EP1920040B1 - Foam regulator granules for use as deposit preventing agents for machine-washing textiles - Google Patents

Abstract

The aim of the invention is to prevent deposits from forming on hydrophobic regions of a washing machine that occur when detergents are used for machine-washing textiles. For this purpose, a particulate foam regulator is used. Said foam regulator comprises a combination of organopolysiloxane having at least one silicon-bound substituent of formula X-Ph, wherein X is a divalent organic group, bound to silicon via a carbon atom, and Ph is an aromatic group, and an organosilicon resin and a hydrophobic filler.

Description

The invention relates to the use of particulate foam control agents which can be used in detergents or cleaners and, in addition to their defoaming action in machine washing processes, make a pronounced contribution to preventing the deposition of residues on washing machine parts.

The foam-regulating effect of certain silicones as well as combinations of paraffins with Bisfettsäureamiden in aqueous surfactant-containing systems is known. For example, the European patent specification describes EP 0 309 931 B1 Particulate foam control agents suitable for use in detergents and cleaners, consisting of a water-soluble surfactant-free carrier material and a siloxane-free defoamer mixture of 5-60% by weight of soft and / or hard paraffin, 20-90% by weight of microcrystalline paraffin wax with a certain melting range and 5-20% by weight of a diamide derived from C _2-7 diamines and C _12-22 fatty acids in finely divided form. The preparation of such particulate foam control agents is carried out by spray-drying an aqueous slurry containing the support material and the defoaming mixture. The defoamer performance of the defoamer mixture is reported to be insufficient when sprayed onto a particulate detergent.

The use of foam-regulating homogeneous mixtures of nonionic surfactant and a foam control system containing paraffin wax and bis-fatty acid amides to improve the manufacturability and product properties of extruded detergents and cleaners is disclosed in the international patent application WO 96/26258 known.

Subject of the German patent application DE 23 38 468 is a detergent containing a silicone defoamer that is protected against interactions with the detergent ingredients. For its preparation, aqueous melts containing the silicone defoamer and a carrier substance, for example polyglycol, are first spray-dried and the resulting particles in a fluidized bed The coating material used can be any of the conventional salts used in detergents, in particular tripolyphosphate or carboxymethylcellulose. Such a multi-stage production process is comparatively technically complicated.

The German patent application DE 31 28 631 describes the preparation of foam-dampened detergents containing silicone defoamers which are microencapsulated. In this case, the silicone is dispersed in an aqueous solution of a film-forming polymer and the dispersion - separated from the other dissolved or dispersed in water detergent ingredients - fed via a special line of the spray-drying plant. The union of the two partial streams takes place in the region of the spray nozzle. Suitable film-forming polymers are, for example, cellulose ethers, starch ethers or synthetic water-soluble polymers and mixtures thereof. The formation of the microcapsules takes place spontaneously in the spray nozzle or by previous precipitation by adding electrolyte salts to the silicone dispersion. The process described is bound to the production of spray-dried detergents. A transfer to otherwise, for example, produced by granulation detergents or other applications, is not possible in this procedure.

The European patent application EP 097 867 describes a method for producing microencapsulated defoamer oils by mixing a silicone emulsion with an aqueous solution of carboxymethylcellulose and precipitating the microcapsules by adding electrolytes, especially polyvalent salts or organic solvents. There is considerable difficulty in homogeneously distributing the small quantities of silicone microcapsules required for adequate foam damping in a comparatively large quantity of washing powder.

From the European patent application EP 0 031 532 there is known a process for the preparation of polysiloxane block polymers which comprises liquid polydimethylsiloxane and spatially crosslinked polysiloxane having Si-bonded phenyl, phenylethyl or alkyl radicals having from 2 to 8 carbon atoms and optionally methyl radicals in the presence of Lewis acid or a basic substance heated and a silica airgel admits. The polysiloxane block polymers can be used as foam inhibitors, especially in detergents, dishwashing detergents and cleaners.

The German patent application DE 34 36 194 describes a process for producing a free-flowing defoamer granules by spray-drying an aqueous defoamer dispersion containing film-forming polymers. For the production of a granulate of the composition 1 to 10% by weight of water-insoluble defoaming agent, 0.2 to 2% by weight of a mixture of sodium carboxymethylcellulose and methylcellulose in a weight ratio of 80:20 to 40:60, 70 to 90% by weight of inorganic, water-soluble or dispersible carrier salts, the remainder being water, leaving a 0, 5 to 8 wt .-% of the cellulose ether mixture containing aqueous solution at a temperature of 15 to 60 ° C swell until the viscosity of the solution is at least 75% of the viscosity, which is measured with complete swelling of the cellulose ether solution, whereupon dispersed in this solution, the defoamer and spray-dried after addition of the carrier salts and optionally water, the homogenized dispersion. As defoamer active ingredients organopolysiloxanes, paraffins and mixtures of organopolysiloxanes and paraffins are used. The antifoam active ingredient content is 1 to 10% by weight, preferably 3 to 7% by weight. The carrier salt is preferably a mixture of sodium silicate, sodium tripolyphosphate and sodium sulfate.

From the European patent EP 0 337 523 B1 is a process for the preparation of powdered detergents which contain at least 5 wt .-% anionic surfactant, 20-80 wt .-% aluminosilicate and in water and anionic and nonionic surfactants substantially insoluble paraffin wax, which mitversprühen or subsequent spraying of the paraffin on the prefabricated detergent particle comprises as an essential process step. The paraffin wax can also be used in the form of a mixture with nonionic surfactants.

If, according to the variant disclosed in the last-mentioned document, the paraffin wax is not used alone but in combination with a bis-fatty acid amide which is known to enhance its foam regulator action but is generally solid at room temperature, it can be used according to International Patent Application WO 00/36063 the problem of clogging of the piping and nozzles used because of the risk of solidification of the Bisfettsäureamids by the use of an aqueous foam regulator emulsion, the 16 wt .-% to 70 wt .-% foam regulator active paraffin wax and / or silicone oil-based, 2 wt .-% to 15 wt.% Nonionic and / or anionic emulsifier and not more than 80 wt .-% water, dissolve. Particles with even greater stability can be made in accordance with international standards Patent application WO 02/074894 when solid support material containing alkali carbonate and a Brønsted acid is used.

When washing detergents containing conventional particulate foam regulators are used in machine washing processes, the occurrence of deposits on some washing machines, but especially on hydrophobic areas of the washing machine such as, for example, on the rubber sleeves sealing the dispensing area, is observed in many washing machines. Even if the washing result is not affected by such deposits, they are perceived by the consumer as not aesthetically pleasing and are thus undesirable. It is noteworthy that the deposits also occur when using particulate detergents, which consist for the most part of readily water-soluble ingredients and, for example, are completely free of water-insoluble builder material such as zeolite.

Surprisingly, it has now been found that these deposits can be avoided or at least significantly reduced with at least the same good defoamer performance if a foam control agent with a suitable silicone foam regulator system is used.

The invention relates to the use of a particulate formulated foam regulator comprising a combination of an organopolysiloxane (A) having at least one silicon-bonded substituent of the formula X-Ph, wherein X is a divalent organic group which is bonded via a carbon atom to silicon, and Ph a aromatic group means containing an organosilicon resin (B) and a hydrophobic filler (C), for preventing deposits on hydrophobic areas of a washing machine in the foam control of detergents used in automatic washing processes.

Suitable components (A), (B) and (C) are in particular in the European patent specification EP 1 075 864 described. The sum of the components (A), (B) and (C) is optionally also referred to below as silicone oil. In a preferred embodiment of the invention, the combination additionally contains foam-regulating Paraffin wax (D), which is solid at room temperature and in 100 ° C in completely liquid form.

The particulate foam regulator granules are preferably prepared by spraying an aqueous foam regulator emulsion comprising 6% to 75% by weight of the foam regulator active ingredient combination of (A), (B) and (C), and optionally (D) and 2% by weight to Contains 15 wt .-% nonionic and / or anionic emulsifier in water, on a solid support material, which optionally followed by a drying step prepared. The carrier material preferably contains alkali carbonate and a Brønsted acid.

It is preferred that a Brønsted acid used as part of the support material is in solid form at 25 ° C. It has at 25 ° C a water solubility of preferably at least 100 g / l. Preferably, it is selected from the di- and tricarboxylic acids, their acidic salts, the acidic salts of inorganic acids, in particular NaHSO ₄ , Na ₂ HPO ₄ and NaH ₂ PO ₄ , and mixtures thereof. In a preferred embodiment of the invention, the Brønsted acid is citric acid. The support material used preferably contains alkali carbonate and a Brønsted acid in weight ratios of 1: 1 1 to 100: 1, in particular from 20: 3 to 80: 3. The support material preferably has 40% by weight to 90% by weight, in particular 60% by weight to 80% by weight, of alkali carbonate and 1-20% by weight, in particular 3% by weight to 9% by weight. a Brønsted acid. It may consist solely of alkali metal carbonate and Brønsted acid or additionally contain other particulate components, solid and / or formulated in solid form washing or cleaning agent components come into question. These include, for example, conventional powders prepared by spray-drying aqueous slurries of their ingredients, solid oxygen-based bleaches, for example alkali percarbonates or alkali metal perborates, which may be present as so-called monohydrates or tetrahydrates, bleach activators formulated in powder form, for example tetraacetylethylenediamine granules, anionic surfactant compounds not prepared by conventional spray-drying Content of over 80 wt .-%, in particular more than 90 wt .-% of alkyl sulfate having alkyl chain lengths in the range of C ₁₂ to C ₁₈ , the remainder consisting essentially of inorganic Salts and water, present in granular form enzymes, such as a Enzymextrudat or Mehrenzymgranülat, powder formulated Soil release agent, powdered polycarboxylate co-builder, for example, alkali, and optionally also solid inorganic builder materials, such as zeolite A, zeolite P, zeolite -X and crystalline sheet silicates, and other inorganic salts such as alkali metal sulfate, alkali metal bicarbonate and alkali silicate and mixtures thereof. Preferably, the carrier material comprises a combination of alkali metal bicarbonate and alkali carbonate, the weight ratio of which is preferably 99: 1 to 10:90, in particular 95: 5 to 50:50. Preferred alkali metal in the salts mentioned as well as in the alkali carbonate is sodium.

In a preferred embodiment of the process, essentially as in the international patent application WO 00/36063 described in a granulation a build-up granulation in such a way that one mixes an amount of 40 to 110 parts by weight, in particular 60 to 90 parts by weight of support material, which may preferably additionally contain alkali metal sulfate and / or alkali metal bicarbonate, intensive and granulating an amount of 15 to 50 parts by weight , in particular 25 to 35 parts by weight of the foam regulator emulsion, optionally heated to a temperature in the range of 70 ° C to 180 ° C. Small amounts of water, preferably not more than 10 parts by weight, in particular from 1 to 5 parts by weight of water, may, if desired, also be added after or preferably before the addition of the foam regulator emulsion.

A foam regulator emulsion containing paraffin wax which can be used according to the invention is preferably prepared by melting the paraffin wax in the presence of the emulsifier, optionally cooling the melt to at most about 100 ° C. and stirring in water. If mixtures of nonionic emulsifier and anionic emulsifier are used, it is preferred to incorporate the nonionic emulsifier as described in the melt of paraffin wax and the anionic emulsifier not the melt, but before stirring the melt added to the water. When using paraffin wax in molten, uncooled form, it is preferable to use cold water having a maximum room temperature To use temperature. If the melt is cooled before stirring in water to a temperature of at most about 100 ° C, it is preferred to use water at a temperature of about 50 ° C to 80 ° C. Conventional stirring devices are usually sufficient to achieve the uniform distribution of all components and thus to produce the aqueous emulsion useful in this invention; The use of high-speed mixers or homogenizers (for example Ultra Turrax®) is generally not required. The incorporation of silicone oil is possible at any point of this process. If foam regulator emulsions are to be prepared which contain silicone oil as the sole foam regulator active ingredient or in comparison with the amount of paraffin wax in a higher amount, it is preferred to first mix the silicone oil with the nonionic and / or anionic emulsifier, add a portion of the water quantity with stirring so that a Forms emulsion of the type of water in silicone, continues to add more water until it comes to an inversion of the emulsion, stirred vigorously and then with stirring, the remaining water to. The emulsion thus obtained may optionally have partially multiple character, that is, in the outer water phase may also be droplets of the original core emulsion type water in silicone.

The foam regulator emulsions which can be used in the process according to the invention are stable and preferably have viscosities below 2500 mPa.s at 60 ° C., in particular in the range from 100 mPa.s to 500 mPa.s, measured for example with a Brookfield rotational viscometer, spindle no 2, 5 revolutions per minute, up.

It is preferred that in the organopolysiloxane (A) the group Ph is a moiety containing at least one benzene ring -C ₆ R ₅ wherein each R is independently hydrogen, halogen, hydroxyl, an alkoxy group of 1 to 6 carbon atoms or a monovalent hydrocarbon group with 1 to 12 carbon atoms or wherein two or more R groups together represent a divalent hydrocarbon group. The average number of siloxane units per molecule preferably ranges from 5 to 5,000. It is further preferred that in the organopolysiloxane (A) at least 50% of diorganosiloxane units of the formula -SiYY'O- and up to 50% diorganosiloxane units Y is an alkyl group having 1 to 4 carbon atoms and Y 'is an aliphatic hydrocarbon group having 1 to 24 carbon atoms, especially 1 to 6 carbon atoms. Preferably, the group X is an alkylene group having 1 to 24 carbon atoms and Ph is a phenyl group. Most preferably, the group is -X-Ph 2-phenylpropyl. The organopolysiloxane (A) preferably contains at least one crosslink site between siloxane polymer chains corresponding to the formula -X'- or -X'-Sx-X'-, wherein X 'is a divalent aliphatic organic group bonded to carbon via silicon, and Sx is an organosiloxane group.

The organosilicon resin (B) is preferably a non-linear silicone consisting of siloxane units of the formula R ' _a SiO _{(4-a) / 2} wherein R' represents a hydroxyl, hydrocarbyl or hydrocarbonoxy group and a has an average value of 0.5 until 2.4 has. It consists in particular of monovalent trihydroxycarbonsiloxy groups of the formula R "SiO _1/2 and tetrafunctional groups SiO _4/2 in the numerical ratio range from 0.4: 1 to 1.1: 1, where R" denotes an alkyl group. It preferably has an average particle size in the range from 2 μm to 50 μm.

The hydrophobic filler (C) is preferably selected from the group consisting of silica, titania, ground quartz, alumina, aluminosilicates, polyethylene waxes, microcrystalline waxes, zinc oxide, magnesium oxide, salts of aliphatic carboxylic acids, cyclohexylamine, alkylamides, SiO ₂ and mixtures thereof. In this case, pyrogenic or precipitated, in particular hydrophobicized silica having a surface area of at least 50 m ² / g is particularly preferred, as it is commercially available, for example, under the names Aerosil® or Sipemat®. Silicas preferably have an average particle size of 0.5 .mu.m to 30 .mu.m.

The viscosity of the silicone oil is preferably in the range from 1,000 mPa.s to 30,000 mPa.s, in particular from 1,500 mPa.s to 3,000 mPa.s.

The paraffin waxes in question in accordance with the invention are generally complex mixtures without a sharp melting point. The characterization is usually determined their melting range by differential thermal analysis (DTA) as described in "The Analyst" 87 (1962), 420, and / or their solidification point. This is the temperature at which the wax passes from the liquid to the solid state by slow cooling. According to the invention, paraffins which are completely liquid at room temperature, ie those having a solidification point below 25.degree. C., and solid paraffins which are solid at room temperature are useful. Preferably, the paraffin wax is solid at room temperature and is at 100 ° C in a completely liquid form. Can be used, for example, from the European patent application EP 0 309 931 known paraffin wax mixtures of, for example, 26 wt .-% to 49 wt .-% microcrystalline paraffin wax having a freezing point of 62 ° C to 90 ° C, 20 wt .-% to 49 wt .-% hard paraffin 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. up to 40 ° C. Preferably, paraffins or paraffin mixtures are used, which solidify in the range of 30 ° C to 90 ° C. It should be noted that even at room temperature appearing paraffin wax mixtures may contain different proportions of liquid paraffin. In the case of the paraffin waxes which can be used according to the invention, the liquid fraction at 40 ° C. is as high as possible without being 100% beautiful at this temperature. Preferred paraffin wax mixtures have at 40 ° C a liquid content of at least 50 wt.%, In particular from 55 wt .-% to 80 wt .-%, and at 60 ° C, a liquid content of at least 90 wt .-% to. The temperature at which a liquid content of 100% by weight of the paraffin wax is achieved is, with particularly preferred paraffin wax mixtures, still below 85 ° C., in particular at 75 ° C. to 82 ° C. It should also be ensured that the paraffins contain as far as possible no volatile components. Preferred paraffin waxes contain less than 1 wt .-%, in particular less than 0.5 wt .-% at 110 ° C and atmospheric pressure vaporizable fractions. Paraffin waxes which can be used according to the invention can be obtained, for example, under the trade names Lunaflex® from Fuller and Deawax® from DEA Mineralöl AG.

In one embodiment of the invention, silicone oil is preferably used in mixtures of paraffin wax and silicone oil in amounts such that the foam regulator emulsion used in the process according to the invention has a content of silicone oil in the range from 0.1% by weight to 10% by weight, in particular 1% by weight. -% to 5 wt .-% has. In a In another preferred embodiment, the foam regulator emulsion to be sprayed onto the carrier material contains a mixture of paraffin wax and silicone oil in a weight ratio of 11: 1 to 1.8: 1, in particular 5: 1 to 2: 1.

A foam regulator emulsion used with particular preference contains from 5% by weight to 40% by weight, in particular from 10% by weight to 35% by weight of silicone oil, from 1% by weight to 10% by weight, in particular 2% by weight 5 wt .-% paraffin wax and 50 wt .-% to 94 wt .-% water.

The foam regulator emulsion useful according to the invention and a foam regulator used according to the invention are preferably free of bis-fatty acid amides.

Nonionic emulsifiers which can be used in emulsions which can be used according to the invention are, in particular, the alkoxylates, preferably the ethoxylates and / or propoxylates of alcohols, alkylamines, vicinal diols, carboxylic acids and / or carboxamides, the alkyl groups having 8 to 22 C atoms, preferably 12 to 18 carbon atoms, understood. The average degree of alkoxylation of these compounds is generally from 1 to 10, preferably 2 to 5. They can be prepared in a known manner by reaction with the corresponding alkylene oxides. Also, products obtained by alkoxylation of fatty acid alkyl esters having 1 to 4 carbon atoms in the ester part according to the method of the international patent application WO 90/13533 can be produced, come into question. Suitable alcohol alkoxylates include the ethoxylates and / or propoxylates of linear or branched-chain alcohols having 8 to 22 C atoms, preferably 12 to 18 C atoms. Particularly suitable are the derivatives of fatty alcohols, although their branched-chain isomers can be used for the preparation of usable alkoxylates. Accordingly, in particular the ethoxylates of primary alcohols with linear dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are useful. The use of corresponding alkoxylates of mono- or polyunsaturated fatty alcohols, which include, for example, oleyl alcohol, elaidyl alcohol, linoleyl alcohol, linolenyl alcohol, gadoleyl alcohol and eruca alcohol, is also possible. Also esters or partial esters of carboxylic acids corresponding C chain length with polyols such as glycerol or oligoglycerol can be used. Preferred anionic emulsifiers are alkali metal salts of alkylbenzenesulfonic acids having 9 to 13 carbon atoms in the alkyl group, in particular sodium dodecylbenzenesulfonate. In addition to such emulsifiers, small amounts, optionally up to 4% by weight, of anionic and / or nonionic cellulose ethers, such as carboxymethylcellulose and / or hydroxyethylcellulose, may be present.

Essential for the preparation according to the invention useful emulsions is that one uses a homogeneous mixture of foam control system and in particular nonionic emulsifier. These can advantageously be achieved in a simple manner by melting the paraffin solid at room temperature in the presence of the silicone oil and the emulsifier, expediently with stirring or homogenization. Subsequent to the preferably at temperatures in the range of 60 ° C to 150 ° C, in particular 80 ° C to 150 ° C made formation of the mixture of defoamer and emulsifier this is, optionally after cooling, mixed with the water, wherein the water previously a in particular anionic emulsifier may have been added. In this case, the concentration of anionic emulsifier in water is preferably 5 wt% to 15 wt%.

The emulsion obtainable in this way is storage-stable at room temperature and preferably 3 to 60% by weight, in particular 15 to 45% by weight, of the carrier material is applied to it. After spraying the aqueous emulsion, a drying step, for example using conventional fluidized bed dryer, be connected, or bringing the emulsion with simultaneous drying, for example, also in a fluidized bed, on. The foam regulator granules according to the invention or obtainable by the process according to the invention preferably contain 5% by weight to 50% by weight, in particular 8% by weight to 35% by weight, of foam regulator active ingredient.

example

Essentially as in WO 02/074894 was described by applying a foam regulator emulsion containing paraffin wax having a freezing point according to DIN ISO 2207 of 45 ° C and a liquid content at 40 ° C of about 66 wt .-% and at 60 ° C of about 96% (Lunaflex®, manufacturer DEA), bistearylic acid ethylenediamide, silicone oil, anionic (Na-dodecylbenzenesulfonate) and nonionic (3-times ethoxylated C _12/14 fatty alcohol, manufacturer Cognis Germany GmbH) emulsifier, balance water, in a mixer to a presented therein combination of sodium carbonate (704 wt .) And citric acid (63 parts by weight), which had been previously mixed with 30 parts by weight of water, granules D1 and E1 with the following formulations (in each case wt .-%) prepared, wherein in the case of granules D1 differing from WO 02/074894 was dispensed with the use of Bisfettsäreamid and silicone oil as a silicone oil compound according to EP 1075864 was used. recipes D1 E1. Alkylbenzenesulfonate (Na salt) 0.98 1.4 Fatty alcohol C12-C14 + 3 EO 1.45 1.3 Hydroxypropane-1,2,3-tricarboxylic acid * 1H ₂ O 5.87 5.6 paraffin 11.4 10.7 Bistearylsäureethylendiamid - 1.6 sodium 65.4 62 Polyacrylic acid sodium salt 1.96 - silicone oil 3.19 1.2 water Rest on 100

The granules were incorporated into particulate universal detergents and used in machine washing processes. After 250 and in particular after 450 washes, the rubber cuffs of the washing machine were visually inspected:

Result after 450 washes: D1 E1 no deposits deposits

Claims (15)

1. Use of a foam regulator formulated in particulate form which contains a combination of an organopolysiloxane (A) with at least one silicon-attached substituent of the formula X-Ph, in which X means a divalent organic group, which is attached via a carbon atom to silicon, and Ph means an aromatic group, an organosilicon resin (B) and a hydrophobic filler (C), for preventing deposits on hydrophobic zones of a washing machine in the case of foam regulation of washing agents which are used in machine washing processes.
2. Use according to claim 1, characterised in that, in the organopolysiloxane (A), the group Ph is a unit which contains at least 1 benzene ring -C₆R₅, in which each R mutually independently means hydrogen, halogen, hydroxyl, an alkoxy group with 1 to 6 carbon atoms or a monovalent hydrocarbon group with 1 to 12 carbon atoms or in which two or more R groups together represent a divalent hydrocarbon group.
3. Use according to claim 1 or claim 2, characterised in that, in the organopolysiloxane (A), the average number of siloxane units per molecule ranges from 5 to 5,000.
4. Use according to any one of claims 1 to 3, characterised in that the organopolysiloxane (A) contains at least 50% of diorganosiloxane units of the formula -SiYY'O- and up to 50% of diorganosiloxane units of the formula -SiYXPhO-, wherein Y is an alkyl group with 1 to 4 carbon atoms and Y' is an aliphatic hydrocarbon group with 1 to 24 carbon atoms, in particular 1 to 6 carbon atoms.
5. Use according to any one of claims 1 to 4, characterised in that, in the organopolysiloxane (A), the group X is an alkylene group with 1 to 24 carbon atoms and Ph is a phenyl group.
6. Use according to any one of claims 1 to 5, characterised in that, in the organopolysiloxane (A), the group -X-Ph is 2-phenylpropyl.
7. Use according to any one of claims 1 to 6, characterised in that the organopolysiloxane (A) contains at least one crosslink site between siloxane polymer chains which is of the formula -X'- or -X'-Sx-X'-, in which X' is a divalent aliphatic organic group which is attached to carbon via silicon and Sx is an organosiloxane group.
8. Use according to any one of claims 1 to 7, characterised in that the organosilicon resin (B) is a nonlinear silicone which consists of siloxane units of the formula R'_aSiO_(4-a)/2, in which R' means a hydroxyl, hydrocarbon or hydrocarbonoxy group and a has an average value of 0.5 to 2.4.
9. Use according to any one of claims 1 to 8, characterised in that the organosilicon resin (B) is a siloxane resin which consists of monovalent trihydroxycarbonsiloxy groups of the formula R"SiO_1/2 and tetrafunctional groups SiO_4/2 in a numerical ratio range from 0.4:1 to 1.1:1, wherein R" means an alkyl group.
10. Use according to any one of claims 1 to 9, characterised in that the organosilicon resin (B) exhibits an average particle size in the range from 2 µm to 50 µm.
11. Use according to any one of claims 1 to 10, characterised in that the hydrophobic filler (C) is selected from the group consisting of silica, titanium dioxide, ground quartz, aluminium oxide, aluminosilicates, polyethylene waxes, microcrystalline waxes, zinc oxide, magnesium oxide, salts of aliphatic carboxylic acids, cyclohexylamine, alkylamides, SiO₂ and mixtures thereof.
12. Use according to any one of claims 1 to 11, characterised in that the hydrophobic filler (C) is a silica with an average particle size of 0.5 µm to 30 µm.
13. Use according to any one of claims 1 to 12, characterised in that the combination in the foam regulator formulated in particulate form additionally comprises a foam-regulating paraffin wax (D) which is solid at room temperature and assumes completely liquid form at 100°C.
14. Use according to claim 13, characterised in that, at 40°C, the paraffin wax exhibits a liquid fraction of at least 50 wt.%, in particular of 55 wt.% to 80 wt.%, and, at 60°C, a liquid fraction of at least 90 wt.%.
15. Use according to any one of claims 1 to 14, characterised in that the combination is present on a support material which contains alkali metal carbonate and a Brønsted acid, wherein the Brønsted acid assumes solid form at 25°C.