WO1993017772A1

WO1993017772A1 - Paraffin-based foam control agent

Info

Publication number: WO1993017772A1
Application number: PCT/EP1993/000462
Authority: WO
Inventors: Wolfgang Seiter; Claus-Peter KURZENDÖRFER; Hans-Josef Beaujean; Edmund Schmadel
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1992-03-10
Filing date: 1993-03-01
Publication date: 1993-09-16
Also published as: DE4207552A1

Abstract

In granular, pourable foam control agents, especially for use in washing and cleaning agents, consisting of a granular, tenside-free carrier (1) and a homogenous adsorbed anti-foaming mixture (II) containing no siloxane polymers or tensides but containing 70 to 95 wt % of a paraffin wax and 5 to 30 wt % of a bisamide derived from C2-7 diamines and saturated C12-22 carboxylic acids, the effectiveness over a wide temperature range, i.e. in particular in the cold-wash range and at medium washing temperatures, and the shelf and effective lives when mixed with conventional washing agent components are to be improved. This has been achieved by the development of an agent with no silicic acid, the carrier of which contains no phosphates and is soluble or dispersible in water and in which the paraffin wax is solid at room temperature and is liquid to 100 wt % at a temperature below 90°C.

Description

"Paraffin-based foam control agent ¹

The invention relates to a defoamer mixture which consists of carboxylic acid bisa iden and certain paraffin waxes, a pourable and free-flowing foam regulating agent, in particular for use in the production of detergents and cleaning agents, comprising water-soluble or water-dispersible carrier material and defoamer mixture adsorbed thereon. and a method for producing such foam control agents.

The use of bisa iden as a defoamer for detergents is known from the German patent application DT 2043087. However, the formulations mentioned there do not have a uniform defoamer effect over a wide temperature range. European patent EP 87 233 describes a process for producing a low-foaming detergent in which mixtures of an oily or wax-like substance and bisamides are applied to a carrier powder, in particular a spray-dried detergent containing surfactants. The oily or wax-like substance can consist, for example, of petroleum jelly with a melting point of 20 ° C. to 120 ° C. Mineral oil is used in the examples for this purpose. Obviously, this component primarily serves as a carrier or dispersant for the bis-amide. When using a 2% by weight defoamer mixture, based on the agent, satisfactory values are obtained according to the Ross Miles test, but these amounts appear far too high in practice. In addition, with this type of assembly, namely spraying the defoamer mixture onto the spray-dried detergent-containing detergent, there is a risk that the manufacturing process will adversely affect the shelf life of the foam regulating component on the surface of the foam regulating agent, with the result that the latter Activity decreases with increasing storage time. In order to increase their effect and at the same time reduce the required application concentration, these defoamers are often known Foam inhibitors added, in particular polysiloxanes or polysiloxane-silicic acid mixtures. However, polysiloxanes are known to be comparatively complex to produce with a known good defoaming effect and have the disadvantage that they are often perceived as not completely satisfactory in terms of their biodegradability in the waste water. Other agents containing bisamides are known from European patents EP 75437 and EP 94250. Agents described there, however, contain silicones and are out of the question for the reasons mentioned. The German published patent application DT 2857 155 discloses detergents with a foam regulating agent which contains hydrophobic silicon dioxide and a mixture of solid and liquid hydrocarbons, optionally in a mixture with fatty acid esters. Due to the high content of hydrocarbon which is liquid at room temperature from 22.5% by weight to about 98% by weight, there is a risk of clumping in such foam regulating agents.

The object was accordingly to provide a defoaming mixture which is used in detergents and cleaning agents over a wide temperature range, that is to say in particular in the cold washing range and at medium washing temperatures, but also in the hot washing range, suppressing disruptive foaming. Continue to be erungsmittel attachable mixing to a pourable Schaumregul the Entschäumerge¬, the storage- mixed with conventional detergent ingredients and ^'effective remains stable and lungsgut no adverse effects on the Behand¬ and exerts the environment.

European patent application EP 309931 describes foam regulating agents which do not achieve the stated object optimally only because they are dependent on a relatively complex mixture of paraffin wax and microcrystalline paraffin wax. In addition, in the case of machine washing in the low temperature range which is becoming increasingly important in recent times, these agents in some cases have a defoamer performance which is perceived as inadequate and cannot always be incorporated satisfactorily in a stable manner in powdered detergents or cleaning agents. Surprisingly, it has now been found that the existing object can be achieved by foam regulating agents which contain carboxylic acid bisamide and paraffin wax with a relatively narrow melting range.

The invention accordingly relates to a defoamer mixture which is free from siloxane polymers and emulsifying or dispersing surfactants, comprising a) 70% by weight to 99.9% by weight of a paraffin wax or paraffin wax mixture which is solid at room temperature and which a temperature below 90 ° C is 100% by weight in liquid form, and b) 0.1% by weight to 30% by weight of one of C2-7-diamines and Ci2-22 "^ ^ar ' ^DOn ' acid-derived muskrid.

Another object of the invention is a granular, free-flowing foam control agent consisting of

(I) a granular, surfactant-free carrier material and

(II) an adsorbed homogeneous defoamer mixture which is free from silicon oxypolymers and has emulsifying or dispersing surfactants and the

(a) 70% by weight to 95% by weight of a paraffin wax or paraffin wax mixture and

(b) contains 5% by weight to 30% by weight of a bisamide derived from C2-7 diamines and saturated Ci2-22 "carboxylic acids, the agent being characterized in that it is free from silica, the carrier material (I ) is phosphate-free and water-soluble or water-dispersible and the paraffin wax (component Ha) is solid at room temperature and is 100% by weight in liquid form at a temperature below 90 ° C.

The defoamer mixture preferably contains 80% by weight to 92% by weight, in particular 82% by weight to 90% by weight of paraffin wax (a) and 8% by weight to 20% by weight, in particular 10% by weight .-% to 18 wt .-% bisamide (b).

The defoamer mixture according to the invention is used in particular for the production of detergents or cleaning agents. The foam regulating agent according to the invention preferably contains 80% by weight to 99.5% by weight, in particular 88% by weight to 98% by weight of carrier material (I) and 0.5% by weight to 20% by weight, contain in particular 2% by weight to 12% by weight of defoaming mixture (II).

The phosphate-free carrier material (I) has a granular structure and consists of water-soluble or water-dispersible, surfactant-free compounds, primarily of inorganic and / or organic salts which are suitable for use in detergents and cleaning agents. It preferably contains both alkali carbonate and alkali silicate, the latter in particular being responsible for the good storage properties of the agents according to the invention. The carrier material preferably contains 1% by weight to 50% by weight of alkali carbonate, up to 70% by weight of alkali sulfate, up to 50% by weight of alkali alumosilicate and 10% by weight to 50% by weight of alkali silicate, but can additionally contain other water-soluble or water-insoluble, water-dispersible substances. The materials which can additionally be used include, in particular, alkali metal chloride and layered silicate, for example bentonite. The alkali silicate is 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 which can be used in the carrier material for the foam regulating agents according to the invention include, in particular, the zeolites, for example zeolite NaA and NaX. Examples of suitable organic carrier materials are the acetates, tartrates, succinates, carboxyethylsuccinates and the alkali metal salts of aminopolycarboxylic acids, such as NTA or EDTA, hydroxyalkanephosphonates and aminoalkane polyphosphonates, such as l-hydroxyethane-1, l-diphosphonate, ethylenediamine and diethylene triamine pentamethylene phosphonate. It is also possible to use water-soluble salts of polymeric or copolymeric carboxylic acids, for example polyacrylates and copolymers of acrylic acid and maleic acid. Mixtures of inorganic and organic salts can often be used with advantage. Such additional organic carrier materials are preferably not contained in the carrier salt mixture in excess of 20% by weight, in particular in amounts of 2% by weight to 15% by weight, in each case based on the total carrier material. Loading preferred alkali metal in the alkali salts mentioned is sodium in all cases.

The carrier material can moreover contain film-forming polymers, for example polyethylene glycols, polyvinyl alcohols, polyvinylpyrrolidones, polyacrylates and cellulose derivatives. Usable cellulose ethers are, in particular, alkali carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and so-called cellulose mixed ethers, such as methyl hydroxyethyl cellulose and methyl hydroxypropyl cellulose, and mixtures thereof. Mixtures of sodium carboxymethyl cellulose and methyl cellulose are preferably used, the carboxymethyl cellulose usually having a degree of substitution of 0.5 to 0.8 carboxymethyl groups per anhydroglucose unit and the methyl cellulose having a degree of substitution of 1.2 to 2 methyl groups per anhydroglucose unit. The mixtures preferably contain alkali carboxymethyl cellulose and nonionic cellulose ethers in weight ratios of 80:20 to 40:60, in particular 75:25 to 50:50. Such cellulose ether mixtures can be used in solid form or as aqueous solutions, which can be pre-swollen in the usual way. Such film-forming polymers are preferably not contained in the carrier material in excess of 5% by weight, in particular from 0.5% by weight to 2% by weight, based on the total carrier material.

The paraffin wax (component a) contained in the defoamer mixture (II) generally represents a complex mixture of substances without a sharp melting point. For characterization, its melting range is usually determined by differential thermal analysis (DTA), as described in "The Analyst" B∑ (1962), 420, and / or its freezing point. This is the temperature at which the paraffin changes from the liquid to the solid state by slow cooling. At room temperature, completely liquid paraffins, that is to say those with a solidification point below 25 ° C., cannot be used according to the invention. Waxes which solidify in the range from 30 ° C. to 90 ° C., in particular in the range from 55 ° C. to 71 ° C., are preferably used. It should be noted that even paraffin wax mixtures which appear solid at room temperature can contain different proportions of liquid paraffin. In the paraffin waxes which can be used according to the invention, this liquid fraction is so low as possible and preferably missing entirely. Preferred paraffin wax mixtures have a liquid fraction of less than 10% by weight at 30 ° C., in particular 2% to 5% by weight, and a liquid fraction of less than 30% by weight at 40 ° C. 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 from 30% by weight to 60% by weight, in particular by 40 % By weight to 55% by weight, at 80 ° C a liquid fraction of 80% by weight to 100% by weight, and at 90 ° C a liquid fraction of 100% by weight. The temperature at which a liquid content of 100% by weight of the paraffin wax is reached is still below 85 ° C., in particular at 75 ° C. to 82 ° C., in particularly preferred paraffin wax mixtures.

Paraffin waxes which can be used according to the invention are, for example, Lunafle® ( ^R ) 902 E 36 from Füller and Deawaχ ( ^R ) DEW 5419 and DEW 5420 from DEA Mineralöl AG.

Component (b) of the defoamer mixture consists of bisamides which are derived from saturated fatty acids with 12 to 22, preferably 14 to 18 C atoms and from alkylenediamines with 2 to 7 C atoms. Suitable fatty acids are lauric acid, myristic acid, stearic acid, arachic acid and behenic acid, and mixtures thereof, as can be obtained from natural fats or hydrogenated oils, such as tallow or hydrogenated palm oil. Suitable diamines are, for example, ethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine. Preferred diamines are ethylenediamine and hexamethylenediamine. Particularly preferred bisamides are bis-myristoyl-ethylenediamine, bis-palmitoyl-ethylenediamine, bis-stearoyl-ethylenediamine and mixtures thereof, and the corresponding derivatives of hexamethylenediamine.

As described in EP 309931, the bisamides are preferably in finely divided form and in particular have an average grain size of less than 50 μm. The maximum grain size of the particles is preferably below 20 μm, with at least 50%, in particular at least 75%, of the particles being smaller than 10 μm. These details regarding the particle size relate to the known determination method with the "Coulter Counter". The defoamer mixture (II) can be prepared in such a way that the finely divided bisamide (component b) is introduced into a melt of component (a) and homogenized therein by intensive mixing. For this purpose, the melt should have a temperature of at least 90 ° C and at most 200 ° C. The temperature is preferably 100 ° to 150 ° C. It is essential for a good effectiveness of the defoamer that a stable dispersion of the bisamide particles is present in the paraffin matrix, which can be brought about by a particle size corresponding to the definition mentioned. In order to achieve this state of dispersion, a bisamide can be used and dispersed which has the appropriate particle size from the outset, or a coarser starting material is used and the melt is subjected to grinding treatment using colloid mills, tooth mills or ball mills until the desired particle size is reached is.

A complete melting of the bisamides in the paraffin melt and subsequent rapid cooling to temperatures below the solidification point of the bisamides with simultaneous homogenization of the melt can also lead to a correspondingly fine particle size distribution of the bisamides.

An essential feature of the defoamer mixture according to the invention as well as the foam regulating agent according to the invention is the absence of surfactants in the mixture of substances. Surfactants are to be understood as surface-active compounds with a hydrophobic part of the molecule and hydrophilic anionic, ampholytic, zwitterionic, cationic and nonionic groups which have a cleaning or emulsifying effect in aqueous solution or dispersion. The hydrophobic part of the molecule generally consists of a hydrocarbon residue or a substituted hydrocarbon residue or a poorly water-soluble polyglycol ether residue, for example a polypropylene glycol or polybutylene glycol ether residue. Compounds with a non-polar molecular structure, in particular the film-forming polymers mentioned, which, under certain conditions, can likewise develop a dispersing effect in water, do not fall under the definition of "surfactants" and can be present in the foam regulating agents according to the invention. In a preferred embodiment, the foam control agent according to the invention contains 2% by weight to 5% by weight of alkali carbonate, in particular sodium carbonate, 10% by weight to 30% by weight of alkali silicate, in particular sodium silicate, 10% by weight to 75% % By weight of alkali sulfate, in particular sodium sulfate, up to 35% by weight, in particular 10% by weight to 30% by weight of zeolite, up to 5% by weight, in particular 1% by weight to 3% by weight % water-soluble or water-swellable polymer, in particular cellulose ether, and up to 17% by weight, in particular 5% by weight to 15% by weight, of water.

A further preferred embodiment of the foam regulating agent according to the invention contains 25% by weight to 45% by weight of alkali carbonate, 5% by weight to 20% by weight of alkali silicate, up to 50% by weight, in particular 15% by weight to 45% by weight, zeolite and / or alkali sulfate, up to 3% by weight, in particular 0.5% by weight to 2% by weight, water-soluble or water-swellable polymer and up to 20% by weight %, in particular 3% by weight to 18% by weight, of water.

A foam regulating agent according to the invention can be produced by applying the molten defoamer mixture (II) to the granular carrier material (I), for example by successive admixing, in particular as a spray, to the carrier grain. The carrier grain, which can be produced in the usual way by spray drying an aqueous suspension of the carrier salts, is kept in motion by mixing elements or by fluidization in order to ensure a uniform loading of the carrier material. The spray mixers used for this can be operated continuously or discontinuously.

One embodiment for the production consists in hurling the granular carrier material in a continuous stream through the likewise continuously generated spray zone of the at least partially melted defoamer mixture, whereby residence times of the carrier material in the hot spray zone of mostly less than 1 second can be achieved . Furthermore, it is possible immediately afterwards to cool the particles of the foam regulating agent with the aid of a gas stream, so that the thermal loads on the material can be kept extremely low. The method described above uses a type of method as is known, for example, from European patent application EP 48312. A wheel-shaped mixing device is described in this document as a device for carrying out the method, in which two individually designed and driven wheel-shaped disks are superimposed. The solid powder is fed to one disk, the liquid component below is charged with the liquid component. Both disks run at high rotational speeds, which can range from a few 100 to a few 1000 revolutions per minute. The respective pressurized writing surfaces and in particular the edge of the disk carrying the liquid are designed such that on the one hand the spray zone is thrown off and continuously reproduced from the edge of the wheel running at high rotational speed, and on the other hand this is continuous with the other wheel-shaped element ¬ nuously supplied granular material thrown through this spray zone of the liquid phase. Because of the high working speed, the two material phases come into contact with each other very briefly and thus only a very short time contact of the solid particles with the warm or hot spray phase. The method can be carried out particularly well with the device described in EP 48 312, but it is not restricted to devices of this type. It is essential to set a relatively short contact time, which is achieved by the solid material being thrown through a continuously generated spray zone, the solid material possibly being cooled in front of and / or behind the spray zone.

In a further embodiment of the invention, the foam regulating agent is prepared in such a way that the carrier material (I) is dissolved or slurried in water, the defoamer mixture (II) is dispersed therein and this slurry is then spray-dried. A water-soluble, non-surfactant dispersion stabilizer in the form of a water-swellable polymer is preferably added to the dispersion, since the components of the defoamer mixture are generally not sufficiently soluble in the aqueous slurry. Examples of these are the cellulose ethers mentioned, homo- and copolymers of unsaturated carboxylic acids, such as acrylic acid, maleic acid and copolymerizable vinyl compounds, such as vinyl ether, acrylamide and ethylene. The addition of such compounds which act as dispersion stabilizers in the aqueous slurry is preferably not more than 5% by weight, in particular 1% by weight to 3% by weight, based on the composition. Depending on the type or solubility of the carrier salt, the water content of the slurry can be 30% to 60% by weight. The spray-drying of the dispersion can be carried out in a known manner in plants provided for this purpose, so-called spray towers, by means of hot drying gases conducted in cocurrent or countercurrent. In this case, drying by drying gases carried in cocurrent with the spray material is preferred, since the activity loss attributable to the potential hot air volatility of some components of the defoamer mixture can be reduced to a minimum.

An inventive foam control agent preferably consists of particles having particle sizes of not more than 2 mm, in particular from 0.1 mm to ^"1.6 mm. Preferably, it contains not more than 5 wt .-%, particularly not more than 2 wt .-% of particles with a particle size of more than 0.8 mm and not more than 30% by weight, in particular not more than 25% by weight of particles with a particle size of less than 0.2 mm The foam control agent according to the invention preferably has a bulk density in the range of 300 grams per liter to 900 grams per liter, in particular from 450 grams per liter to 800 grams per liter It is preferably used for the production of powdered detergents or cleaning agents, another advantage of the foam regulating agents according to the invention being their small amount used and good defoamer performance It is thus possible to achieve the defoamer performance of conventional silicone defoamers in high-temperature washing at about 90 ° C. with the same weight to achieve amounts, based on active substance, of the paraffin-based foam regulating agents according to the invention. In the low temperature range or during the initial heating phase of the medium and high temperature wash, the foam regulators according to the invention are generally superior to the previously used defoamers. The foam control agents according to the invention have a defoamer action which is superior in particular to silicone foam inhibitors in aqueous solutions which contain alkyl polyglycoside and / or linear alkyl sulfate based on fatty alcohol and / or neutralized sulfonation products of fatty acid lower alkyl esters, so-called ester sulfonates, as surfactant component. Accordingly, they are preferably used for the production of powdered detergents or cleaning agents, the surfactant component of which is an alkyl sulfate with an alkyl group with 12 to 22 C atoms, an alkyl polyglycoside, in particular based on glucose, with an alkyl group with 12 to 18 C atoms, an alkali salt a sulfonation product of a methyl or ethyl ester of a fatty acid having 12 to 22 carbon atoms or a mixture of these ent.

Examples

Example 1: Preparation of foam regulators

By mixing cellulose ether which has been pre-swollen in water with the paraffin-bisamide melt, mixing with the separately prepared aqueous

Table 1: Powder composition TGew% 1

a) DEW 5419 (solidification point according to DIN / 502207 67 ° C), manufacturer DEA Mineralöl AG b) N, N'-bis-stearoyl-ethylenediamine c) Laundrosil ( ^R ) DGA, manufacturer Süd-Chemie d) ratio Siθ2 to a2Ö: 3.0 e) 80:20 mixture of Na carboxymethyl cellulose and methyl cellulose slurry of sodium carbonate, sodium sulfate and optionally zeolite and / or layered silicate and subsequent mixing with the sodium silicate, the zeolite in the form of an approximately 50% by weight aqueous slurry and the sodium silicate in the form of approximately 35% by weight water glass Solution was used, aqueous slurries were produced from the raw materials listed in Table 1, each containing about 34% by weight of water. These slurries were heated to temperatures of about 80 ° C to 90 ° C and sprayed in a drying tower, hot air (temperature 238 ° C at the entry point) being passed in cocurrent. The free-flowing powder products SI to S6 characterized in Table 1 by their composition were obtained which were free of particles larger than 2 mm in diameter, 1% by weight of particles larger than 0.8 mm and of Te had less than 0.2 mm of 21 wt .-% and had a bulk density of 650 grams per liter.

Example 2

By simply mixing the amount of the foam regulator SI according to the invention specified in the table below with conventional universal detergent base powders W1 to W3, without foam regulation component, which contained the surfactant components listed in Table 2, detergents were produced. The amounts of the foam regulators given in Table 2 were determined by washing tests (drum washing machine Miele W 717, 3.5 kg clean laundry, water hardness 3 ° d, dosage 98 g detergent) and are with regard to the foam behavior of the respective detergent under these conditions optimized (medium foam formation without foaming and without loss of liquor at 30 ° C, 40 ° C and 90 ° C). It was found that neither in SI nor in the case of foam regulators S2 to S6 did the amount used, based on the respective active substance, of a conventional silicone-based foam inhibitor VI (used in the form of granules containing 8% by weight silicone, 35 % By weight of sodium carbonate, 41% by weight of sodium sulfate, 10% by weight of sodium silicate, 1% by weight of cellulose ether and 5% by weight of water) had to be exceeded.

In contrast to a foam regulator according to EP 309931 tested in comparison, the activity of the foam regulators according to the invention did not decrease significantly over several months when the detergents containing them were stored. Table 2: Foam regulators in detergents TG% by weight active substance

a) Linear Ci2 / 15 alkyl benzene sulfonate, Na salt b) Na Ci6 / 18 alkyl sulfate

Claims

1. Containing defoamer mixture which is free of polysoxoxane polymers and emulsifying or dispersing surfactants

(a) 70% by weight to 99.9% by weight of a paraffin wax or paraffin wax mixture which is solid at room temperature and is 100% by weight in liquid form at a temperature below 90 ° C., and

(b) 0.1 wt .-% to 30 wt .-% of a ^acids from C 2-7 diamines and saturated C ^arD0πs Ci2-22 ~ ä bisamide derived.

2. defoamer mixture according to claim 1, characterized in that there are 80 wt .-% to 92 wt .-%, in particular 82 wt .-% to 90 wt .-% paraffin wax (a) and 8 wt .-% to 20 wt. -%, in particular 10 wt .-% to 18 wt .-% bisamide (b) contains.

3. Granular, free-flowing foam control agent consisting of

(I) a granular, surfactant-free carrier material and

(II) an adsorbed homogeneous defoamer mixture that is free from s loxane polymers and emulsifying or dispersing surfactants and that

(b) 5% by weight to 30% by weight of a bisamide derived from C2-7 diamines and saturated Ci2-22 carboxylic acids, characterized in that it is free of silica, the carrier material is phosphate-free and is water-soluble or water-dispersible and the paraffin wax is solid at room temperature and is 100% by weight in liquid form at a temperature below 90 ° C.

4. Composition according to claim 3, characterized in that it is 80 wt .-% to 99.5 wt .-%, in particular 88 wt .-% to 98 wt .-% carrier material (I) and 0.5 wt .-% Contains up to 20 wt .-%, in particular 2 wt .-% to 12 wt .-% defoamer mixture (II).

5. Composition according to claim 3 or 4, characterized in that the defoamer mixture (II) 80 wt .-% to 92 wt .-%, in particular 82 wt to 90 wt .-% paraffin wax (a) and 8 wt .-% % to 20 wt .-%, in particular 10 wt .-% to 18 wt .-% bisamide (b) contains.

6. Composition according to one of claims 3 to 5, characterized in that the carrier material (I) 1 wt .-% to 10 wt .-% alkali carbonate, up to 70 wt .-% alkali sulfate, up to 50 wt .-% alkali alumosilicate and contains 10 wt% to 50 wt% alkali silicate.

7. Composition according to one of claims 3 to 6, characterized in that the carrier material contains not more than 5 wt .-%, in particular from 0.5 wt .-% to 2 wt .-%, film-forming polymer.

8. Composition according to claim 6, characterized in that the carrier material not more than 20 wt .-%, in particular 2 wt .-% to 15 wt .-% of additional organic material, in particular acetates, tartrates, succinates, carboxymethylsuccinates, alkali salts of Contains aminopolycarboxylic acids, hydroxyalkane phosphonates, aminoalkane polyphosphonates, water-soluble salts of polymeric or copolymeric carboxylic acids and / or their mixtures.

9. Composition according to one of claims 3 to 8, characterized in that the paraffin wax (component II a) at 30 ° C a liquid fraction of less than 10 wt .-%, at 40 ° C a liquid fraction of less than 30 wt .-%, at 60 ° C a liquid fraction from 30% by weight to 60% by weight, at 80 ° C a liquid fraction from 80% by weight to 100% by weight and at 90 ° C a liquid fraction from 100% by weight having.

10. Composition according to one of claims 3 to 9, characterized in that the paraffin wax at 30 ° C has a liquid content of 2 wt .-% to 5 wt .-%, at 40 ° C a liquid content of 5 wt .-% to 25 wt. -%, in particular from 5 wt .-% to 15 wt .-% and at 60 ° C a liquid portion of 40 wt .-% to 55 wt .-%.

11. Agent according to one of claims 3 to 10, characterized in that the temperature at which a liquid content of 100% by weight of the paraffin wax is reached is below 85 ° C, in particular at 75 ° C to 82 ° C .

12. Composition according to one of claims 3 to 11, characterized in that the bisamide (component II b) is a reaction product of ethylenediamine with a saturated Ci4_i8 carboxylic acid.

13. Composition according to one of claims 3 to 12, characterized in that it contains 2% by weight to 5% by weight of alkali carbonate, 10% by weight to 30% by weight of alkali silicate, 10% by weight to 75% by weight of alkali sulfate, up to 35, in particular 10% by weight to 30% by weight of zeolite, up to 5% by weight, in particular 1% by weight to 3% by weight of water-soluble or in Water-swellable polymer and up to 17 wt .-%, in particular 5 wt .-% to 15 wt .-% water.

14. Composition according to one of claims 3 to 12, characterized in that it contains 25 wt.% To 45 wt.% Alkali carbonate, 5 wt.% To 20 wt.% Alkali silicate, up to 50 wt. %, in particular 15% by weight to 45% by weight, zeolite and / or alkali sulfate, up to 3% by weight, in particular 0.5% by weight to 2% by weight of water-soluble or water-swellable polymer, and up to 20% by weight, in particular 3% by weight to 18% by weight, of water.

15. A process for the preparation of a granular foam control agent according to any one of claims 3 to 14, characterized in that the defoamer mixture in an aqueous solution or slurry of the carrier material (I) containing 30 wt .-% to 60 wt .-% water (II), optionally with the addition of not more than 5% by weight of a water-soluble or swellable polymer, and the dispersion is spray-dried.

16. A method for producing a foam regulating agent according to one of claims 3 to 14, characterized in that the granular carrier material (I) in a continuous stream through the likewise continuous or spray zone of the at least partially melted defoamer mixture (II) is thrown.

17. The method according to claim 16, characterized in that the defoamer mixture intended for adsorption on the carrier material (I) (II) by cooling a mixture of components (a) and (b) from a temperature above the melting range of (b) is generated to a temperature below it.

18. Use of a defoamer mixture according to claim 1 or 2 for the manufacture of detergents or cleaning agents.

19. Use of a granular foam control agent according to one of claims 3 to 14 for the production of powdered detergents or cleaners.

20. Use according to claim 18 or 19, characterized in that the surfactant component of the washing or cleaning agent is an alkyl sulfate with an alkyl group with 12 to 22 C atoms, an alkyl polyglycoside, in particular glucose-based, with an alkyl group with 12 to 18 C. -Atoms, an alkali salt of a sulfonation product of a methyl or ethyl ester of a fatty acid having 12 to 22 carbon atoms or a mixture of these.