alkyl chains, preferably with 8 to 18 carbon atoms. Typical examples are di-n-octyl ether, di-isooctyl ether and di-n-stearyl ether; dialkyl ethers which have a melting point above 25 ° C., in particular above 40 ° C., are particularly suitable.

Other suitable defoamer compounds are fatty ketones of the formula ( I ), R ¹ -CO-R ² in which R ¹ and R ² independently of one another represent linear or branched hydrocarbon radicals having 11 to 25 carbon atoms and 0 or 1 double bond. Such ketones are known substances that can be obtained by the relevant methods of preparative organic chemistry. For their preparation, one starts, for example, from carboxylic acid magnesium salts which are pyrolyzed at temperatures above 300 ° C. with the elimination of carbon dioxide and water, for example according to the German laid-open specification DE 2553900 OS . Suitable fat ketones are those which are prepared by pyrolysis of the magnesium salts of lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, petroselinic acid, arachic acid, gadoleic acid, behenic acid or erucic acid. Hentriacontanon-16; (R ¹ and R ² stands for an alkyl radical with 15 carbon atoms), tritriacontanone-17 (R ¹ and R ² stands for an alkyl radical with 16 carbon atoms), stearone (pentatriacontanone-18; R ¹ and R ² stands for an alkyl radical with 17 Carbon atoms), heptatriacontanone-19 (R ¹ and R ² stands for an alkyl radical with 18 carbon atoms), arachinone (nonatriacontanone-20; R ¹ and R ² stands for an alkyl radical with 19 carbon atoms), hentetracontanone-21 (R ¹ and R ² stands for an alkyl radical with 20 carbon atoms) and / or Behenon (triatetracontanone-22: R ¹ and R ² stands for an alkyl radical with 21 carbon atoms).

Other suitable defoamers are fatty acid polyethylene glycol esters of the formula ( II ), R ³ COO (CH ₂ CH ₂ 0) _n H in which R ³ CO is a linear or branched, aliphatic, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms and n is a number from 0.5 to 1.5. Such fatty acid polyethylene glycol esters are preferably obtained by base-homogeneously catalyzed addition of ethylene oxide to fatty acids, in particular addition of ethylene oxide to the fatty acids is carried out in the presence of alkanolamines as catalysts. The use of alkanolamines, especially triethanolamine, leads to an extremely selective ethoxylation of the fatty acids, especially when it comes to producing low-ethoxylated compounds. For the purposes of the present invention, preference is given to fatty acid polyethylene glycol esters of the formula (II) in which R ³ CO is a linear acyl radical having 12 to 18 carbon atoms and n is the number 1. Lauric acid ethoxylated with 1 mol of ethylene oxide is particularly suitable. Within the group of fatty acid polyethylene glycol esters, preference is given to those which have a melting point above 25 ° C., in particular above 40 ° C.

Within the group of wax-like defoamers, the paraffin waxes described are particularly preferably used alone as wax-like defoamers or in a mixture with one of the other wax-like defoamers, the proportion of paraffin waxes in the mixture preferably making up more than 50% by weight, based on the wax-like defoamer mixture. The paraffin waxes can be applied to carriers if necessary. All known inorganic and / or organic carrier materials are suitable as carrier materials. Examples of typical inorganic carrier materials are alkali carbonates, aluminosilicates, water-soluble sheet silicates, alkali silicates, alkali sulfates, for example sodium sulfate, and alkali phosphates. The alkali silicates are preferably a compound with a molar ratio of alkali oxide to SiO ₂ of 1: 1.5 to 1: 3.5. The use of such silicates results in particularly good grain properties, in particular high abrasion stability and nevertheless high dissolution rate in water. The aluminosilicates referred to as carrier material include, in particular, the zeolites, for example zeolite NaA and NaX.

The compounds referred to as water-soluble layered silicates include for example amorphous or crystalline water glass. Silicates can also be used Find those which are commercially available under the name Aerosil® or Sipemat® are. For example, film-forming polymers, for example polyvinyl alcohols, polyvinyl pyrrolidones, poly (meth) acrylates, Polycarboxylates, cellulose derivatives and starch in question. Useful cellulose ethers are in particular alkali carboxymethyl cellulose, methyl cellulose, ethyl cellulose, Hydroxyethyl cellulose and so-called mixed cellulose ethers, such as Methylhydroxyethylcellulose and methylhydroxypropylcellulose, as well as their Mixtures. Particularly suitable mixtures are made of sodium carboxymethyl cellulose and methyl cellulose, the carboxymethyl cellulose usually a degree of substitution of 0.5 to 0.8 carboxymethyl groups per anhydroglucose unit and the methyl cellulose has a degree of substitution of 1.2 to 2 methyl groups per Has anhydroglucose unit.

The mixtures preferably contain alkali carboxymethyl cellulose and nonionic Cellulose ethers in weight ratios from 80:20 to 40:60, in particular from 75:25 to 50:50.

Also suitable as a carrier is native starch, which is composed of amylose and amylopectin is. Starch is called native starch as it is extracted from natural sources is accessible, for example from rice, potatoes, corn and wheat. Native strength is one commercially available product and therefore easily accessible. Can be used as carrier materials one or more of the compounds mentioned above are used, especially selected from the group of alkali carbonates, alkali sulfates, Alkali phosphates, zeolites, water-soluble sheet silicates, alkali silicates, polycarboxylates, Cellulose ether, polyacrylate / polymethacrylate and starch. Are particularly suitable Mixtures of alkali carbonates, especially sodium carbonate, alkali silicates, especially sodium silicate, alkali sulfates, especially sodium sulfate and zeolites.

wobei R⁴ unabhängig voneinander für einen Alkyl- oder einen Arylrest und z für Zahlen im Bereich von 40 bis 1500 stehen kann. Beispiele für geeignete Substituenten R⁴ sind Methyl, Ethyl, Propyl, Isobutyl, tert.-Butyl und Phenyl. Es können aber auch über Siloxan vernetzte Verbindungen eingesetzt werden, wie sie dem Fachmann unter der Bezeichnung Silikonharze bekannt sind. In der Regel enthalten die Polydiorganosiloxane feinteilige Kieselsäure, die auch silaniert sein kann. Insbesondere geeignet sind kieselsäurehaltige Dimethylpolysiloxane. Vorteilhafterweise haben die Polydiorganosiloxane eine Viskosität nach Brookfield bei 25 °C im Bereich von 5 000 mPas bis 30 000 mPas, insbesondere von 15.000 bis 25.000 mPas. Die Silikone sind vorzugsweise auf Trägermaterialien aufgebracht. Geeignete Trägermaterialien sind bereits im Zusammenhang mit den Paraffinen beschrieben worden. Die Trägermaterialien sind in der Regel in Mengen von 40 bis 90 Gew.-%, vorzugsweise in Mengen von 45 bis 75 Gew.-% - bezogen auf Entschäumer - enthalten.According to a further embodiment of the present invention, a mixture of at least one wax-like defoamer, preferably a paraffin wax, and a defoaming silicone compound is used as the defoamer. For the purposes of the present invention, suitable silicones are conventional organopolysiloxanes which can have a content of finely divided silica, which in turn can also be silanated. Such organopolysiloxanes are described, for example, in European patent application EP 0496510 A1 . Polydiorganosiloxanes which are known from the prior art are particularly preferred. Suitable polydiorganosiloxanes can have an almost linear chain and are identified by the following formula (III),

where R ^{4 can} independently represent an alkyl or an aryl radical and z can stand for numbers in the range from 40 to 1500. Examples of suitable substituents R ⁴ are methyl, ethyl, propyl, isobutyl, tert-butyl and phenyl. However, compounds crosslinked via siloxane can also be used, as are known to the person skilled in the art under the name silicone resins. As a rule, the polydiorganosiloxanes contain finely divided silica, which can also be silanized. Silica-containing dimethylpolysiloxanes are particularly suitable. The polydiorganosiloxanes advantageously have a Brookfield viscosity at 25 ° C. in the range from 5,000 mPas to 30,000 mPas, in particular from 15,000 to 25,000 mPas. The silicones are preferably applied to carrier materials. Suitable carrier materials have already been described in connection with the paraffins. The carrier materials are generally present in amounts of 40 to 90% by weight, preferably in amounts of 45 to 75% by weight, based on defoamers.

In the context of a further preferred embodiment of the present invention contain the detergent additives according to the invention as a defoaming compound a waxy compound and / or a silicone compound, or at least one paraffin-based waxy compound or at least one waxy compound optionally based on hydrogenated or partially hydrogenated paraffins waxy compound from the group of ketones or dialkyl ethers or at least a wax-like compound based on amide waxes or at least one waxy compound based on bisstearylethylene amide.

In the context of a further preferred embodiment of the present invention contain the detergent additives according to the invention as a defoaming compound at least one wax-like compound and a defoaming silicone compound.

(a) mindestens ein Weichwachs mit einem Schmelzpunkt im Bereich von 35 bis 50 °C,

(b) mindestens ein Hartwachs mit einem Schmelzpunkt oberhalb von 50 °C,

(c) gegebenenfalls Silicon und

(d) Trägermaterialien (Soda, Natriumsulfat, Zeolith, Silikat, Stärke, Cellulose etc.).

In a further preferred embodiment of the present invention, the detergent additives according to the invention contain as a defoaming compound

(a) at least one soft wax with a melting point in the range from 35 to 50 ° C,

(b) at least one hard wax with a melting point above 50 ° C,

(c) optionally silicone and

(d) carrier materials (soda, sodium sulfate, zeolite, silicate, starch, cellulose etc.).

(e) 5 bis 25 Gew.-% mindestens einem Weichwachs mit einem Schmelzpunkt im Bereich von 35 bis 50 °C,

(f) 1 bis 10 Gew.-% mindestens einem Hartwachs mit einem Schmelzpunkt oberhalb von 50 °C,

(g) 1 bis 10 Gew.-% mindestens einem Amidwachs mit einem Schmelzpunkt oberhalb von 100 °C,

(h) 0 bis 10 Gew.-% Siliconen und

(i) ad 100 Gew.-% Trägermaterialien (Soda, Na-sulfat, Zeolith, Silikat, Stärke, Cellulose etc.).

In a further preferred embodiment of the present invention, the detergent additives according to the invention contain as a defoaming compound

(e) 5 to 25% by weight of at least one soft wax with a melting point in the range from 35 to 50 ° C,

(f) 1 to 10% by weight of at least one hard wax with a melting point above 50 ° C,

(g) 1 to 10% by weight of at least one amide wax with a melting point above 100 ° C.,

(h) 0 to 10% by weight of silicones and

(i) ad 100% by weight of carrier materials (soda, sodium sulfate, zeolite, silicate, starch, cellulose etc.).

In a further preferred embodiment of the present invention, the detergent additives according to the invention contain petrolates or their hydrogenation products in the defoamer component as soft wax. The preferred soft waxes are paraffin mixtures in the C chain range from C ₂₀ to C ₆₀ , with about 80% in the C chain range from C ₂₅ to C ₅₀ . The preferred paraffin mixture contains linear as well as branched paraffins in a ratio of approximately 40:60. The paraffin mixture can also contain hydrogenated paraffins.

In the context of a further preferred embodiment of the present invention, the detergent additives according to the invention contain microcrystalline waxes in the defoamer component as hard wax, which are in the C chain range from C ₂₅ to C ₅₀ and have a softening point of> 50 ° C.

coating substances

In the context of a preferred embodiment of the present invention, as Coating substances surfactants, selected from the group consisting of olefin sulfonates, Ester sulfonates, sulfates based on linear (fatty alcohols and Ziegler alcohols) or branched alcohols (oxo alcohols), alkane sulfonates, fatty acid monoglyceride sulfates, Betaines, alkyl polyglycosides, isethionates, sarcosides, taurates, Fatty alcohol ethoxylates with up to 40 EO units, fatty acid ester ethoxylates with 1 to 5 EO units, polyethylene glycols with a molecular weight of more than about 2000, Fatty acid ethylene glycol esters, acyl lactylates, alkyl oligoglucoside sulfates, protein fatty acid condensates, (especially herbal products based on soy) and alkyl (ether) phosphates used.

The above-mentioned compounds which can be used as coating substances can be used in Within the scope of the present invention individually or as a mixture of two or more Substances from one or more of the substance classes mentioned are used become. In the context of a preferred embodiment of the present invention Compounds are used as coating substances that have a crystalline or have an amorphous structure. Preferably, the shell contains the invention Detergent additives surfactants that work at room temperature or in a range of up to have a non-sticky surface at about 60 ° C or about 50 ° C.

The shell of a detergent additive according to the invention can also contain surfactants have a pasty or sticky in the temperature range mentioned above Have consistency. The proportion of such surfactants in the entire shell must be however, be dimensioned such that the shell of the detergent additives according to the invention overall is not pasty or sticky.

The shell of a detergent additive according to the invention can consist of a layer or be made up of several layers. If the shell is made up of a layer, so should be chosen so that the above requirements in With regard to the stickiness of the outer shell are met. However, if, for example the shell of a detergent additive according to the invention has a stickiness which does not lead to the goal with regard to the present invention, for example such a layer another layer can be applied, which the Regulates the consistency of the casing in such a way that the requirements according to the invention are met are. With regard to the composition of the individual layers of such, from multiple layers existing shell, it is only necessary that the Total composition of the layers forming the shell of the above Requirements for the ingredients of the cover are sufficient.

A detergent additive according to the invention is used in the context of the present Invention then referred to as non-sticky when it is at a temperature of at least about 20 ° C to about 40 ° C in a commercially available big bag after a storage time of 1 Week remains essentially free-flowing, which means that the big bag without Clumps can be emptied.

Within the scope of a first embodiment of the present invention, the Detergent additives according to the invention as coating substance at least one anionic Surfactant or, if as at least one anionic surfactant, an alkali salt organic carboxylic acid with 1 to 22 carbon atoms is contained, a mixture of two or more anionic surfactants.

In principle, all of them are anionic surfactants in the context of the present invention suitable for anionic surfactants. In a preferred embodiment of the In the present invention, at least one anionic is used as the coating substance Surfactant from the group of sulfates or sulfonates.

Suitable surfactants of the sulfonate type are preferably C _8-18 alkylbenzenesulfonates, in particular C _12-16 olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained, for example, from C _8-18 monoolefins with end or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of 2-sulfofatty acids (ester sulfonates), for example the 2-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Among fatty acid glycerol esters are the mono-, di- and triesters and their mixtures to understand how they in the preparation by esterification of a monoglycerol with 1 to 3 moles Obtained fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated Fatty acids with 6 to 22 carbon atoms, for example caproic acid, Caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or Behenic acid.

The alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₈ -C ₁₈ fatty alcohols, for example C ₁₂ -C ₁₆ fatty alcohols, for example made from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. In the context of the present invention, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₄ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C _12-18 - Fatty alcohols with 1 to 4 EO are suitable.

Other anionic surfactants suitable in the context of the present invention are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

If the detergent additives according to the invention are a salt of a coating substance contain organic carboxylic acid with 1 to 12 carbon atoms, the coating substance still has at least one other anionic surfactant that is not an organic salt Is carboxylic acid with 1 to 12 carbon atoms. In a preferred embodiment In the present invention, the proportion of salts of organic carboxylic acids is 1 up to 12 carbon atoms in the coating substance of the detergent additives according to the invention less than about 50% by weight, especially less than about 30% by weight. If the Detergent additives according to the invention as a coating substance, a salt of an organic Contain carboxylic acid with 1 to 12 carbon atoms, is preferably in the coating substance at least one further anionic surfactant, which contains at least one sulfate or Has sulfonate group.

Within the scope of a further embodiment of the present invention, a Detergent additive according to the invention as a coating substance is a nonionic surfactant contain.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 100 moles of ethylene oxide (EO) per mole of alcohol in which the Alcohol residue may be linear or preferably methyl branched in the 2-position or linear and may contain methyl-branched radicals in the mixture, as is usually the case in Oxo alcohol residues are present.

If such nonionic surfactants are used in the context of the present invention the amount of such surfactants used is particularly dependent on their consistency dependent. If, for example, alkoxylated alcohols are used, the liquid or pasty consistency, the amount used is measured so that the above requirements for the shell of the invention Detergent additives are met with regard to the stickiness of the casing. The proportion of such nonionic surfactants in the shell is preferably total less than about 50% by weight, for example less than about 20% by weight or less than about 10% by weight. If alkoxylated alcohols are used as nonionic surfactants whose consistency is amorphous or crystalline, their share of the shell can of a detergent additive according to the invention are above the latter values, for example up to about 100% by weight.

Another class of preferred nonionic surfactants, such as those used in the present invention either as the sole nonionic surfactant or in combination used with other non-ionic surfactants are alkoxylated, preferred ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 up to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters as they are described, for example, in Japanese patent application JP 58/217598 or preferably according to that in international patent application WO-A-90/13533 described methods are produced.

Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). Alkyl polyglycosides which can be used satisfy the general formula RO (G) _z , in which R represents a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, and G is the Is symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.

Linear alkyl polyglucosides, ie alkyl polyglycosides, are preferably used where the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.

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

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Other suitable surfactants are polyhydroxy fatty acid amides of the formula (IV),

in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula (V)

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this rest.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be converted, for example according to the teaching of international application WO-A-95/07331, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst into the desired polyhydroxy fatty acid amides.

Depending on the desired application of the invention Detergent additives can change the weight ratio of shell to core in a wide range Range vary. For example, ratios of shell to core are suitable 10: 1 to about 1: 100 or about 5: 1 to about 1:50. As part of a preferred Embodiment of the present invention should the weight percentage of the shell on total detergent additive about 1 to about 30 wt .-%, for example about 2 to about 20 or about 5 to about 10 wt .-%.

The coating substances are preferably water-soluble compounds, which further preferably has a water solubility at 20 ° C. of at least 1 g / l, preferably have at least 10 g / l and in particular at least about 100 g / l

In the context of a further embodiment of the present invention, the casing of a detergent additive according to the invention in addition to one or more of the above-mentioned compounds still another shell substance or a mixture of two or contain more coating substances.

These further coating substances are preferably water-soluble Compounds which more preferably have a water solubility of at least 20 ° C. 1 g / l, preferably at least 50 g / l and in particular at least 100 g / l and advantageously other properties useful for the overall formulation have, for example, the complexation of hardness and heavy metal ions. Alternatively, meltable ones are generally used instead of water-soluble ones Connections in question.

The other coating substances are used in a preferred embodiment especially then as part of the shell of an inventive Detergent additive used if the hardness, abrasion resistance or water solubility the case should be set to a certain value and this value cannot be achieved with the above-mentioned coating substances.

In a first embodiment of the invention, these substances can be the salts of inorganic mineral acids . Typical examples are the alkali and / or alkaline earth metal salts, aluminum or zinc salts of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid and silicic acid, in particular the alkali metal sulfate, alkali borates and perborates, the various alkali metal silicates (“water glasses”) and alkali metal phosphates to be mentioned. Typical examples are magnesium sulfate heptahydrate or borax.

The salts of organic carboxylic acids are also suitable. Typical examples are the alkali and / or alkaline earth metal salts, aluminum or zinc salts of monocarboxylic acids having 1 to 22 carbon atoms, for example formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, 2-ethylhexanoic acid. The use of sodium acetate is particularly preferred.

Instead of the monocarboxylic acids, corresponding C ₂ -C ₆ dicarboxylic acids can also be used, so that the corresponding salts of succinic acid, maleic acid, fumaric acid, glutaric acid and adipic acid can be used as suitable additional coating substances in the same way as above.

Finally, salts of hydroxy-functionalized polyvalent carboxylic acids can also be used are used, e.g. the above salts of malic acid, tartaric acid and especially citric acid. The use of alkali citrates is particularly important here prefers.

The third group of suitable further coating substances are the water-soluble polymers , which can be, for example, protein hydrolyzates, polyamides, polycarboxylates and polyurethanes. Urea and polyurea are also suitable. Saccharides and polysaccharides, such as sucrose, maltose or starch hydrolysates, are also suitable. The polycarboxylates, for example copolymers of acrylate / methacrylate, copolymers of acrylate / maleinate (for example Sokalan CP 5, manufacturer: BASF), or polyaspartate are particularly preferred.

In the context of a further preferred embodiment of the present invention has the shell of a detergent additive according to the invention as a further shell substance at least one water-soluble polymer. Water-soluble polymers are suitable especially then as part of the shell of an inventive Detergent additive if parameters such as hardness, abrasion resistance or Solubility in water should be influenced. The proportion of such a water-soluble Depending on the desired properties of the shell, the polymer is approximately 0 up to about 50% by weight, based on the total coating substance, in particular about 1 to about 30% by weight, for example about 5 to about 25% by weight.

manufacturing

The detergent additives according to the invention can be prepared by processes which are already known for the production of detergents. Basically, it will first the defoamer grain by drying and optionally granulating one Corresponding emulsion or dispersion prepared, which is then mixed with an aqueous Solution of the coating substance is brought into contact.

This is preferably done at higher temperatures, with the coating substance on precipitates the grain and essentially includes it. Generalized the production of the new detergent additives so that one first aqueous emulsion or dispersion of a defoamer dries and on it forming grain from an aqueous solution or melt a coating substance precipitates, possibly while the water evaporates.

The process according to the invention can be carried out in several stages, for example in two stages, carry out. In the latter case, for example, first a corresponding one Defoamer emulsion or dispersion dried and the dried powder, in which it can in turn also be a conventional market product, then coated.

The drying device in which the defoamer emulsions or dispersions are introduced, preferably sprayed, can be any drying apparatus. In one process control, the drying is carried out as spray drying in a drying tower. The preferably aqueous emulsions or dispersions are exposed in a known manner to a drying gas stream in finely divided form. Defoamer powders are obtained which are then intimately mixed with the required amount of coating substances in the form of an aqueous solution in a second step. Components such as, for example, paddle mixers from Lödige or in particular spray mixers from Schugi or fluidized bed devices, in which the defoamer powder is placed in the mixing chamber and the aqueous solutions of the coating materials are sprayed on, are advantageous for this process.

A particularly preferred option is to subject the optionally aqueous defoamer precursors to fluidized bed granulation ("SKET" granulation). This is understood to mean granulation with simultaneous drying, which is preferably carried out batchwise or continuously. The defoamers can be used both in the dried state and as an aqueous preparation. The aqueous solutions or melts of the coating materials are introduced into the fluidized bed with dry defoamer powder simultaneously or successively via one or more nozzles. Preferably, defoamer powder is blown in continuously via a nozzle and the coating materials are metered in via a second nozzle. This corresponds to a continuous solid / liquid production, but presupposes that appropriately dried defoamer powder is already available.

Fluidized bed apparatuses used with preference have base plates with dimensions from 0.4 to 5 m. The granulation is preferably carried out at fluidizing air speeds in the Range from 1 to 8 m / s. The discharge of the granules from the fluidized bed is preferably done by size classification of the granules. The classification can for example by means of a screening device or by an opposing one Air flow (classifier air) take place, which is regulated so that only particles from one certain particle size removed from the vertebral layer and smaller particles in the Fluidized bed are retained. The inflowing air is usually exposed the heated or unheated classifier air and the heated bottom air together. The Soil air temperature is between 80 and 400, preferably between 90 and 350 ° C. Advantageously, at the start of the granulation of a starting mass, for example a defoamer granulate from a previous trial, submitted. In the Fluidized bed evaporates the water from the emulsions or dispersions, whereby Dried up to dried germs arise, which with further amounts of defoamers coated, granulated and again dried at the same time.

In a particularly preferred embodiment of the invention, the aqueous emulsions or dispersions of the defoamers separately in a spray tower or dried in a fluidized bed and in a second step the aqueous ones Solutions of the coating substances on the dried defoamer powder with simultaneous Applying drying and granulation in the fluidized bed. It is particularly suitable here the SKET process e.g. of the companies Glatt and Haase.

In the context of a further preferred embodiment of the present invention the detergent additives according to the invention are prepared by liquid, approx. 120 - 160 ° C hot paraffin mixtures on the powdery Mount carrier materials in a mixing unit (e.g. from Lödige) and in one second step an aqueous silicone oil emulsion and the aqueous solutions of Enveloping substances on the defoamer powder while drying and Applying granulation in a fluidized bed (SKET process or fluid bed).

As already explained, the aqueous solutions of the coating substances can also be used together with the defoamer precursors, but this can lead to some of the fillers ending up in the grain and the coating of the grain being incomplete. In some cases this may be sufficient for the intended effect, but it is more advantageous to add the aqueous solutions to the granulation only at the end of the drying process in order to ensure that the grain is essentially completely coated. In this context, reference is made to the teaching of German patent applications DE 4303211 A1 and DE 4303176 A1 , which is expressly regarded as part of the disclosure of the present text. For the purposes of the invention, it is also possible to use agglomerates which are formed by the granules caking together.

Industrial applicability

Another object of the present invention relates to the use of Detergent additives according to the invention as defoamers for the production of Detergents, preferably as defoamers in detergents that have a high Contain anionic surfactants in the form of powders, granules, Extrudates are available in or tablets. The present invention therefore also relates Detergents which contain detergent additives according to the invention.

Other preferred ingredients of such detergents that are made using the Detergent additives according to the invention are available are inorganic and organic builder substances, mainly as inorganic builder substances Zeolites, crystalline layered silicates and amorphous silicates with image properties and - where permissible - phosphates, for example tripolyphosphates, are also used. The Builder substances are preferably in amounts in the detergents according to the invention from about 10 to about 60% by weight, based on the total detergent. Provided these compounds are water-soluble, they can also be used, for example, as further Enveloping substances in the above sense in the inventive Detergent additives are used. This applies equally to those below described silicates, dextrins, polyacrylates and the like.

Zeolite A and / or P, which is often used as detergent images and contains no crystalline, synthetic and bound water, is preferably Zeolite A and / or P. As Zeolite P, for example Zeolite MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures which contain two or more zeolites selected from the group consisting of zeolite A, X, P or Y are also suitable. Of particular interest is also a cocrystallized sodium / potassium aluminum silicate from zeolite A and zeolite X, which is commercially available as VEGOBOND AX® (commercial product from Condea Augusta SpA). The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.

Suitable zeolites have an average particle size of less than 10 µm (Volume distribution; measurement method: Coulter Counter) and preferably contain 18 up to 22% by weight, in particular 20 to 22% by weight, of bound water.

Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi _x O2 _{x + 1} * yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP 0164514 A1 . Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ O ₅ * yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO 91/08171 . Further suitable layered silicates are known, for example, from patent applications DE 2334899 A1, EP 0026529 A1 and DE 3526405 A1 . Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here. Suitable sheet silicates, which belong to the group of water-swellable smectites, are, for example, those of the general formulas
(OH) ₄ Si _8-y Al _y (Mg _x Al _4-x ) O ₂₀ montmorrilonite
(OH) ₄ Si _8-y Al _y (Mg _6-z Li _z ) O ₂₀ hectorite
(OH) ₄ Si _8-y Al _y (Mg _6-z Al _z ) O ₂₀ saponite with x = 0 to 4, y = 0 to 2, z = 0 to 6. In addition, the layered silicate according to the above can be incorporated into the crystal lattice Formulas small amounts of iron must be incorporated. Furthermore, due to their ion-exchanging properties, the layered silicates can contain hydrogen, alkali, alkaline earth ions, in particular Na ⁺ and Ca ²⁺ . The amount of water of hydration is usually in the range of 8 to 20% by weight and depends on the swelling condition or the type of processing. Useful layer silicates are known, for example, from US 3,966,629, US 4,062,647, EP 0026529 A1 and EP 0028432 A1 . Layer silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.

The preferred builder substances also include amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delayed release and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE 4400024 A1 . Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

Of course, it is also possible to use the generally known phosphates as builders, provided that such use should not be avoided for ecological reasons. The sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable. Their content is generally not more than 25% by weight, preferably not more than 20% by weight, in each case based on the finished composition. In some cases, it has been shown that tripolyphosphates in particular, even in small amounts up to a maximum of 10% by weight, based on the finished agent, in combination with other builder substances lead to a synergistic improvement in the secondary washing ability.

Usable organic builders are, for example, the polycarboxylic acids that can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

The acids themselves can also be used. The acids have besides theirs Builder effect typically also the property of an acidifying component and thus also serve to set a lower and milder pH value of washing or Detergents. In particular, citric acid, succinic acid, To name glutaric acid, adipic acid, gluconic acid and any mixtures of these.

Other suitable organic builder substances are dextrins , for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000. A polysaccharide with a dextrose equivalent ( DE ) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure for the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2,000 to 30,000 can be used. A preferred dextrin is described in British patent application GB 9419091 A1 , The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP 0232202 A1, EP 0427349 A1, EP 0472042 A1 and EP 0542496 A1 as well as from international patent applications WO 92/18542, WO 93/08251, WO 93/16110, WO 94 / 28030, WO 95/07303, WO 95/12619 and WO 95/20608 are known. An oxidized oligosaccharide according to German patent application DE 19600018 A1 is also suitable . A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Other suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate . Also particularly preferred in this context are glycerol disuccinates and glycerol trisuccinates , as described, for example, in US Pat. Nos. 4,524,009, 4,639,325, in European patent application EP 0150930 A1 and in Japanese patent application JP 93/339896 . Suitable amounts used in formulations containing zeolite and / or silicate are 3 to 15% by weight.

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

Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid and measured in each case against polystyrene sulfonic acid). Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000 (measured in each case against polystyrene sulfonic acid). The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution, with 20 to 55% by weight aqueous solutions being preferred. Granular polymers are usually subsequently mixed into one or more basic granules. Also particularly preferred are biodegradable polymers composed of more than two different monomer units, for example those which, according to DE 4300772 A1, are monomeric salts of acrylic acid and maleic acid, and vinyl alcohol or vinyl alcohol derivatives, or, according to DE 4221381 C2, are monomeric salts of acrylic acid and the 2-alkylallylsulfonic acid and sugar derivatives. Further preferred copolymers are those which are described in German patent applications DE 4303320 A1 and DE 4417734 A1 and which preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers. Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Polyaspartic acids or their salts and derivatives are particularly preferred.

Other suitable builder substances are polyacetals , which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP 0280223 A1 . Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

In addition, the agents can also contain components that make the oil and fat washable made of textiles. Among the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as Methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups from 15 to 30% by weight and from 1 to 15% by weight of hydroxypropoxyl groups, each based on the nonionic cellulose ether, and those from the prior art Technically known polymers of phthalic acid and / or terephthalic acid or their Derivatives, in particular polymers of ethylene terephthalates and / or Polyethylene glycol terephthalates or anionically and / or nonionically modified Derivatives of these. Of these, the sulfonated derivatives of are particularly preferred Phthalic acid and terephthalic acid polymers.

Other suitable ingredients of the detergents according to the invention are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates, normal water glasses, which have no outstanding builder properties, or mixtures of these: especially alkali carbonate and / or amorphous alkali silicate, especially Sodium silicate with a molar ratio Na20: Si02 of 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5. The content in the invention Detergent in sodium carbonate is preferably up to 40% by weight, advantageously between 2 and 35% by weight. The content of the means in sodium silicate (without special builder properties) is generally up to 10% by weight and preferably between 1 and 8% by weight.

In addition to the ingredients mentioned, the detergents can contain other known detergents commonly used additives, for example salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, small amounts of neutral filling salts as well as dyes and fragrances, opacifiers or pearlescent agents.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.

Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. The bleaching agent content of the agents is preferably 5 to 35% by weight and in particular up to 30% by weight, advantageously using perborate monohydrate or percarbonate.

Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multi-acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetyloxy, 2,5-acetiacetyl, ethylene glycol 2,5-dihydrofuran and the enol esters known from German patent applications DE 19616693 A1 and DE 19616767 A1 as well as acetylated sorbitol and mannitol or their mixtures described in European patent application EP 0525239 A1 (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose , Tetraacetylxylose and Octaacetyllactose as well as acetylated, optionally N-alkyl ized glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, which are known from international patent applications WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626, WO 95/14759 and WO 95 / 17498 are known.

The hydrophilically substituted acylacetals known from German patent application DE 19616769 A1 and the acyl lactams described in German patent application DE 19616 770 and international patent application WO 95/14075 are also preferably used. The combinations of conventional bleach activators known from German patent application DE 4443177 A1 can also be used. Bleach activators of this type are present in the customary quantitative range, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total agent.

In addition to the conventional bleach activators listed above or in their place, the sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP 0446982 B1 and EP 0453 003 B1 can also be present as so-called bleaching catalysts. The transition metal compounds in question include in particular the manganese, iron, cobalt, ruthenium or molybdenum-salt complexes known from German patent application DE 19529905 A1 and their N-analog compounds known from German patent application DE 19620267 A1 , which are known from German Patent application DE 19536082 A1 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, the manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium described in German patent application DE 196 05 688 - and copper complexes with nitrogen-containing tripod ligands that from German patent application DE 19620411 A1 known cobalt-, iron-, copper- and ruthenium-ammine complexes, the manganese described in the German patent application DE 4416438 A1, copper and cobalt complexes , in European Patent application EP 0272030 A1 described cobalt complexes known from European patent application EP 0693550 A1 manganese Complexes, the manganese, iron, cobalt and copper complexes known from European patent EP 0392592 A1 and / or those described in European patent EP 0443651 B1 or European patent applications EP 0458397 A1, EP 0458398 A1, EP 0549271 A1, Manganese complexes described in EP 0549272 A1, EP 0544490 A1 and EP 0544519 A1 . Combinations of bleach activators and transition metal bleach catalysts are known, for example, from German patent application DE 19613103 A1 and international patent application WO 95/27775 .

Bleach-enhancing transition metal complexes, especially with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru are used in conventional amounts, preferably in one Amount up to 1 wt .-%, in particular from 0.0025 wt .-% to 0.25 wt .-% and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the total Means used.

Particularly suitable enzymes are those from the class of hydrolases, such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains, such as stains containing protein, fat or starch, and graying in the laundry. By removing pilling and microfibrils, cellulases and other glycosyl hydrolases can contribute to color retention and increase the softness of the textile. Oxidoreductases can also be used for bleaching or for inhibiting color transfer. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, in particular, however, mixtures containing protease and / or upase or mixtures with lipolytically active enzymes of particular interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. Cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since the different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

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

In addition to the mono- and polyfunctional alcohols, the agents can contain further enzyme stabilizers . For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. In addition to calcium salts, magnesium salts also serve as stabilizers. However, the use of boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates, such as the salts of orthoboric acid (H ₃ BO ₃ ), metaboric acid (HBO ₂ ) and pyrobic acid (tetraboric acid H ₂ B ₄ O ₇ ), is particularly advantageous.

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed. Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, cellulose ethers, such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the detergent, are preferred used.

As optical brighteners, the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the morpholino- Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryldiphenyls) or 4- (4- Chlorstyryl) -4 '- (2-sulfostyryl) diphenyls. Mixtures of the above-mentioned brighteners can also be used. Uniformly white granules are obtained if, apart from the usual brighteners, the agents are used in the usual amounts, for example between 0.1 and 0.5% by weight .-%, preferably between 0.1 and 0.3 wt .-%, also small amounts, for example 10 ^-6 to 10 ^-3 wt .-%, preferably around 10 ^-5 wt .-%, of a blue dye. A particularly preferred dye is Tinolux® (commercial product from Ciba-Geigy).

As soil-repellants, such substances come into question that preferably ethylene terephthalate and / or polyethylene glycol terephthalate groups included, the molar ratio of ethylene terephthalate to polyethylene glycol terephthalate can range from 50:50 to 90:10. The molecular weight of the linking Polyethylene glycol units are particularly in the range of 750 to 5000, i.e. the Degree of ethoxylation of the polymers containing polyethylene glycol groups can be approximately 15 to 100 be. The polymers are characterized by an average molecular weight of about 5000 to 200,000 and can be a block, but preferably a random structure exhibit. Preferred polymers are those with molar ratios Ethylene terephthalate / polyethylene glycol terephthalate from about 65:35 to about 90:10, preferably from about 70:30 to 80:20. Also preferred are those polymers that linking polyethylene glycol units with a molecular weight of 750 to 5000, preferably from 1000 to about 3000 and a molecular weight of the polymer of about 10,000 to about 50,000. Examples of commercially available polymers are Products Milease® T (ICI) or Repelotex® SRP 3 (Rhône-Poulenc).

Individual fragrance compounds , for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances . Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl benzylatepylpropionate, stally. The ethers include, for example, benzyl ethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, ulial and bourgeonal, the ketones, for example, the jonones, (α-isomethylionone and methylcedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene, but preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures contain as they are accessible from plant sources, e.g. pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.Muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil are also suitable , Juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil. The fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release. Cyclodextrins, for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.

If desired, the detergents according to the invention can also contain inorganic salts as fillers or fillers, such as sodium sulfate, which is preferably present in amounts of 0 to 10, in particular 1 to 5% by weight, based on the composition.

manufacturing

The detergents obtainable using the additives according to the invention can be found in Manufactured or used in the form of powders, extrudates, granules or tablets become. For the production of such agents, the corresponding, from the state of the Technique known, suitable. The agents are preferably produced by that various particulate components that contain detergent ingredients be mixed together. The particulate components can Spray drying, simple mixing or complex granulation processes, for example Fluidized bed granulation. It is particularly preferred that at least one surfactant-containing component is produced by fluidized bed granulation becomes. Furthermore, it can be particularly preferred if aqueous preparations of the Alkali silicate and the alkali carbonate together with other detergent ingredients be sprayed in a drying device, with a simultaneous with the drying Granulation can take place. In the drying device, in which the aqueous Preparation is sprayed, it can be any drying apparatus.

In a preferred process, the drying is carried out as spray drying in a drying tower. The aqueous preparations are exposed to a drying gas stream in finely divided form in a known manner. Patent publications by Henkel describe an embodiment of spray drying with superheated steam. The working principle disclosed there is hereby expressly made the subject of the present disclosure of the invention. Reference is made here in particular to the following publications: DE 4030688 A1 and the further publications according to DE 4204035 A1, DE 4204090 A1, DE 4206050 A1, DE 4206521 A1, DE 4206495 A1, DE 4208773 A1, DE 4209432 A1 and DE 4234376 A1 . This process has already been presented in connection with the production of the defoamer.

In another, especially if medium bulk densities are to be obtained, In a preferred variant, the mixtures are then subjected to a compacting step subject to further ingredients of the agents only after the compacting step be added. The compacting of the ingredients takes place in a preferred one Embodiment of the invention in a press agglomeration process instead. The Press agglomeration process to which the solid premix (dried basic detergent) subject can be realized in various devices. Depending on Different types of agglomerators are used Differentiated press agglomeration process. The four most common and under the The preferred press agglomeration process according to the present invention are Extrusion, roller pressing or compacting, hole pressing (pelleting) and that Tableting so that preferred in the present invention Press agglomeration processes extrusion, roller compacting, pelletizing or Tableting processes are. All processes have in common that the premix is under Pressure is compressed and plasticized, reducing the individual particles Porosity are pressed together and adhere to each other. With all procedures (with the Tableting with restrictions), the tools can be adjusted to higher ones Heat up temperatures or dissipate the heat generated by shear forces cool. In all processes, one or more can be used as an aid to compression Binders are used. However, it should be made clear that in itself always the use of several different binders and mixtures of different Binders is possible. In a preferred embodiment of the invention, a Binder used that at temperatures up to 130 ° C, preferably up to a maximum of 100 ° C and in particular up to 90 ° C is already completely in the form of a melt. The Binder must therefore be selected depending on the process and process conditions or the process conditions, in particular the process temperature, must - if a certain binder is desired - be adapted to the binder. The actual compression process is preferably carried out at Processing temperatures that at least in the compression step at least Temperature of the softening point, if not the temperature of the melting point of the binder.

In a preferred embodiment of the invention, the process temperature is significantly above the melting point or above the temperature at which the binder is present as a melt. In particular, however, it is preferred that the process temperature in the compression step not more than 20 ° C above the melting temperature or the upper one Limit of the melting range of the binder is. Technically, it is possible to set even higher temperatures; but it has been shown that a Temperature difference to the melting temperature or the softening temperature of the Binder of 20 ° C is generally sufficient and even higher Temperatures have no additional advantages. That's why it is - especially for energetic reasons - particularly preferred, above, but as close as possible at the melting point or at the upper temperature limit of the melting range of the Binder to work. Such a temperature control has the further advantage that also thermally sensitive raw materials, such as peroxy bleach such as Perborate and / or percarbonate, but also enzymes, increasingly without serious Active substance losses can be processed. The possibility of exact Temperature control of the binder in particular in the crucial step of Compression, i.e. between the mixing / homogenization of the premix and the shape, allows an energetically very favorable and for the temperature-sensitive components of the premix extremely gentle Process management, since the premix is only at the higher temperatures for a short time is exposed.

In preferred press agglomeration processes, the working tools of the Press agglomerator (the screw (s) of the extruder, the roller (s) of the roller compactor and the press roller (s) of the pellet press) a temperature of maximum 150 ° C, preferably a maximum of 100 ° C and in particular a maximum of 75 ° C and the Process temperature is 30 ° C and in particular a maximum of 20 ° C above that Melting temperature or the upper temperature limit of the melting range of the Binder. The duration of the temperature effect is preferably in Compression range of the press agglomerators is a maximum of 2 minutes and lies in particular in a range between 30 seconds and 1 minute.

Preferred binders which can be used alone or in a mixture with other binders are polyethylene glycols, 1,2-polypropylene glycols and also modified polyethylene glycols and polypropylene glycols. The modified polyalkylene glycols include in particular the sulfates and / or the disulfates of polyethylene glycols or polypropylene glycols with a relative molecular weight between 600 and 12,000 and in particular between 1,000 and 4,000. Another group consists of mono- and / or disuccinates of the polyalkylene glycols, which again have relative molecular weights between 600 and 6,000, preferably between 1,000 and 4,000. For a more detailed description of the modified polyalkylene glycol ethers, reference is made to the disclosure of the international patent application WO 93/02176 . In the context of this invention, polyethylene glycols include those polymers which, in addition to ethylene glycol, also use C ₃ -C ₅ glycols and glycerol and mixtures of these as starting molecules. Ethoxylated derivatives such as trimethylolpropane with 5 to 30 EO are also included. The polyethylene glycols preferably used can have a linear or branched structure, linear polyethylene glycols being particularly preferred. The particularly preferred polyethylene glycols include those with relative molecular weights between 2,000 and 12,000, advantageously around 4,000, polyethylene glycols with relative molecular weights below 3,500 and above 5,000, in particular in combination with polyethylene glycols with a relative molecular weight of around 4,000, can be used such combinations advantageously have more than 50% by weight, based on the total amount of polyethylene glycols, of polyethylene glycols with a relative molecular weight of between 3,500 and 5,000. However, polyethylene glycols can also be used as binders, which are per se in liquid state at room temperature and a pressure of 1 bar; Here we are mainly talking about polyethylene glycol with a relative molecular mass of 200, 400 and 600. However, these per se liquid polyethylene glycols should only be used in a mixture with at least one further binder, this mixture again having to meet the requirements according to the invention, that is to say having a melting point or softening point of at least above 45 ° C. Likewise suitable as binders are low molecular weight polyvinylpyrrolidones and derivatives thereof with relative molecular weights of up to a maximum of 30,000. Relative molecular weight ranges between 3,000 and 30,000, for example around 10,000 are preferred. Polyvinylpyrrolidones are preferably not used as sole binders, but in combination with other used in particular in combination with polyethylene glycols.

The compacted material points directly after it leaves the manufacturing apparatus preferably temperatures not above 90 ° C, with temperatures between 35 and 85 ° C are particularly preferred. It has been found that Exit temperatures - especially in the extrusion process from 40 to 80 ° C, for example up to 70 ° C, are particularly advantageous.

In a preferred embodiment, the detergent according to the invention is produced by means of an extrusion , as described, for example, in European patent EP 0486592 B1 or international patent applications WO 93/02176 and WO 94/09111 or WO 98/12299 . In this case, a solid premix is pressed in the form of a strand under pressure and the strand is cut to the predeterminable size of the granulate after it has emerged from the hole shape by means of a cutting device. The homogeneous and solid premix contains a plasticizer and / or lubricant, which causes the premix to become plastically softened and extrudable under the pressure or under the entry of specific work. Preferred plasticizers and / or lubricants are surfactants and / or polymers. To explain the actual extrusion process, reference is hereby expressly made to the patents and patent applications mentioned above. The premix is preferably fed to a planetary roller extruder or a 2-shaft extruder or 2-screw extruder with co-rotating or counter-rotating screw guidance, the housing and the extruder pelletizing head of which can be heated to the predetermined extrusion temperature. Under the shear action of the extruder screws, the premix is compressed, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally, under pressure, which is preferably at least 25 bar, but can also be lower at extremely high throughputs depending on the apparatus used the extrudate is preferably reduced to approximately spherical to cylindrical granules by means of a rotating knife. The hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granulate dimension. In this way, the production of granules of an essentially uniformly predeterminable particle size succeeds, and in particular the absolute particle sizes can be adapted to the intended use. In general, particle diameters up to at most 0.8 cm are preferred. Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from approximately 0.8 to 3 mm. The length / diameter ratio of the chipped primary granules is preferably in the range from about 1: 1 to about 3: 1. It is also preferred to feed the still plastic primary granules to a further shaping processing step: edges present on the crude extrudate are rounded off, see above that ultimately spherical to approximately spherical extrudate grains can be obtained. If desired, small amounts of dry powder, for example zeolite powder such as zeolite NaA powder, can also be used in this step. This shape can be done in standard rounding machines. Care should be taken to ensure that only small amounts of fine grain are produced in this stage. Drying, which is described as a preferred embodiment in the abovementioned prior art documents, is subsequently possible, but not absolutely necessary. It may just be preferred not to carry out any drying after the compacting step. Alternatively, extrusions / pressings can also be carried out in low-pressure extruders, in the Kahl press (from Amandus Kahl) or in the Bepex extruder. The temperature control in the transition region of the screw, the pre-distributor and the nozzle plate is preferably designed such that the melting temperature of the binder or the upper limit of the melting range of the binder is at least reached, but preferably exceeded. The duration of the temperature influence in the compression range of the extrusion is preferably less than 2 minutes and in particular in a range between 30 seconds and 1 minute.

The detergents according to the invention can also be produced by means of roller compaction . Here, the premix is metered in between two smooth rollers or with recesses of a defined shape and rolled out under pressure between the two rollers to form a sheet-like compact, the so-called Schülpe. The rollers exert a high line pressure on the premix and can be additionally heated or cooled as required. When using smooth rollers, smooth, unstructured sliver belts are obtained, while by using structured rollers, correspondingly structured slugs can be produced in which, for example, certain shapes of the later detergent particles can be specified. The sliver belt is subsequently broken down into smaller pieces by a knocking-off and comminution process and can be processed in this way into granules which can be refined by further surface treatment processes known per se, in particular in an approximately spherical shape. In the case of roller compaction, too, the temperature of the pressing tools, that is to say the rollers, is preferably at a maximum of 150 ° C., preferably at a maximum of 100 ° C. and in particular at a maximum of 75 ° C.

Particularly preferred manufacturing processes work with roller compacting Process temperatures that are 10 ° C, in particular a maximum of 5 ° C above Melting temperature or the upper temperature limit of the melting range of the Binder. It is further preferred that the duration of the Effect of temperature in the compression area of the smooth or with depressions of rollers in a defined form is a maximum of 2 minutes and in particular in is between 30 seconds and 1 minute.

The detergent according to the invention can also be produced by pelleting . The premix is applied to a perforated surface and pressed through the holes by means of a pressure-producing body with plasticization. In conventional embodiments of pellet presses, the premix is compressed under pressure, plasticized, pressed through a perforated surface by means of a rotating roller in the form of fine strands and finally comminuted into granules using a knock-off device. The most varied configurations of the pressure roller and perforated die are conceivable here. For example, flat perforated plates are used as well as concave or convex ring matrices through which the material is pressed using one or more pressure rollers. The press rolls can also be conical in the plate devices, in the ring-shaped devices dies and press roll (s) can have the same or opposite direction of rotation.

An apparatus suitable for carrying out the method is described, for example, in German laid-open specification DE 3816842 A1 . The ring die press disclosed in this document consists of a rotating ring die interspersed with press channels and at least one press roller which is operatively connected to its inner surface and which presses the material supplied to the die space through the press channels into a material discharge. In this case, the ring die and press roller (s) can be driven in the same direction, which means that a reduced shear stress and thus a lower temperature increase in the premix can be achieved. Of course, it is also possible to work with heatable or coolable rollers in the pelletizing in order to set a desired temperature of the premix. In pelletizing, too, the temperature of the pressing tools, that is to say the pressure rollers or pressure rollers, is preferably at most 150 ° C., preferably at most 100 ° C. and in particular at most 75 ° C. Particularly preferred production processes work in roller compacting with process temperatures which are 10 ° C., in particular a maximum of 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder.

Another pressing agglomeration process that can be used to produce the detergents according to the invention is tableting . Due to the size of the tablets produced, it may be useful for tableting to add conventional disintegration aids, e.g. cellulose and its derivatives, in particular in coarser form, or cross-linked PVP in addition to the binder described above, which facilitate the disintegration of the pressed length in the wash liquor. The particulate press agglomerates obtained can either be used directly as detergents or aftertreated and / or prepared beforehand by customary methods. The usual aftertreatments include, for example, powdering with finely divided ingredients from washing or cleaning agents, which generally further increases the bulk density. However, a preferred aftertreatment is also the procedure according to German patent applications DE 19524287 A1 and DE 19547457 A1 , in which dusty or at least finely divided ingredients (the so-called fine fractions) are adhered to the particulate end products of the process, which serve as the core, and thus give rise to means , which have these so-called fines as an outer shell. In turn, this advantageously takes place by melting agglomeration.

For melt agglomeration of the fine fractions, reference is expressly made to the disclosure in German patent applications DE 19524287 A1 and DE 19547457 A1 . In the preferred embodiment of the invention, the solid detergents are in tablet form, these tablets preferably having rounded corners and edges, in particular for storage and transport reasons. The base of these tablets can be circular or rectangular, for example. Multi-layer tablets, in particular tablets with 2 or 3 layers, which can also have different colors, are particularly preferred. Blue-white or green-white or blue-green-white tablets are particularly preferred. Detergent tablets generally contain a disintegrant, which is said to bring about the rapid dissolution of the tablet or the rapid disintegration of the tablet in the aqueous liquor. In this context, reference is expressly made to the content of the German patent applications DE 19709991 A1 and DE 19710254 A1 , in which preferred cellulose-based disintegrant granules are described.

The present invention therefore also relates to detergents, at least containing a detergent additive according to the invention or one after Detergent additive prepared according to the method.

The invention furthermore relates to the use of inventive Detergent additives as defoamers for the production of detergents.

The invention also relates to the use of inventive Detergent additives or by a method according to the invention manufactured detergent additives for the production of detergents in the form of Powders, granules, extrudates, agglomerates or tablets.

The invention is explained in more detail below by examples.

Examples Manufacturing example H1 Defoamer H1

10,000 kg of an aqueous slurry consisting of 0.75% by weight of Sokalan CP 5 (Acrylate / maleinate copolymer), 0.5% by weight of water glass, 1.75% by weight of cellulose ether, 1.0 % By weight sodium sulfate, 35.5% by weight sodium carbonate, 1.1% by weight Ethylenediamine bisstearate, 6.6% by weight of a petrolatum wax mixture consisting of Paraffin-hydrogenated, soft paraffin and paraffin wax with an oil content of 20 - 25% and a softening point of ERP 35-55 ° C, 1.3 wt .-% of a microcrystalline Paraffins with a softening point of ERP 125-130 ° C and 1.5% silicone oil were with constant homogenization under a pressure of 40 bar in a spray tower atomized and by means of hot, countercurrent combustion gases (temperature in the Ring channel 250 ° C, dried in the tower outlet 98 ° C).

Coating the defoamer H2 (from H 1) with surfactant (according to the invention)

In a fluidized bed apparatus (SKET system) with a circular fluidized bed, through which drying air flowed with approx. 20,000 m ³ air / h at a temperature of 140 ° C, 1,000 kg of the powdered defoamer produced were continuously fed in and out via a solids metering this powdered defoamer continuously sprayed 150 kg per hour of an aqueous, 30% C 12/14 fatty alcohol sulfate paste through a second nozzle. The temperature in the fluidized bed above the fluidized bed was 75 ° C, the exhaust air 70 ° C. The granules obtained with <2% water had a bulk density of 600 g / l and a particle size distribution in which 95% by weight of the particles had an average diameter below 1.5 mm and 90% by weight of the particles had an average diameter of > 0.2 mm. With regard to the appearance of its grain, the product showed a typical granulate structure with a very good flowability and had practically no dust content.

Application tests.

a) The defoamer granules H 2 and the defoamer H 1 were used with 5 wt .-% in a detergent formulation. With these Detergent products were made right after they were made Washing machine (Miele W 918) 3.5 kg standard laundry in one full wash cycle washed at 30 ° C and 90 C (Examples 1 and 2 or Comparative Examples 1 and 2).

b) The detergent products with defoamer granules H 2 and the defoamer H 1 were also stored at 40 C for several weeks and after each week as in a) tested for their defoaming effect.

(1) = sehr wenig Schaum,

(2) = akzeptabler Schaum,

(3) = gerade noch akzeptable Schaummenge,

(4) = halbe Trommel mit Schaum gefüllt,

(5) = gesamte Trommel mit Schaum gefüllt,

(6) = Maschine schäumt über.

Die Ergebnisse der Waschversuche sind Tabelle 1 zu entnehmen. Testrezeptur für Entschäumer und Waschversuche (Angaben in Gew.-%, Wasser ad 100 %) Zusammensetzung 1 2 V1 V2 Dodecylbenzolsulfonat-Natriumsalz 7,2 7,2 7,2 7,2 C_12/18 -Kokosfettalkohol+7EO 6,2 6,2 6,2 6,2 Palmkemfettsäure-Natriumsalz 1,3 1,3 1,3 1,3 Natriumcarbonat 8,3 8,3 8,3 8,3 Natriumsulfat 22,2 22,2 22,2 22,2 Natriumsilicat 2,0 2,0 2,0 2,0 Natriumpercarbonat 12,0 12,0 12,0 12,0 Zeolith A 24,0 24,0 24,0 24,0 TAED 4,3 4,3 4,3 4,3 Entschäumergranulat H 2 (erfindungsgemäß) 3,0 3,0 - - Entschäumerpulver H 1 (zum Vergleich) - - 3,0 3,0 Lagerung bei 40 C Anzahl der Wochen, nach denen geprüft wurde 0 8 0 4 Schaumnoten Waschversuch bei 30 °C 2 2 2 6 Waschversuch bei 90 °C 2 2 2 6 During the wash cycle, the foam height was continuously determined and recorded in the drum. Here:

(1) = very little foam,

(2) = acceptable foam,

(3) = just acceptable amount of foam,

(4) = half drum filled with foam,

(5) = entire drum filled with foam,

(6) = machine foams.

The results of the washing tests are shown in Table 1. Test formulation for defoamers and washing tests (data in% by weight, water ad 100%) composition 1 2 V1 V2 Dodecylbenzenesulfonate sodium salt 7.2 7.2 7.2 7.2 C _12/18 coconut _fatty alcohol + 7EO 6.2 6.2 6.2 6.2 Palmkemfettsäure sodium salt 1.3 1.3 1.3 1.3 sodium 8.3 8.3 8.3 8.3 sodium sulphate 22.2 22.2 22.2 22.2 sodium 2.0 2.0 2.0 2.0 Sodium percarbonate 12.0 12.0 12.0 12.0 Zeolite A 24.0 24.0 24.0 24.0 TAED 4.3 4.3 4.3 4.3 Defoamer granules H 2 (according to the invention) 3.0 3.0 - - Defoamer powder H 1 (for comparison) - - 3.0 3.0 Storage at 40 C. Number of weeks after which it was checked 0 8th 0 4 foam Sheet Wash attempt at 30 ° C 2 2 2 6 Wash attempt at 90 ° C 2 2 2 6

Preparation example V 3 (comparative example).

In a fluidized bed apparatus (SKET system) with a circular fluidized bed, through which drying air with approx. 20,000 m ³ air / h flowed at a temperature of 140 ° C, 1,000 kg of the powdered defoamer H1 produced were fed in continuously via a solids metering and 100 kg per hour of an aqueous, 56% sodium sulfate solution were continuously sprayed onto this powdered defoamer via a second nozzle. The temperature in the fluidized bed above the fluidized bed was 95 ° C, the exhaust air 80 ° C. The grain structure of the product obtained was little changed compared to the defoamer H 1 used, ie the coated product did not have a granular structure, but rather a powder structure.

The coated defoamers H 2 (according to the invention) and V 3 were 1 hour in one Turbula vibrator, machine T 2 C from Willy A. Bachhofen AG CH-4005 Basel shaken and then the fine fraction determined. The fine fraction (particles with <0.1 mm) was 0% by weight for defoamer H 2 and 4% by weight for defoamer V 3.

Claims (15)

Detergent additives in solid form, characterized in that they consist of a defoaming compound as the core and a shell, the shell as the shell substance at least one anionic surfactant or, if at least one anionic surfactant, an alkali metal salt of an organic carboxylic acid having 1 to 22 carbon atoms is contained, contains a mixture of two or more anionic surfactants, or at least one nonionic surfactant or at least one zwitterionic surfactant or a mixture of two or more of the surfactants mentioned. Detergent additives according to claim 1, characterized in that they contain a waxy compound and / or a silicone compound as the defoaming compound. Detergent additives according to claims 1 and / or 2, characterized in that they contain at least one wax-like paraffin-based compound as a defoamer. Detergent additives according to at least one of claims 1 to 3, characterized in that they contain at least one wax-like compound based on hydrogenated or partially hydrogenated paraffins as a defoamer. Detergent additives according to one of claims 1 to 4, characterized in that they contain, as defoamers, at least one waxy compound from the group of ketones, dialkyl ethers, fatty alcohols, fatty acids, fatty alkyl esters, dialkyl carbonate esters, fatty acid ethylene glycol esters, hydroxystearic acid esters. Detergent additives according to at least one of claims 1 to 5, characterized in that they contain at least one wax-like compound based on amide waxes as a defoamer. Detergent additives according to at least one of claims 1 to 6, characterized in that they contain at least one wax-like compound based on bisstearylethylene amide as defoamer. Detergent additives according to at least one of claims 1 to 7, characterized in that they contain at least one wax-like compound and a defoaming silicone compound as defoamers. Detergent additives according to one of claims 1 to 8, characterized in that the casing has a water solubility of at least 1 g / l at 20 ° C. A process for the preparation of detergent additives in solid form, characterized in that firstly an aqueous emulsion or dispersion of a defoamer is dried and a coating substance is deposited on the resulting grain from an aqueous solution or melt close to claim 1 while the water evaporates. Process according to Claim 10, characterized in that the aqueous emulsions or dispersions of the defoamers are subjected to spray drying, the resulting powders are intimately mixed with the aqueous solutions or melts of the coating substances and, if appropriate, the water is removed in the process. Process according to Claim 10, characterized in that defoamer powder and aqueous solutions or melts of the coating substances are subjected to simultaneous drying and granulation in the Wibel layer. Detergent, at least containing a detergent additive according to one of the Claims 1 to 9 or one produced according to one of claims 10 to 12 Detergent additive. Use of detergent additives according to one of claims 1 to 13 as Defoamers for the production of detergents. Use of detergent additives according to one of claims 1 to 9 or of detergent additive prepared according to one of claims 10 to 12 for Production of detergents in the form of powders, granules, extrudates, Agglomerates or tablets.