DEFOAMING COMPOSITIONS FOR DETERGENTS

Description

[0001] The invention relates to defoaming powders which, in addition to a defoaming formulation, contain a waxy non-silicone-containing component, a polycarboxylate binder and a powdered, water-soluble carrier material, their manufacturing method and their use for defoaming media, preferably aqueous media, in particular aqueous surfactant formulations.

[0002] In many liquid, especially aqueous, systems containing surfactant compounds as desired or undesired components, problems can arise due to foaming when these systems come into more or less intensive contact with gaseous substances, for example during the aeration of wastewater, intensive stirring of liquids, distillation, washing or dyeing processes, or filling operations.

[0003] This foam can be controlled mechanically or by adding defoamers. Siloxane-based defoamers have proven particularly effective. For example, siloxane-based defoamers are produced according to US 3383327 A by heating hydrophilic silica in polydimethylsiloxanes. Polyorganosiloxanes with lateral, longer-chain n-alkyl groups are also described as a basis for the production of effective defoamers in US 2009 / 0137446 A1.

[0004] In the application of solid products, such as detergents and cleaning agents, agrochemicals, and pharmaceutical formulations, powdered defoamers are primarily used. It is advantageous to convert these defoamers, which are normally oily, viscous liquids, into powder form, which can be achieved by adsorption of the defoamer onto solid carrier materials. It is particularly beneficial when used in washing powders if the carrier materials do not impede the washing process or are themselves components of the detergent. Most defoaming powders obtained by simply applying the defoamer to a carrier material share the characteristic that they rapidly lose their effectiveness during storage, especially in the presence of alkaline compounds.

[0005] To counteract this disadvantage, various solutions have been proposed. One possible solution involves encapsulating or coating the carrier material to improve the fixation of the defoamer. EP 0 995 473 A1 proposes the use of acidic polycarboxylates in combination with polyether-functionalized polysiloxanes on the zeolite carrier material for this purpose.

[0006] EP 0 210 731 A2 describes the use of glycerol monoesters as wax-like additives. Storage stability can be demonstrated when the described glycerol monoesters are used in excess with the polydimethylsiloxane-based defoamer.

[0007] Defoamers based on polyorganosiloxanes functionalized with alpha-methylstyryl groups and supported on sodium carbonate, starch, or zeolite are described in WO 2004 / 018073 A1, whereby a glycerol triester, such as glycerol tristearate, is mandatory as an additive. The additives have a positive effect on the effectiveness of the defoamer powders in the application of foam control in washing powders. No statement is made regarding storage stability.

[0008] WO 2004 / 018074 A1 describes defoaming powders that also contain waxy glycerol triesters as an additive. Sometimes in combination with other more polar additives, such as glycerol monoesters, alkylphenols, fatty alcohols, or fatty acids, the glycerol triesters are sprayed together with the defoaming agent onto a carrier, in particular sodium carbonate or starch. The amount of additives is at least 50% by weight based on the defoaming agent. Here, too, a positive effect on the effectiveness of the defoaming powders in the application of foam control of washing powders was demonstrated. No statement is made regarding storage stability.

[0009] The disadvantage of the described solutions lies in the sometimes considerable quantities of the additionally required organic additives, their still insufficient storage stability in a solid surfactant matrix, and their suboptimal aqueous solubility or aqueous dispersibility.

[0010] The object of the invention was therefore to provide defoaming powders which, in addition to the defoaming formulation and the carrier material, contain only small amounts of additional components, exhibit excellent storage stability, and demonstrate excellent aqueous solubility and dispersibility. In particular, the produced defoaming powders should be suitable for use in washing and cleaning agents.

[0011] The invention relates to defoamer powders containing (A) 100 parts by weight of a defoaming formulation, comprising (Aa) a polysiloxane comprising units of formula (I) R1< R2< SiO2 / 2 (I), wherein R1< is the same or different and represents a monovalent, optionally branched, SiC-bonded hydrocarbon residue with 1 to 5 C atoms, R2< is the same or different and represents a monovalent, optionally branched, SiC-bonded hydrocarbon residue with 6 to 30 C atoms, (Ab) a filler, (Ac) an organopolysiloxane resin comprising units of the general formula R3< a (R4< O) b SiO2 (4-ab) / 2 (II), wherein R3< is the same or different and represents a monovalent, optionally substituted, SiC-bonded hydrocarbon residue with 1 to 30 C atoms, R4< is the same or different and represents a hydrogen atom or a monovalent, possibly substituted hydrocarbon residue with 1 to 4 C atoms means, a is 0, 1, 2 or 3 and b is 0, 1, 2 or 3, with the proviso thatthat the sum a + b , ≤ 3 is and in less than 50% of all units of the formula (II)in the organopolysiloxane resin the sum a + b = 2, optionally (Ad) a further organopolysiloxane consisting of units of formula (III) and (IV) R 1< 2 SiO 2 / 2 (III), R 5< R 1< 2 SiO 1 / 2 (IV), wherein R 1< has the meaning given above, R 5< may be the same or different and R 1< or -OR 6<, where R 6< means a hydrogen atom or a monovalent, optionally substituted hydrocarbon residue with 1 to 25 C atoms, optionally (Ae) a water-insoluble organic compound, optionally (Af) an alkaline or acidic catalyst or its reaction product with components (Aa) to (Ad) (B) 10 to 45 parts by weight based on 100 parts by weight of the defoaming formulation (A) of a waxy additive containing a monoester (B') made from glycerin and a fatty acid, free from a polysiloxane-containing additive and containing less than 5% by weight.(C) Contains -% of a triester (B'') of glycerol and a fatty acid, (D) 10 to 50 parts by weight, based on 100 parts by weight of the defoaming formulation (A), of a polycarboxylate binder having a pH of 3 or less when dissolved in water. (D) 120 to 5000 parts by weight, based on 100 parts by weight of the defoaming formulation (A), of at least one powdered carrier material, provided that the carrier material contains less than 50% by weight alkaline carrier material, preferably less than 40% by weight alkaline carrier material, preferably less than 25% by weight alkaline carrier material.

[0012] The term defoamer powder includes both powdered and granulated products.

[0013] Surprisingly, it has now been found that the defoamer powders composed in this way are characterized by significantly improved storage stability in washing powders as well as significantly improved water solubility or water dispersibility in the washing lye, while requiring less additional agents compared to the state of the art.

[0014] The defoamer powders according to the invention preferably contain 10 to 42 parts by weight of the waxy additive (B), 10 to 47 parts by weight of the polycarboxylate binder (C) and 200 to 2000 parts by weight of the powdered carrier material (D), each based on 100 parts by weight of the defoamer formulation (A), and particularly preferably 13 to 40 parts by weight of the waxy additive (B), 13 to 45 parts by weight of the polycarboxylate binder (C) and 300 to 1200 parts by weight of the powdered carrier material (D), each based on 100 parts by weight of the defoamer formulation (A).

[0015] The defoamer powders according to the invention preferably consist essentially of the components (A), (B), (C) and (D).

[0016] Preferably the defoaming formulation (A) consists of the components (Aa), (Ab), (Ac) and optionally the components (Ad), (Ae) and (Af).

[0017] Preferably the defoaming formulations contain (A) (1) at least 55 wt.%, preferably at least 65 wt.%, particularly preferably at least 75 wt.%, and preferably at most 97 wt.%, preferably at most 90 wt.%, particularly preferably at most 85 wt.% polysiloxanes (Aa), (2) at least 1 wt.%, preferably at least 2 wt.%, particularly preferably at least 3 wt.%, and preferably at most 15 wt.%, preferably at most 12 wt.%, particularly preferably at most 10 wt.% fillers (Ab), (3) at least 1 wt.%, preferably at least 2 wt.%, particularly preferably at least 3 wt.%, and preferably at most 15 wt.%, preferably at most 12 wt.%, particularly preferably at most 10 wt.% organopolysiloxane resins (Ac) from units of formula (II), (4) at least 0 wt.% and preferably at most 15 wt.%, preferably at most 10 wt.%, particularly preferably at most 7.5 wt.% organopolysiloxanes (Ad) consisting of units of formula (III) and (IV), (5) at least 0 wt.% and preferably at most 15 wt.%, preferably at most 10 wt.%(6) at least 0 wt.%, preferably at least 0.05 wt.%, particularly preferably at least 0.1 wt.%, and preferably at most 1 wt.%, preferably at most 0.5 wt.%, particularly preferably at most 0.3 wt.%, alkaline or acidic catalysts (Af) or their reaction products with components (Aa) to (Ad).

[0018] Preferably, the organopolysiloxanes (Aa) used in the defoaming formulations (A) are those of formula (VIII) R 5< R 1< 2 SiO-(SiR 1< 2 O) x -(SiR 1< R 2< O) y -SiR 1< 2 R 5< (VIII), wherein R1<, R2< and R5< have the meanings given above, x is greater than or equal to 0 or on average less than 200, preferably less than 100, particularly preferably less than 50, y is on average greater than 5, preferably greater than 10, and less than 200, preferably less than 100, particularly preferably less than 50. Organopolysiloxanes (Aa) may additionally have branches by including units of formula (IX) and (X). SiO4 / 2 (IX) R1< SiO3 / 2 or R2< SiO3 / 2 or R5< SiO3 / 2 (X) R1< LSiO2 / 2 or R2< LSiO2 / 2 or R5< LSiO2 / 2 (XI) wherein R1<, R2< and R5< have the meanings given above and L represents a divalent structure linking two organopolysiloxane chains together. L can be an alkylene group, such as e.g.an ethylene, propylene, butylene, hexylene, or octylene group, preferably a hexylene or octylene group, a divalent aromatic group such as the 1,2-bis-ethylenebenzene, 1,4-bis-ethylenebenzene, or 1,8-bis-ethylenenaphthalene group, a cycloalkylene group such as the 1,4-bisethylenecyclohexane group, or a divalent organosiloxane chain.

[0019] Examples of hydrocarbon residues R 1< are alkyl residues, such as the methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl, tert-pentyl residues; and cycloalkyl residues, such as the cyclopentyl residue.

[0020] Preferred examples for R 1< are methyl and ethyl groups. A particularly preferred example is the methyl group.

[0021] Examples of hydrocarbon residues R 2< are alkyl residues, for example hexyl residues, such as n-hexyl, heptyl residues, such as n-heptyl, octyl residues, such as n-octyl and iso-octyl, such as 2,2,4-trimethylpentyl and 2-ethylhexyl, nonyl residues, such as n-nonyl, decyl residues, such as n-decyl, dodecyl residues, such as n-dodecyl, tetradecyl residues, such as n-tetradecyl, hexadecyl, such as n-hexadecyl and octadecyl; cycloalkyl residues, such as cyclohexyl, cycloheptyl, methylcyclohexyl and 4-ethylcyclohexyl; Aryl groups, such as the phenyl, naphthyl, anthryl and phenanthryl groups; alkaryl groups, such as o-, m-, p-tolyl groups, xylyl groups and ethylphenyl groups; and aralkyl groups, such as the benzyl group, the 2-phenylpropyl group and the alpha- and beta-phenylethyl groups.

[0022] Preferred examples for R 2< are the n-octyl group, the n-decyl group, the n-dodecyl group, the n-tetradecyl group, the n-hexadecyl group, the n-octadecyl group, the phenyl group, the benzyl group, and the 2-phenylpropyl group. Particularly preferred examples are the n-octyl group, the n-dodecyl group, the phenyl group, and the 2-phenylpropyl group.

[0023] Examples, preferred examples and particularly preferred examples for R 5< are the examples, preferred examples and particularly preferred examples for R 1< or remainders of the formula -OR 6< .

[0024] Examples of R 6< are the hydrogen atom or alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl groups, hexyl groups, such as n-hexyl, heptyl groups, such as n-heptyl, octyl groups, such as n-octyl and iso-octyl groups, such as 2,2,4-trimethylpentyl and 2-ethylhexyl, nonyl groups, such as n-nonyl, decyl groups, such as n-decyl, dodecyl groups, such as n-dodecyl, tetradecyl groups, such as the n-tetradecyl group, hexadecyl groups such as the n-hexadecyl group and octadecyl groups such as the n-octadecyl group; cycloalkyl groups such as the cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl and 4-ethylcyclohexyl groups.

[0025] Preferred examples for R 6< are the hydrogen atom or methyl and ethyl groups.

[0026] Particularly favored examples are the hydrogen atom or the methyl group.

[0027] Preferably, the fillers (Ab) used in the defoaming formulations (A) have a BET surface area of ​​20 to 1000 m² / g. Preferably, the fillers (Ab) have a particle size of less than 10 µm and an agglomerate size of less than 100 µm.

[0028] Examples of fillers (Ab) include silicon dioxide (silica), titanium dioxide, aluminum oxide, metal soaps, quartz flour, PTFE powder, fatty acid amides, e.g. ethylene bisstearamide, and finely divided hydrophobic polyurethanes.

[0029] Preferably, silicon dioxide (silica), titanium dioxide, or aluminum oxide with a BET surface area of ​​20 to 1000 m² / g are used as fillers. These fillers preferably have a particle size of less than 10 µm and an agglomerate size of less than 100 µm.

[0030] Preferably, silicas are used as fillers (Ab), particularly those with a BET surface area of ​​50 to 800 m² / g. These silicas can be pyrogenic or precipitated. Both pretreated silicas, i.e., hydrophobic silicas, and hydrophilic silicas can be used as fillers (Ab). Examples of commercially available hydrophobic silicas that can be used according to the invention are HDK® < H2000, a pyrogenic silica treated with hexamethyldisilazanes with a BET surface area of ​​140 m² / g (commercially available from Wacker Chemie AG, Germany), and a precipitated silica treated with polydimethylsiloxane with a BET surface area of ​​90 m² / g (commercially available under the name "Sipernat® < D10" from Evonik, Germany).

[0031] Hydrophilic silicas can also be hydrophobized in situ if this is advantageous for the desired efficacy of the defoamer formulation. Numerous methods for hydrophobizing silicas are known. The in situ hydrophobization of hydrophilic silica can be achieved, for example, by heating the silica dispersed in component (Aa) or in a mixture of components (Aa), (Ac), optionally (Ad), and optionally (Ae) to temperatures of 100 to 200°C for several hours. The reaction can optionally be supported by the addition of catalysts (Af) and hydrophobizing agents such as short-chain OH-terminated polydimethylsiloxanes, silanes, or silazanes.

[0032] The component (Ac) used in the defoaming formulations (A) is preferably a silicone resin consisting of units of formula (II), in which the sum a+b is equal to 2 preferably in less than 30%, preferably in less than 5%, of the units in the resin.

[0033] Preferably, R 3< signifies a hydrocarbon residue with 1 to 30 carbon atoms.

[0034] Examples of hydrocarbon residues R 3< are alkyl residues, such as methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl residues; hexyl residues, such as n-hexyl; heptyl residues, such as n-heptyl; octyl residues, such as n-octyl and iso-octyl, such as 2,2,4-trimethylpentyl and 2-ethylhexyl; nonyl residues, such as n-nonyl; decyl residues, such as n-decyl; dodecyl residues, such as n-dodecyl; and tetradecyl residues, such as... n-tetradecyl groups, hexadecyl groups such as n-hexadecyl and octadecyl groups such as n-octadecyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl and 4-ethylcyclohexyl; aryl groups such as phenyl, naphthyl, anthryl and phenanthryl; alkaryl groups such as o-, m-, p-tolyl, xylyl and ethylphenyl; and aralkyl groups such as benzyl, 2-phenylpropyl and alpha- and beta-phenylethyl.

[0035] Preferred examples of residues R 3< are the methyl, ethyl and phenyl residues.

[0036] A particularly favored example of the residue R 3< is the methyl residue.

[0037] Examples of residues R 4< are the hydrogen atom and alkyl residues, such as the methyl, ethyl, n-propyl, iso-propyl and n-butyl residues.

[0038] Preferably, the residue R 4< is a hydrogen atom or a methyl or ethyl residue.

[0039] The organopolysiloxane resins (Ac) preferably consist of units of formula (II) MQ resins made from units of the formulas SiO 2 (IX) and R 3< 3 SiO 1 / 2 (XII), where R 3< has the meaning given above.

[0040] The molar ratio of M to Q units is preferably in the range of 0.5 to 2.0, more preferably in the range of 0.6 to 1.0. In addition to the M and Q units, the MQ resins may optionally contain small amounts of R3SiO3 / 2 or (R4O)SiO3 / 2(T) units or R3 / 2SiO2 / 2(D) units, in amounts preferably of 0.01 to 20 mol%, more preferably of 0.01 to 5 mol%, based on the sum of all siloxane units, where R3 and R4 have the meanings given above. These MQ resins may also contain up to 10 wt% free Si-bound hydroxy or alkoxy groups, such as methoxy or ethoxy groups.

[0041] Preferably, these organopolysiloxane resins (Ac) have a viscosity greater than 1000 mPa·s at 25°C and 101.425 kPa or are solids. The weight-average molecular weight (based on a polystyrene standard) of these resins, determined by gel permeation chromatography, is preferably 200 to 200,000 g / mol, and in particular 1000 to 20,000 g / mol.

[0042] Organopolysiloxanes (Ad), which are different from polysiloxanes (Aa), may be used in the defoaming formulations (A).

[0043] Preferably the organopolysiloxanes (Ad) are of formula (IXX) R 5< R 1< 2 SiO-(SiR 1< 2 O) z -SiR 1< 2 R 5< (IXX), wherein R 1< and R 5< have the meanings given above, where on average greater than 5, preferably greater than 10, and less than 500, preferably less than 200, particularly preferably less than 100.

[0044] Water-insoluble organic compounds (Ae) may be used in the defoaming formulations (A).

[0045] For the purposes of the present invention, the term "water-insoluble" shall be understood to mean a solubility in water at 25°C and a pressure of 101.425 kPa of a maximum of 3 percent by weight.

[0046] The optionally used component (Ae) is preferably a water-insoluble organic compound with a boiling point greater than 100°C at atmospheric pressure, i.e., at 900 to 1100 hPa, and a melting point of less than 35°C, in particular those selected from mineral oils, virgin oils, isoparaffins, polyisobutylenes, residues from oxo alcohol synthesis, esters of low molecular weight synthetic carboxylic acids, such as pentanediol-1,3-diisobutyrate, fatty acid esters, such as octyl stearate, octyl oleate, isopropyl laurate, methyl laurate or isopropyl myristate, fatty alcohols that are liquid at temperatures greater than 35°C, ethers of low molecular weight alcohols, phthalates and esters of phosphoric acid.

[0047] Examples of alkaline catalysts (Af) are alkali and alkaline earth hydroxides, such as NaOH, KOH, CsOH, LiOH and Ca(OH)₂. Examples of acidic catalysts (Af) are hydrochloric acid, sulfuric acid and phosphorus nitrile chlorides.

[0048] The reaction products of (Af) with components (Aa) to (Ad) include, for example, the product of the silica preferred as filler (Ab) with

[0049] Alkali hydroxides, such as potassium silicate or sodium silicate, are used. The catalysts can be dosed in typical organic solvents such as alcohols (e.g., methanol, ethanol, isopropanol) or esters (e.g., ethyl acetate).

[0050] The components (Aa) to (Af) used in the defoaming formulations (A) can each be one type of such component as well as a mixture of at least two types of each component.

[0051] The defoaming formulations (A) have a viscosity of preferably 100 to 2,000,000 mPa·s, preferably 500 to 80,000 mPa·s, particularly preferably 1,000 to 15,000 mPa·s, each at 25°C and 101.425 kPa.

[0052] The preparation of the defoamer formulations (A) according to the invention can be carried out by known methods, such as by mixing all components, for example, by applying high shear forces in colloid mills, dissolvers, or rotor-stator homogenizers. The mixing process can be carried out at reduced pressure to prevent the incorporation of air, which may be contained, for example, in highly dispersed fillers. Subsequently, the fillers can be hydrophobized in situ if required.

[0053] It is also possible to first introduce and, if necessary, heat component (Aa) and then successively add components (Ab), (Ac), (Ad), (Ae) if necessary and (Af) if necessary.

[0054] In a preferred embodiment, component (Ac) is added in dissolved form as a solution to component (Ad) or (Ae) or parts of component (Ad) or (Ae).

[0055] The waxy additive (B) used is an organic material with a melting point in the range of 35 to 85°C, the main component of which is a monoester of glycerol and a fatty acid (also known as 1-monoacylglycerol).

[0056] These are specifically monoesters of glycerol and aliphatic fatty acids with a carbon chain containing 12 to 20 carbon atoms. This includes both racemic and optically active forms. Examples of such monoesters are glycerol monolaurate, glycerol monomyristate, glycerol monopalmitate, and glycerol monostearate. A particularly favored example of a monoester is glycerol monostearate.

[0057] The waxy additive (B) used can be an organic material with a melting point in the range of 35 to 85°C, which, due to its manufacturing process, is a mixture of several components, the main component being a monoester of glycerol and a fatty acid.

[0058] Technical products containing 1-monoacylglycerols are generally mixtures of a 1-monoacylglycerol and a diacylglycerol with varying monoacylglycerol contents. Furthermore, these technical products may also contain small amounts of triacylglycerol, free glycerol, and free fatty acids.

[0059] In the case of glyceryl monostearate, it is usually a mixture of glyceryl monostearate, glyceryl instearate and possibly glyceryl monopalmitate, as well as small amounts of glyceryl tristearate and free glycerol (in the case of non-emulsifying or non-self-emulsifying glyceryl monostearate) or a certain amount of soap (in the case of self-emulsifying glyceryl monostearate).

[0060] The waxy additive (B) used can also be an organic material with a melting point in the range of 35 to 85°C, in which an additional waxy organic material has been deliberately added to the monoester of glycerol and a fatty acid as the main component. This additional waxy organic material, which is not an ester of fatty acid and glycerol, has a melting point in the range of 35 to 85°C.

[0061] Examples of an additional waxy material are semi-synthetic waxes such as amide waxes (for example, stearamide, behenamide, erucamide, oleamide), alcohol waxes or ketone waxes, or synthetic waxes such as polyolefin waxes or waxy hydrocarbons (for example, hard paraffins with a melting point of 50 to 62°C).

[0062] Regardless of whether it is due to the manufacturing process or whether an additional waxy material is used, the content of 1-monoacylglycerol is preferably greater than or equal to 30 wt.%, preferably greater than or equal to 50 wt.% and in particular greater than or equal to 70 wt.%, and the content of triacyclglycerol is preferably less than 5 wt.% in the total mixture of the waxy component (B) used.

[0063] Essential for the defoamer powders according to the invention is the combination of the waxy additive (B) and at least one polycarboxylate binder (C) which has a pH of 3 or less when dissolved or dispersed in water.

[0064] It has been shown that this combination is essential for good storage stability of the defoamer powder according to the invention in a washing powder.

[0065] The polycarboxylate binder (C) is a water-soluble or water-dispersible polymer, homopolymer, copolymer, or a salt thereof. It comprises at least 60% by weight segments with the general formula (CR 8< 2 -CR 8< 2 ) n (V), where n takes on a value between 10 and 100,000, preferably between 20 and 10,000, particularly preferably between 30 and 1,000, R 8< is selected from hydrogen, (optionally substituted) hydrocarbon residues with 1 to 30 carbon atoms, carboxyl groups or their salts, and groups of the general formula -C(O)-OR 9< (VI), -C(O)-N(R 10< ) 2 (VII), wherein R 9< represents an optionally functionalized hydrocarbon residue with 1 to 30 carbon atoms and R 10< is either hydrogen, the residue R 9< or R 11< is -SO 3 X, wherein R 11< is a divalent alkylene residue with 1 to 12 carbon atoms and X is a hydrogen atom or a cation, provided that at least 5 mol%, preferably at least 10 mol%, particularly at least 15 mol% of the Residues R 8< acidic group are selected from the carboxyl group or its salts and groups containing a sulfonyl group or its salts,preferably selected from the carboxyl group and its salts.

[0066] The residues R 8< can be the same or different.

[0067] Examples of residues R 8< are the hydrogen atom, monovalent (possibly substituted) alkyl, aryl, aralkyl and cycloaliphatic hydrocarbon residues, such as methyl, ethyl, heptyl, octyl, 2-ethylhexyl, decyl, isodecyl, dodecyl, lauryl, myristyl, stearyl, phenyl, (sulfonyl)phenyl, such as (4-sulfonyl)phenyl or (2-sulfonyl)phenyl, 1-naphthyl, and (sulfonyl)naphthyl residues, carboxyl group or groups of formulas (VI) and (VII).

[0068] Preferred residues R 8< are the hydrogen atom, the methyl residue, the ethyl residue, the (sulfonyl)phenyl residue, the carboxyl group or groups of formulas (VI) and (VII).

[0069] The residues R 9< can be the same or different monovalent alkyl, aryl, aralkyl and cycloaliphatic hydrocarbon residues.

[0070] Examples of residues R 9< are the methyl, ethyl, n-butyl, iso-butyl, tert-butyl, 2-ethylhexyl, lauryl, stearyl, benzyl, isopropyl, neopentyl, cyclohexyl, 2-hydroxyethyl and 2-hydroxypropyl groups.

[0071] The residues R 10< can be the same or different and can mean either hydrogen, the residue R 9< or R 11< -SO 3 X.

[0072] Examples of the divalent alkylene residue R 11< are the methylene group, the 1,2-ethylene group, the 1,3-propylene group, the 1,2-propylene group or the (2-methyl-)1,2-propylene group.

[0073] Examples of X are the hydrogen atom or a cation, such as the sodium, potassium, calcium, magnesium, lithium cation or ammonium cations, for example derived from ammonia, monoethanolamine, diethanolamine, triethanolamine or isopropylamine.

[0074] Examples of preferred segments according to the general formula (V) are: (CH 2 -C(CH 3 )R 12< ) n (XIII) (CH 2 -C(C 2 H 5 )R 12< ) n (XV) (CH 2 -CHR 12< ) n (XVI) (CHR 12< -CHR 12< ) n (XVII) where R 12< is selected from the groupings -C(O)-OH (XVIII), and -C(O)-NR 10< 2 (VII), where R 10< has the meaning given above.

[0075] The carboxyl group (XVIII) as well as the sulfonyl group can also be partially neutralized by bases, preferably bases with a singly positively charged cation, such as alkali cations or ammonium cations, while still fulfilling the condition that the binder (C) has a pH of 3 or less when dissolved in water.

[0076] Examples of monomers that lead to these structures include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, methylenemalonic acid, 4-vinylbenzenesulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid (AMPS).

[0077] Maleic anhydride or maleic imide can also be used as monomers. In this case, it is preferred that the incorporated anhydride or imide groups are wholly or partially reacted with water, alcohols, amines, or ammonia solution to form carboxyl, ester, and / or amide groups.

[0078] Preferred examples of monomers that lead to these structures are acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, itaconic acid, aconitic acid, mesaconic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), maleic anhydride and maleic imide.

[0079] Particularly favored examples of monomers that lead to these structures are acrylic acid, maleic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and maleic anhydride.

[0080] Copolymerization with smaller amounts of monomeric materials that do not contain carboxylic acids, i.e., methyl acrylate, ethyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, neopentyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate, acrylamide, methacrylamide, vinylmethyl, vinyl methyl ether, styrene, and ethylene, is suitable for the use of Polycarboxylates in the foam suppressants according to the invention are not harmful.Depending on the type of polycarboxylate, this content can be kept low or it can be up to about 40 percent by weight of the total polymer or copolymer.

[0081] Such and similar compounds (C) that can be used within the scope of the present invention are known and commercially available; for example, Sokalan® PA80S and Sokalan® PA110S (BASF, Germany), which have a pH of about 1.5, acrylic-malein copolymers, for example, Sokalan® CP12S (BASF, Germany) with a pH of about 1, and modified polyacrylic acid polymers, for example, Sokalan® CP10S and 13S (also BASF, Germany), which have a pH of about 1.5, or Aquatreat® AR-540 (Nouryon, copolymer of acrylic acid and sulfonated monomers).

[0082] The defoamer powders according to the invention preferably contain carrier materials (D) which are not alkaline carrier materials. Alkaline carrier materials are those which, when dissolved or dispersed in water, result in an alkaline pH value, i.e., a pH value greater than or equal to 11.

[0083] This is determined from a 0.02 wt% solution or a 5 wt% suspension. It has been found that the storage stability of the defoamer powders according to the invention in washing powder is significantly improved when predominantly non-alkaline carrier materials are used.

[0084] The carrier materials (D) contained in the defoamer powder according to the invention can each be one type of such component as well as a mixture of at least two types of each component.

[0085] If only one type of component is used as the carrier material, it should be a non-alkaline carrier material.

[0086] If several components are used as carrier material, a non-alkaline carrier material should be the main component. This is the case if the proportion of non-alkaline carrier materials is greater than 50 wt.%, preferably greater than 60 wt.%, and particularly preferably greater than 75 wt.% of the total amount of carrier material (D).

[0087] Examples of non-alkaline carrier materials include phosphates, such as powdered or granular sodium tripolyphosphate, sodium sulfate, sodium bicarbonate, sodium citrate, sodium acetate, or cellulose derivatives such as sodium carboxymethylcellulose.

[0088] Examples of alkaline support materials that can be used in amounts of less than 50 wt.%, preferably less than 40 wt.%, and particularly preferably less than 25 wt.%, are sodium carbonate, zeolites, for example zeolite A or zeolite X, aluminosilicates or silicates, for example magnesium silicate.

[0089] Carrier materials that exhibit good water solubility are particularly preferred, such as sodium sulfate, sodium bicarbonate, sodium citrate, sodium acetate and cellulose derivatives such as sodium carboxymethylcellulose.

[0090] Good water solubility within the meaning of the present invention is given when a solubility in water at 25°C and a pressure of 101.425 kPa of at least 3 percent by weight is achieved.

[0091] If only one type of component is used as the carrier material, it should be a carrier material that is highly water-soluble.

[0092] If several components are used as the carrier material, a highly water-soluble carrier material should be the main component. This is the case if the proportion of highly water-soluble carrier materials is greater than 50 wt.%, preferably greater than 60 wt.%, and particularly preferably greater than 75 wt.% of the total amount of carrier materials (D).

[0093] It has been shown that the water solubility or water dispersibility of the defoamer powders according to the invention is significantly improved when a water-soluble carrier material is used as the main component.

[0094] Examples of carrier materials that are readily soluble in water include phosphates, such as powdered or granular sodium tripolyphosphate, sodium sulfate, sodium bicarbonate, sodium citrate, sodium acetate, or cellulose derivatives such as sodium carboxymethylcellulose.

[0095] Examples of poorly water-soluble support materials that can be used in amounts of less than 50 wt.%, preferably less than 40 wt.%, and particularly preferably less than 25 wt.%, are zeolites, for example zeolite A or zeolite X, aluminosilicates or silicates, for example magnesium silicate.

[0096] The invention further relates to a method for producing the defoamer powders, in which a premix, preferably in the form of a dispersion, in particular an aqueous dispersion, is produced from defoamer formulation (A), waxy additive (B) and binder (C) and this premix is ​​mixed with the powdered carrier material.

[0097] The premix is ​​preferably obtained by dispersing an emulsion or dispersion of defoamer formulation (A) and waxy additive (B) in a solution or dispersion of the binder (C), preferably aqueous.

[0098] The production of the defoamer powders according to the invention can be carried out, for example, by mixing a premixture of the defoamer formulation (A) and the waxy additive (B) with the powdered carrier material (D), and subsequently or simultaneously incorporating a solution or dispersion of a binder (C).

[0099] Alternatively, it is also possible to prepare an emulsion or dispersion of a premix of the defoaming formulation (A) and the waxy additive (B) in a solution or dispersion of a binder (C) in a known manner and then to incorporate this onto the powdered carrier material (D).

[0100] This manufacturing method, using an emulsion or dispersion of a premix of the defoaming formulation (A) and the waxy additive (B) in a solution or dispersion of a binder (C), is the preferred approach.

[0101] The powdery mass obtained after mixing can be dried if necessary to ultimately obtain a free-flowing powder. Drying can take place directly in the mixer or subsequently in a separate dryer of known design, e.g., a belt dryer, a spray dryer, a screw dryer, a paddle dryer, or an adsorption dryer. Preferably, drying is carried out at a temperature of 60°C to 150°C.

[0102] Various known mixers can be used to produce the defoamer powders according to the invention, which are preferably heatable and / or evacuable to enable drying in the same unit.

[0103] Examples of suitable mixers are plowshare mixers, Z-mixers, screw extruders, or planetary mixers. The technologically determined residual water content of the defoamer powder according to the invention is less than 10 wt.%, preferably less than 5 wt.%.

[0104] The defoamer powders according to the invention are preferably used in washing and cleaning agents.

[0105] However, they can be used wherever foaming needs to be controlled or prevented. An example of this is powdered pesticides, especially those containing large amounts of surfactants. The defoamer powders according to the invention can also be advantageously used in chemical processes or wastewater treatment.

[0106] The defoamer powders according to the invention are dosed by simply mixing them, for example, with the detergent. This is advantageously carried out at the time when the detergent is mixed with other components, such as enzymes or bleaching agents. However, it is also possible to dose the defoamer powder according to the invention directly into the foaming medium.

[0107] The defoamer powders according to the invention are preferably used in surfactant-containing solid media whose use in aqueous environments leads to foam formation, preferably in washing and cleaning agents, in particular in solid (powdered or granular) washing and cleaning agents. The invention therefore relates to washing or cleaning agents containing the defoamer powders according to the invention.

[0108] The viscosity of the individual components, in particular components (Aa), is determined according to DIN 53019-1 (2008-09) (fundamentals and measurement geometry), DIN 53019-2 (2001-2)

[0109] (Viscometer calibration and determination of measurement uncertainty) and DIN 53019-3 (2008-09) (Measurement deviations and corrections) or according to DIN EN ISO 3219 (1994) (Plastics - Polymers / resins in liquid, emulsified or dispersed state - Determination of viscosity using a rotational viscometer at a defined velocity gradient) with a cone-plate viscometer MCR 300 (Paar-Physika) at 25°C and a shear gradient as specified accordingly.

[0110] The viscosity of the defoamer formulation (A) is determined according to DIN EN ISO 3219 using a cone-plate viscometer MCR 300 (Paar-Physika) at 25°C and a shear rate of 50 / s.

[0111] The amount of monoacylglycerol or triacylglycerol in commercially available monoacylglycerols is determined by high-performance liquid chromatography (HPLC) using a Phenomenex Luna 5 µm C5 100 Å (250 × 4.6 mm) HPLC column. A mixture of 0.05% aqueous trifluoroacetic acid and THF is used as the mobile phase, with a gradient from 30% THF to 100% THF at a flow rate of 1.0 mL / min and a column temperature of 30°C. Detection is performed using an evaporative light scattering detector (ELSD) (1.4 SLM - 30° Neb - 30°C Evap - 50% light source intensity). 10 mg of the samples are dissolved in 10 mL of THF, mixed with 1 mL of water, and made up to a total of 10 mL with additional THF. It is calibrated against chemically pure monoacylglycerols or triacylglycerols.

[0112] In the following examples, all parts and percentages refer to weight unless otherwise stated. Unless otherwise stated, the following examples are performed at atmospheric pressure (approximately 1000 hPa) and room temperature (approximately 20°C), or at the temperature reached when the reactants are combined at room temperature without additional heating or cooling. Example 1: Production of the defoaming formulations (A): Production of the defoaming formulations (A1):

[0113] 82.3 parts by weight of a trimethylsiloxy-terminated methyloctylsiloxane with an average chain length of 55 and a viscosity of 700 mPa·s (measured at 25°C and a shear rate of 10 / s), 5 parts of a pyrogenic silica with a BET surface area of ​​300 m² / g (available under the name HDK® T30 from Wacker Chemie AG, Munich), 5 parts of a hydrocarbon mixture with a boiling range of 235–270°C (commercially available under the name Exxsol D 100 S from Staub & Co., Nuremberg, Germany), 5 parts of a room-temperature solid silicone resin consisting of the following units (according to 29Si NMR and IR analysis): 40 mol% (CH₃)₃SiO₂, 50 mol% SiO₄²⁻, 8 mol% C₂H₅ OSiO 3 / 2 - and 2 mol-% HOSiO 3 / 2 -, wherein this resin has a weight-average molar mass of 7900g / mol (based on polystyrene standard), and 0.7 parts of a 20 wt% solution of KOH in glycerol were mixed with a dissolver and heated to 110°C for 4 hours.A defoamer formulation with a viscosity of 35500 mPa·s (2.5 rpm, 25°C) was obtained. Production of the defoaming formulations (A2):

[0114] The preparation method for the defoamer formulation (A1) is repeated, using as the organopolysiloxane (Aa) 82.3 parts by weight of a trimethylsiloxy-terminated dodecylmethylsiloxane with an average chain length of 55 and a viscosity of 1100 mPa·s (measured at 25°C and a shear rate of 10 / s). A defoamer formulation (A2) with a viscosity of 28700 mPa·s (2.5 rpm, 25°C) was obtained. Production of the defoaming formulations (A3):

[0115] 85 parts of a trimethylsiloxy-terminated dimethylsiloxy-(alpha-methylstyryl)methylsiloxy-methyloctylsiloxy copolymer of average chain length 60 and a ratio of dimethylsiloxy units to (alpha-methylstyryl)methylsiloxy units to methyloctylsiloxy of 10:9:1 with a viscosity of 1500 mPa·s (measured at 25°C and a shear rate of 10 / s), 5 parts of pyrogenic silica as in defoamer formulation (A1), 5 parts of hydrocarbon mixture as in defoamer formulation (A1), 5 parts of silicone resin as in defoamer formulation (A1) and 0.7 parts of a 20 wt% methanolic KOH solution were mixed with a dissolver and heated to 110°C for 4 hours. A defoamer formulation with a viscosity of 9500 mPa·s (2.5 rpm, 25°C) was obtained. Example 2: Production of the defoamer powders according to the invention: Production of the defoamer powder (P1):

[0116] Ten parts of the defoamer formulation (A1) are mixed with 1.25 parts of glycerol monostearate (available from Faci under the name GMS90 with a glycerol tristearate content of less than 1 wt% (according to HPLC analysis)) at a temperature of 50°C. The resulting mixture is dispersed in 2.5 parts of a polyacrylic acid solution heated to 50°C and having a pH of 2.5 (a 50 wt% polyacrylic acid solution commercially available as Sokalan® CP 10 S from BASF). This results in a white, creamy, free-flowing dispersion. The resulting dispersion is applied under strong shear to a mixture of 72.5 parts sodium sulfate and 15 parts zeolite 4A. After drying at 80°C until constant weight is achieved, the defoamer powder (P1) according to the invention is obtained. Production of the defoamer powder (P2):

[0117] Analogous to the description for defoamer powder (P1), a dispersion is prepared from 3.75 parts glycerol monostearate GMS90, 2.5 parts Sokalan CP 10 S, and 10 parts of the defoamer formulation (A1). Adding this dispersion to a mixture of 70 parts sodium sulfate and 15 parts zeolite 4A, followed by drying, yields the defoamer powder (P2). Production of the defoamer powder (P3):

[0118] Analogous to the description for defoamer powder (P1), a dispersion is prepared from 1.25 parts glycerol monostearate GMS90, 7.5 parts Sokalan CP 10 S, and 10 parts of the defoamer formulation (A1). Adding this dispersion to a mixture of 70 parts sodium sulfate and 15 parts zeolite 4A, followed by drying, yields the defoamer powder (P3). Production of the defoamer powder (P4):

[0119] Analogous to the description for defoamer powder (P1), a dispersion is prepared from 3.75 parts glycerol monostearate GMS90, 7.5 parts Sokalan CP 10 S, and 10 parts of the defoamer formulation (A1). Adding this dispersion to a mixture of 70 parts sodium sulfate and 15 parts zeolite 4A, followed by drying, yields the defoamer powder (P4). Production of the defoamer powder (P5):

[0120] Analogous to the description for defoamer powder (P1), a dispersion is prepared from 1.9 parts glycerol monostearate GMS90, 1.9 parts paraffin (melting range: 56-58°C), 8.0 parts Sokalan CP 10 S, and 10 parts of the defoamer formulation (A1). Adding this dispersion to a mixture of 67 parts sodium sulfate and 15 parts zeolite 4A, followed by drying, yields the defoamer powder (P5). Production of the defoamer powder (P6):

[0121] Analogous to the description for defoamer powder (P1), a dispersion is prepared from 3.8 parts glycerol monostearate GMS90, 8.0 parts Sokalan CP 10 S, and 10 parts of the defoamer formulation (A3). Adding this dispersion to a mixture of 66 parts sodium sulfate and 15 parts zeolite 4A, followed by drying, yields the defoamer powder (P6). Production of the defoamer powder (P7):

[0122] Analogous to the description for defoamer powder (P1), a dispersion is prepared from 3.8 parts glycerol monostearate GMS90, 8.0 parts Sokalan CP 10 S, and 10 parts of the defoamer formulation (A2). Adding this dispersion to a mixture of 66 parts sodium sulfate and 15 parts zeolite 4A, followed by drying, yields the defoamer powder (P7). Example 3: Production of non-inventive defoaming powders: Production of the defoamer powder (VP1):

[0123] 3.8 parts of glycerol monostearate GMS90 and 10 parts of the defoamer formulation (A1) are mixed together at 50°C and the warm mixture is added to a mixture of 70 parts sodium sulfate and 15 parts zeolite 4A, so that the (non-inventive) defoamer powder (VP1) is obtained. Production of the defoamer powder (VP2):

[0124] Analogous to the description for defoamer powder (P1), a dispersion is prepared from 3.8 parts of glycerol monostearate GMS90, 11.1 parts of a polyacrylic acid with a pH of 8.5 (45 wt% solution of polyacrylic acid commercially available as Sokalan® CP 10 from BASF), and 10 parts of the defoamer formulation (A1). Adding this dispersion to a mixture of 66 parts sodium sulfate and 15 parts zeolite 4A, followed by drying, yields the (non-inventive) defoamer powder (VP2). Production of the defoamer powder (VP3):

[0125] Analogous to the description for defoamer powder (P1), a dispersion is prepared from 3.8 parts of glycerol monostearate GMS90, 8.0 parts of an acrylic acid-maleic acid copolymer with a pH of 8.0 (40 wt% solution of acrylic acid-maleic acid copolymers commercially available as Sokalan® CP 5 from BASF), and 10 parts of the defoamer formulation (A1). Adding this dispersion to a mixture of 67 parts sodium sulfate and 15 parts zeolite 4A and subsequent drying yields the (non-inventive) defoamer powder (VP3). Production of the defoamer powder (VP4):

[0126] Analogous to the description for defoamer powder (P1), a dispersion is prepared from 3.8 parts Steareth-4, 8.0 parts Sokalan CP 10 S and 10 parts of the defoamer formulation (A1). By adding this dispersion to a mixture of 66 parts sodium sulfate and 15 parts zeolite 4A and subsequent drying, the (non-inventive) defoamer powder (VP4) is obtained. Production of the defoamer powder (VP5):

[0127] Analogous to the description for defoamer powder (P1), a dispersion is prepared from 10.0 parts of Sokalan CP 10 S and 10 parts of the defoamer formulation (A1). By adding this dispersion to a mixture of 70 parts sodium sulfate and 15 parts zeolite 4A and subsequent drying, the (non-inventive) defoamer powder (VP5) is obtained. Production of the defoamer powder (VP6):

[0128] A mixture of 3.8 parts glycerol monostearate GMS90 and 10 parts of the defoamer formulation (A1) are combined with 8.0 parts Sokalan CP 10 S on parts sodium carbonate and final drying yields the (non-inventive) defoamer powder (VP6). Production of the defoamer powder (VP7):

[0129] Ten parts of the defoamer formulation (A1) are dispersed in 8.0 parts of Sokalan CP 10 S. By adding this dispersion to 85 parts of zeolite 4A and subsequent drying, the (non-inventive) defoamer powder (VP7) is obtained. Production of the defoamer powder (VP8):

[0130] Ten parts of the defoaming formulation (A3) are mixed with 3.8 parts of glycerol monostearate GMS 90, and the mixture is dispersed in 8.0 parts of Sokalan CP 10 S. By adding this dispersion to 82 parts of corn starch and subsequent drying, the (non-inventive) defoaming powder (VP8) is obtained. Example 4: Tests of the defoamer effectiveness in the washing machine

[0131] 0.5% by weight of antifoaming powder was added to 130 g of WFK ECE-2 washing powder. The washing powder was then placed in a drum washing machine (Miele Novotronik W918 type without fuzzy logic) along with 3500 g of clean cotton laundry. The wash program was then started. The program ran at a temperature of 40°C and a water hardness of 3°GH. The foam level was recorded over a period of 55 minutes. The average foam level was determined from the foam scores recorded over the entire period (0% no foam measurable to 100% excessive foaming). The lower this average, the more effective the antifoaming powder was over the entire period.

[0132] Storage tests in ECE-2 washing powder are carried out as follows: 0.5 wt% of defoaming powder is added to 130 g of the washing powder and mixed thoroughly. The mixture is placed in a 50 µm thick PE bag, sealed, and stored in a climate chamber for 4, 8, or 12 weeks at 35°C / 70% relative humidity. After storage as described above, the contents of one bag are tested in a drum washing machine to verify foam control.

[0133] Each foam rating is an average of several individual measurements. Table 1: Defoaming effect of 0.05% of the defoamer powder according to the invention in washing powder ECE-2 with and without storage: Defoamer powder average foam note without storage Average foam note after 12 weeks of storage P1 ++ ++ P2 ++ ++ P3 ++ ++ P4 ++ ++ P5 ++ ++ 0-10% foam: ++ 11-20% foam: + 21-40% foam: o 41-60% foam: - > 60% foam: --

[0134] All defoamer powders according to the invention exhibit excellent defoamerizing properties in washing powder ECE-2. Even after 12 weeks of storage, the defoamer powders still show excellent defoamerizing properties. Table 2: Defoaming effect of 0.05% of the non-inventive defoamer powder VP1 in the washing powder ECE-2 with and without storage: Defoamer powder average foam note without storage Average foam note after 12 weeks of storage VP1 ++ --

[0135] In the case where polyacrylic acid is not used (as described in EP 0 210 731, EP 1 534 403 and EP 1 528 954), the (non-inventive) antifoam powder (VP1) exhibits excellent defoamering efficacy without storage. However, after storage for more than 12 weeks, the defoamering efficacy completely collapses.

[0136] The combination of acidic polyacrylic acid and glycerol monostearate (as used in the defoamer powders P1 to P5 according to the invention) is therefore necessary to achieve very good storage stability. Table 3: Defoaming effect of 0.05% of the non-inventive defoamer powders VP2 and VP3 in the washing powder ECE-2 with and without storage: Defoamer powder average foam note without storage Average foam note after 8 weeks of storage VP2 ++ -- VP3 ++ --

[0137] If no acidic polyacrylic acid is used, excellent defoaming efficacy is also present without storage. However, the defoaming efficacy completely collapses after just 8 weeks.

[0138] If, on the other hand, an acidic polyacrylic acid is used (as in the defoamer powders P1 to P5 according to the invention), excellent storage stability is achieved. Table 4: Defoaming effect of 0.05% of the non-inventive defoamer powders VP4 and VP5 in washing powder ECE-2 with and without storage: Defoamer powder average foam note without storage Average foam note after 12 weeks of storage VP4 + -- VP5 + --

[0139] If stearyl polyether is used instead of glycerol monostearate (VP4) or if glycerol monostearate is omitted entirely (VP5), a slightly reduced efficacy is already observed without storage. After 12 weeks of storage, the defoaming efficacy is significantly reduced.

[0140] If, on the other hand, a glycerol monostearate is used (as in the defoamer powders P1 to P5 according to the invention), both excellent effectiveness without storage and excellent storage stability are achieved. Table 5: Defoaming effect of 0.05% of the non-inventive defoamer powder VP6 in washing powder ECE-2 with and without storage: Defoamer powder average foam note without storage Average foam quality after 4 weeks of storage VP6 o --

[0141] If only an alkaline carrier is used and the polycarboxylate binder and the defoaming formulation are not added as an aqueous premix, the defoaming efficacy is reduced without storage. Furthermore, after 8 weeks of storage, the defoaming efficacy has significantly decreased.

[0142] If, on the other hand, the alkaline carrier is not a main component (as in the defoamer powders P1 to P5 according to the invention with approx. 18 wt.% based on the total amount of carrier materials) and the polycarboxylate binder is added to the carrier materials together with the antifoam formulation as an aqueous premix (as in the defoamer powders P1 to P5 according to the invention), excellent effectiveness is achieved without storage, and the defoamering effect is still present even after 12 weeks of storage. Example 5: Dispersibility of the defoaming powders:

[0143] 150 g of water are placed in a 250 mL glass bottle. The antifoaming powder is added and stirred with a spatula. A visual assessment is carried out after 10 seconds and after 60 seconds. Table 6: Solubility / dispersibility of 0.1 wt.% of defoaming powders in water after 10 and 60 seconds: Defoamer powder Visual evaluation after 10 seconds Visual evaluation after 60 seconds P7 Clear solution, little sediment Clear solution, sediment largely dissolved. VP7 Turbid solution, sediment The turbidity has increased further. VP8 Slight turbidity of the solution, sediment The turbidity of the solution has increased further.

[0144] If only zeolite or only starch is used as the carrier material (VP7 and VP8), the solution has low solubility. In both cases, the result is a cloudy solution that becomes even cloudier over time. If a water-soluble carrier material (sodium sulfate) is used as the main component (P7), the result is a clear solution. The sediment that initially forms (though less than with VP7 or VP8) largely dissolves over time.

[0145] The use of water-soluble carrier materials as the main component of the defoamer powders according to the invention clearly shows an advantage over the prior art.

Claims

1. Defoamer powders containing (A) 100 parts by weight of a defoamer formulation containing (Aa) a polysiloxane containing units of formula (I)         R1R2SiO2 / 2     (I), in which R1 may be identical or different and is a monovalent, optionally branched, SiC-bonded hydrocarbon radical having 1 to 5 carbon atoms, R2 may be identical or different and is a monovalent, optionally branched, SiC-bonded hydrocarbon radical having 6 to 30 carbon atoms, (Ab) a filler, (Ac) an organopolysiloxane resin composed of units of the general formula         R3a(R4O)bSiO(4-a-b) / 2     (II), in which R3 may be identical or different and is a monovalent, optionally substituted, SiC-bonded hydrocarbon radical having 1 to 30 carbon atoms, R4 may be identical or different and is a hydrogen atom or a monovalent, optionally substituted hydrocarbon radical having 1 to 4 carbon atoms, a is 0, 1, 2 or 3 and b is 0, 1, 2 or 3, with the proviso that the sum total of a + b is ≤ 3 and in less than 50% of all units of formula (II) in the organopolysiloxane resin the sum total of a + b = 2, (Ad) optionally a further organopolysiloxane consisting of units of formula (III) and (IV)         R12SiO2 / 2     (III),         R5R12SiO1 / 2     (IV), in which R1 has the definition as described above, R5 may be identical or different and may be R1 or -OR6, where R6 is a hydrogen atom or a monovalent, optionally substituted hydrocarbon radical having 1 to 25 carbon atoms, (Ae) optionally water-insoluble organic compounds, (Af) optionally an alkaline or acidic catalyst or the reaction product thereof with components (Aa) to (Ad) (B) 10 to 45 parts by weight, based on 100 parts by weight of the defoamer formulation (A), of a waxy additive containing a monoester (B') of glycerol and a fatty acid that is free of a polysiloxane-containing additive and that contains less than 5% by weight of a triester (B'') of glycerol and a fatty acid, (C) 10 to 50 parts by weight, based on 100 parts by weight of the defoamer formulation (A), of a polycarboxylate binder that has a pH of 3 or less when it is dissolved in water, (D) 120 to 5000 parts by weight, based on 100 parts by weight of the defoamer formulation (A), of at least one pulverulent carrier material, with the proviso that the carrier material contains less than 50% by weight of alkaline carrier material, preferably less than 40% by weight of alkaline carrier material, more preferably less than 25% by weight of alkaline carrier material.

2. The defoamer powders as claimed in claim 1, characterized in that the polysiloxane (Aa) is an organopolysiloxane of the formula         R5R12SiO-(SiR12O)x-(SiR1R2O)y-SiR12R5     (VIII), where R1, R2 and R5 have the definition given for them in claim 1, x is greater than or equal to 0 and on average less than 200 and y is on average greater than 5 and less than 200.

3. The defoamer powders as claimed in claim 1 or 2, characterized in that silicas are used as fillers (Ab).

4. The defoamer powders as claimed in claim 1, 2 or 3, characterized in that the organopolysiloxane resins (Ac) used are MQ resins composed of units of the formulae SiO2 (Q units) and R33SiO1 / 2 (M units), where the molar ratio of M to Q units is in the range from 0.5 to 2.0, the MQ resins may also contain, in addition to the M and Q units, small amounts of R3SiO3 / 2 or (R4O)SiO3 / 2 (T) units or R32SiO2 / 2 (D) units, in amounts from 0.01 to 20 mol%, based on the sum total of all siloxane units, and the MQ resins may contain up to 10% by weight of free Si-bonded hydroxyl or alkoxy groups, such as methoxy or ethoxy groups, where R3 and R4 have the definition given for them in claim 1.

5. The defoamer powders as claimed in any of claims 1 to 4, characterized in that the waxy additive (B) contains greater than or equal to 30% by weight, preferably greater than or equal to 50% by weight and in particular greater than or equal to 70% by weight of a monoester of glycerol and a fatty acid and less than 5% by weight of a triacylglycerol in the total mixture of the waxy component (B) used.

6. The defoamer powders as claimed in any of claims 1 to 5, characterized in that the monoester of glycerol and a fatty acid is glycerol monolaurate, glycerol monomyristate, glycerol monopalmitate or glycerol monostearate.

7. The defoamer powders as claimed in any of claims 1 to 6, characterized in that the polycarboxylate binder (C) is a water-soluble or water-dispersible homopolymer, copolymer or a salt thereof comprising at least 60 percent by weight of segments of the general formula         (CR82-CR82)n     (V), where n has a value between 10 and 100 000, preferably between 20 and 10 000, particularly preferably between 30 and 1000, R8 is selected from hydrogen, (optionally substituted) hydrocarbon radicals having 1 to 30 carbon atoms, carboxyl groups or salts thereof, and groups of the general formula         -C(O)-O-R9     (VI),         -C(O)-N(R10)2     (VII), where R9 is an optionally functionalized hydrocarbon radical having 1 to 30 carbon atoms and R10 is either hydrogen, the radical R9 or R11-SO3X, where R11 is a divalent alkylene radical having 1 to 12 carbon atoms and X is a hydrogen atom or a cation, with the proviso that at least 5 mol%, preferably at least 10 mol%, particularly at least 15 mol% of the radicals R8 are acidic groups selected from the carboxyl group or salts thereof and groups containing a sulfonyl group or salts thereof, preferably selected from the carboxyl group and salts thereof.

8. The defoamer powders as claimed in any of claims 1 to 7, characterized in that the polycarboxylate binder (C) is a homo- or copolymer of monomers selected from the group of acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, itaconic acid, aconitic acid, mesaconic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), maleic anhydride and maleimide.

9. The defoamer powders as claimed in any of claims 1 to 8, characterized in that non-alkaline carrier materials such as phosphates, sodium sulfate, sodium bicarbonate, sodium citrate, sodium acetate or cellulose derivatives such as sodium carboxymethyl cellulose are used to an extent of greater than 50% by weight as pulverulent carrier materials.

10. A process for producing the defoamer powders as claimed in any of claims 1 to 9, in that a premix, preferably in the form of a dispersion, of defoamer formulation (A), waxy additive (B) and binder (C) is produced and this premix is mixed with the pulverulent carrier material.

11. The process as claimed in claim 10, characterized in that the premix is mixed in the form of an aqueous dispersion with the pulverulent carrier material.

12. The process as claimed in claim 10 or 11, characterized in that the defoamer powder is subsequently dried.

13. A detergent or cleaning composition containing defoamer powder as claimed in any of claims 1 to 9 or produced as claimed in claim 10.