Defoaming composition for detergents

Abstract

The invention relates to a novel defoaming agent powder comprising (A) 100 parts by weight of a defoaming agent formulation comprising (Aa) a polysiloxane containing units of formula (I) R1R2SiO2 / 2, where R1 is a monovalent, optionally branched, SiC-bonded hydrocarbon group having 1 to 5 carbon atoms, R2 is a monovalent, optionally branched, SiC-bonded hydrocarbon group having 6 to 30 carbon atoms, (Ab) a filler, and (Ac) a silane coupling agent, (Ac) an organopolysiloxane resin consisting of units of general formula (II): R3a (R4O) bSiO (4-a-b) / 2, where R3 is a monovalent, optionally substituted, SiC-bonded hydrocarbon group having 1 to 30 carbon atoms, R4 is a hydrogen atom or a monovalent, optionally substituted hydrocarbon group 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 of a + b = 2 in less than 50% of all units of formula (II), and the sum of a + b = 2 in less than 50% of all units of formula (II). Optionally further organopolysiloxane (Ad), optionally a water-insoluble organic compound (Ae), and optionally a catalyst (Af), (B) 10 to 45 parts by weight of a waxy additive, the present invention relates to a wax additive comprising a monoester of glycerol and a fatty acid (B ') which is free of a polysiloxane-containing additive and comprises less than 5% by weight of a triester of glycerol and a fatty acid (B' '), (C) 10 to 50 parts by weight of a polycarboxylate binder having a pH of 3 or less when dissolved in water, and (D) 120 to 5000 parts by weight of at least one powdered carrier material, with the proviso that the carrier material comprises less than 50% by weight of an alkaline carrier material.

Description

[0001] The invention relates to a defoamer powder which, in addition to the defoamer preparation, comprises a waxy, non-silicone-containing component, a polycarboxylate binder and a pulverulent, water-soluble carrier material, to a process for its production and to its use for defoaming media, preferably aqueous media, in particular aqueous surfactant preparations.

[0002] In many liquid systems, especially aqueous systems, which contain surface-active compounds as desired or undesired components, foam formation can cause problems when these systems are brought into more or less intimate contact with gaseous substances, for example in the bubbling of waste water, in intensive stirring of liquids, in distillation, washing or dyeing processes, or in filling operations.

[0003] This foam can be controlled by mechanical means or by adding defoamers. In this regard, silicone-based defoamers have been found to be particularly useful. For example, according to US 3383327 A, defoamers based on silicone are produced by heating hydrophilic silica in polydimethylsiloxane. Polyorganosiloxanes with relatively long-chain n-alkyl side chains are also described in US 2009 / 0137446A1 as the basis for producing effective defoamers.

[0004] When solid products are used, for example in detergents and cleaning compositions, in agrochemical products and in pharmaceutical formulations, mainly powdered defoamers are used. In this case, it is advantageous to convert the defoamer, which is usually present as an oily, viscous liquid, into a powder form, which can be achieved by adsorbing the defoamer onto a solid carrier material. In the case of detergent powders, it is particularly advantageous that the carrier material used does not hinder the washing process or is itself a detergent component. The common feature of most defoamer powders obtained by simply applying the defoamer to a carrier material is that they quickly lose their effectiveness when stored, especially in the presence of alkaline compounds.

[0005] In order to counteract this disadvantage, various solutions have been proposed. One possible solution consists in encapsulating or coating the carrier material in order to better fix the defoamer. For this purpose, EP 0 995473 A1 proposes the use of a combination of an acidic polycarboxylate and a polyether-functionalized polysiloxane on a carrier material zeolite.

[0006] EP 0210731 A2 describes the use of glycerol monoesters as waxy additives. If the described glycerol monoesters are used in excess relative to defoamers based on polydimethylsiloxane, storage stability can be demonstrated.

[0007] WO 2004 / 018073 A1 describes defoamers based on polyorganosiloxanes which are functionalized with side groups of α-methylstyrene groups supported on sodium carbonate, starch or zeolites, wherein triglycerides (such as tristearate) must be used as additives. When used for foam control in detergent powders, the additives have a positive influence on the efficacy of the defoamer powders. No statements are made about storage stability.

[0008] WO 2004 / 018074 A1 describes defoamer powders in which waxy triglycerides are likewise used as additives. The triglycerides are sprayed together with the defoamer on a carrier, in particular sodium carbonate or starch, partly in combination with other more polar additives (e.g. monoglycerides, alkylphenols, fatty alcohols or fatty acids). The amount of additive is at least 50% by weight, based on the defoamer. When used for foam control of washing powders, a positive influence on the efficacy of the defoamer powder can also be shown here. Likewise, no statements are made about storage stability.

[0009] Disadvantages of the solutions described are the considerable amounts of organic additives which are additionally required in some cases, their lack of storage stability in a solid surfactant matrix, and their suboptimal solubility or dispersibility in water.

[0010] It was therefore an object of the present invention to provide defoamer powders which, in addition to the defoamer formulation and the carrier material, contain only small amounts of further components and have excellent storage stability and excellent aqueous solubility or dispersibility. In particular, the resulting defoamer powders should be able to be used in cleaning agents and cleaning compositions.

[0011] The present invention provides a defoamer powder, comprising:

[0012] (A) 100 parts by weight of a defoamer preparation comprising

[0013] (Aa) polysiloxane containing units of formula (I)

[0014] R 1 R 2 SiO 2 / 2 (I)

[0015] in,

[0016] R 1 are identical or different and are monovalent, optionally branched, SiC-bonded hydrocarbon radicals having 1 to 5 carbon atoms,

[0017] R 2 are identical or different and are monovalent, optionally branched, SiC-bonded hydrocarbon radicals having 6 to 30 carbon atoms,

[0018] (Ab) filler,

[0019] (Ac) an organopolysiloxane resin composed of units of the following general formula:

[0020] R 3 a (R 4 O) b SiO (4-a-b) / 2 (II)

[0021] in,

[0022] R 3 are identical or different and are monovalent, optionally substituted, SiC-bonded hydrocarbon radicals having 1 to 30 carbon atoms,

[0023] R 4 are the same or different and are a hydrogen atom or a monovalent, optionally substituted hydrocarbon group having 1 to 4 carbon atoms,

[0024] a is 0, 1, 2, or 3, and

[0025] b is 0, 1, 2, or 3,

[0026] Provided that the sum of a+b is ≤3, and that less than 50% of all units of formula (II) in the organopolysiloxane resin have a sum of a+b=2,

[0027] Optionally

[0028] (Ad) Another organopolysiloxane composed of units of formula (III) and (IV)

[0029] R 12 SiO 2 / 2 (III)

[0030] R 5 R 1 2SiO 1 / 2 (IV),

[0031] in,

[0032] R 1 With the definitions given above,

[0033] R 5 can be the same or different and can be R 1 OR 6 ,in

[0034] R 6 is a hydrogen atom or a monovalent, optionally substituted hydrocarbon group having 1 to 25 carbon atoms, optionally

[0035] (Ae) water-insoluble organic compounds,

[0036] Optionally

[0037] (Af) a basic or acidic catalyst or a reaction product thereof with components (Aa) to (Ad)

[0038] (B) 10 to 45 parts by weight of a waxy additive comprising a monoester (B') of glycerol and a fatty acid, based on 100 parts by weight of the defoamer formulation (A);

[0039] Does not contain additives containing polysiloxane, and

[0040] It contains less than 5% by weight of triesters of glycerol and fatty acids (B"),

[0041] (C) 10 to 50 parts by weight of a polycarboxylate binder having a pH of 3 or less when dissolved in water, based on 100 parts by weight of the defoamer preparation (A),

[0042] (D) based on 100 parts by weight of the defoamer preparation (A), 120 to 5000 parts by weight 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.

[0043] The term "antifoam powder" is understood to mean both powdered and granulated products.

[0044] It has now surprisingly been found that, compared with the prior art, antifoam powders having such a composition are distinguished by significantly improved storage stability in washing powders and significantly improved water solubility or water dispersibility in the washing liquor, while using less additional agents.

[0045] The defoamer powder according to the invention preferably contains 10 to 42 parts by weight of waxy additive (B), 10 to 47 parts by weight of polycarbonate binder (C) and 200 to 2000 parts by weight of pulverulent carrier material (D), in each case based on 100 parts by weight of defoamer preparation (A), and particularly preferably 13 to 40 parts by weight of waxy additive (B), 13 to 45 parts by weight of polycarboxylate binder (C) and 300 to 1200 parts by weight of pulverulent carrier material (D), in each case based on 100 parts by weight of defoamer preparation (A).

[0046] The defoamer powder according to the invention preferably consists essentially of components (A), (B), (C) and (D).

[0047] Preferably, the defoamer preparation (A) consists of the components (Aa), (Ab), (Ac) and optionally the components (Ad), (Ae) and (Af).

[0048] Preferably, the defoamer formulation (A) comprises:

[0049] (1) at least 55% by weight, preferably at least 65% by weight, particularly preferably at least 75% by weight, and preferably at most 97% by weight, more preferably at most 90% by weight, particularly preferably at most 85% by weight, of polysiloxane (Aa),

[0050] (2) at least 1 wt. %, preferably at least 2 wt. %, particularly preferably at least 3 wt. %, and preferably at most 15 wt. %, more preferably at most 12 wt. %, particularly preferably at most 10 wt. % of filler (Ab),

[0051] (3) at least 1% by weight, preferably at least 2% by weight, particularly preferably at least 3% by weight, and preferably up to 15% by weight, more preferably up to 12% by weight, particularly preferably up to 10% by weight, of an organopolysiloxane resin (Ac) composed of units of the formula (II),

[0052] (4) at least 0% by weight and preferably at most 15% by weight, more preferably at most 10% by weight, particularly preferably at most 7.5% by weight, of organopolysiloxane (Ad) composed of units of the formulae (III) and (IV),

[0053] (5) at least 0% by weight and preferably at most 15% by weight, more preferably at most 10% by weight, particularly preferably at most 7.5% by weight of water-insoluble organic compounds (Ae),

[0054] as well as

[0055] (6) at least 0% by weight, preferably at least 0.05% by weight, particularly preferably at least 0.1% by weight, and preferably at most 1% by weight, more preferably at most 0.5% by weight, particularly preferably at most 0.3% by weight, of a basic or acidic catalyst (Af) or its reaction products with components (Aa) to (Ad).

[0056] Preferably, the organopolysiloxanes (Aa) used in the defoamer formulation (A) are those of the formula (VIII)

[0057] R 5 R 1 2SiO-(SiR 1 2O) x -(SiR 1 R 2 O) y -SiR 1 2R 5 (VIII)

[0058] in

[0059] R1 , R 2 and R 5 With the definitions given above,

[0060] x is greater than or equal to 0 or on average less than 200, preferably less than 100, particularly preferably less than 50,

[0061] On average, y is greater than 5, preferably greater than 10, and less than 200, preferably less than 100, particularly preferably less than 50.

[0062] The organopolysiloxane (Aa) may additionally contain branches by comprising units of the formulae (IX) and (X).

[0063] SiO 4 / 2 (IX)

[0064] R 1 SiO 3 / 2 or R 2 SiO 3 / 2 or R 5 SiO 3 / 2 (X)

[0065] R 1 LSiO 2 / 2 or R 2 LSiO 2 / 2 or R 5 LSiO 2 / 2 (XI)

[0066] in

[0067] R 1 , R 2 and R 5 With the definitions given above, and

[0068] L is a divalent structure connecting two organopolysiloxane chains to each other.

[0069] L can be an alkylene group such as ethylene, propylene, butene, hexene, octenyl, preferably hexylene or octylene; a divalent aromatic group such as 1,2-diphenylene, 1,4-diphenylene or 1,8-diphenylnaphthalene; a cycloalkylene group such as 1,4-diphenylene cyclohexane group or a divalent organosiloxane chain.

[0070] Hydrocarbon R 1 Examples of are alkyl groups such as methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl; and cycloalkyl groups such as cyclopentyl.

[0071] R 1 Preferred examples are methyl and ethyl. A particularly preferred example is methyl.

[0072] Hydrocarbon R 2 Examples are alkyl groups such as hexyl groups such as n-hexyl, heptyl groups such as n-heptyl, octyl groups such as n-octyl and isooctyl 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 n-tetradecyl, hexadecyl groups such as n-hexadecyl and octadecyl groups such as n-octadecyl; cycloalkyl groups such as cyclohexyl, cycloheptyl, methylcyclohexyl and 4-ethylcyclohexyl; aryl groups such as phenyl, naphthyl, anthracenyl and phenanthryl; alkaryl groups such as o-, m-, p-tolyl, xylyl and ethylphenyl; and aralkyl groups such as benzyl, 2-phenylpropyl and α-phenethyl and β-phenethyl.

[0073] R 2 Preferred examples are n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, phenyl, benzyl and 2-phenylpropyl. Particularly preferred examples are n-octyl, n-dodecyl, phenyl and 2-phenylpropyl.

[0074] R 5 An example, a preferred example and a particularly preferred example is R 1 Or has the formula -OR 6 Examples, preferred examples and particularly preferred examples of the group.

[0075] R 6 Examples of are a hydrogen atom or an alkyl group such as methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl such as n-hexyl, heptyl such as n-heptyl, octyl such as n-octyl and isooctyl such as 2,2,4-trimethylpentyl and 2-ethylhexyl, nonyl such as n-nonyl, decyl such as n-decyl, dodecyl such as n-dodecyl, tetradecyl such as n-tetradecyl, hexadecyl such as n-hexadecyl and octadecyl such as n-octadecyl; and cycloalkyl such as cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl and 4-ethylcyclohexyl.

[0076] R 6 Preferred examples of are a hydrogen atom or a methyl group and an ethyl group.

[0077] Particularly preferred examples are a hydrogen atom or a methyl group.

[0078] Preferably, the filler (Ab) used in the defoamer formulation (A) has a particle size of 20 to 1000 m 2 Preferably, the fillers (Ab) have a particle size of less than 10 μm and an agglomerate size of less than 100 μm.

[0079] Examples of fillers (Ab) are silicon dioxide (silica), titanium dioxide, aluminum oxide, metal soaps, ground quartz, PTFE powder, fatty acid amides (eg ethylene bisstearamide), and finely divided hydrophobic polyurethanes.

[0080] Preferred as fillers (Ab) are 2 / g of BET surface area of ​​silicon dioxide (silica), titanium dioxide or aluminum oxide. Preferably, these fillers have a particle size of less than 10 μm and an agglomerate size of less than 100 μm.

[0081] Preferred fillers (Ab) are silicon dioxide, in particular those having a density of 50 to 800 m 2 / g of BET surface area. These silicas can be fumed silica or precipitated silica. Both pretreated silica (i.e., hydrophobic silica) and hydrophilic silica can be used as filler (Ab). Examples of commercially available hydrophobic silicas that can be used according to the present invention are H2000, with 140m 2 / g BET surface area of ​​fumed hexamethyldisilazane treated silica (commercially available from Wacker Chemie AG, Germany) and a silica having a BET surface area of ​​90 m 2 / g BET surface area of ​​precipitated polydimethylsiloxane treated silica (commercially available from Evonik, Germany, under the name “ D10”).

[0082] If this is advantageous for the desired efficacy of the defoamer formulation, the hydrophilic silica can also be hydrophobized in situ. Many methods for hydrophobizing silica are known. The in situ hydrophobization of the hydrophilic silica can be carried out, for example, by heating the silica dispersed in component (Aa) or in a mixture of components (Aa), (Ac), optionally (Ad) and optionally (Ae) to a temperature of 100° C. to 200° C. for several hours. The reaction here can optionally be assisted by the addition of catalysts (Af) and hydrophobizing agents, such as short-chain OH-terminated polydimethylsiloxanes, silanes or silazanes.

[0083] Component (Ac) used in the defoamer formulation (A) is preferably a silicone resin consisting of units of formula (II), wherein, preferably, in less than 30%, more preferably less than 5% of the units in the resin, the sum of a+b is equal to 2.

[0084] Preferably, R 3 is a hydrocarbon group having 1 to 30 carbon atoms.

[0085] Hydrocarbon R 3 Examples are alkyl groups,

[0086] Such as methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, such as n-hexyl, heptyl, such as n-heptyl; octyl, such as n-octyl and isooctyl, such as 2,2,4-trimethylpentyl and 2-ethylhexyl, nonyl, such as n-nonyl; decyl, such as n-decyl; dodecyl, such as n-dodecyl; tetradecyl, such as n-tetradecyl, hexadecyl, such as n-hexadecyl and octadecyl, such as n-octadecyl; cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl and 4-ethylcyclohexyl; aryl, such as phenyl, naphthyl, anthracenyl and phenanthryl; alkylaryl, such as o-, m-, p-tolyl, xylyl, and ethylphenyl; and aralkyl, such as benzyl, 2-phenylpropyl, and α-phenethyl and β-phenethyl.

[0087] Group R 3 Preferred examples are methyl, ethyl and phenyl.

[0088] Group R 3 A particularly preferred example of is methyl.

[0089] Group R 4 Examples of are a hydrogen atom and an alkyl group such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group and a n-butyl group.

[0090] Group R 4 Preferred is a hydrogen atom or a methyl group or an ethyl group.

[0091] Preferably, the organopolysiloxane resin (Ac) composed of units of formula (II) is

[0092] MQ resins are composed of units of the following chemical formula

[0093] SiO2(IX)

[0094] as well as

[0095] R 3 3SiO 1 / 2 (XII),

[0096] Where R 3 has the definition given thereto above.

[0097] The molar ratio of M units 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 units and Q units, the MQ resin may optionally contain a small amount of R 3 SiO 3 / 2 or (R 4 O)SiO 3 / 2 (T) unit or R 3 2SiO 2 / 2(D) units, preferably in an amount of 0.01 to 20 mol%, more preferably 0.01 to 5 mol%, wherein R 3 and R 4 have the definitions given above for them. These MQ resins may also contain up to 10% by weight of free Si-bonded hydroxyl or alkoxy groups, such as methoxy or ethoxy groups.

[0098] Preferably, these organopolysiloxane resins (Ac) have a viscosity of greater than 1000 mPa·s or are solid at 25° C. and 101.425 kPa. The weight average molecular weight of these resins, determined by gel permeation chromatography (based on polystyrene standards), is preferably from 200 to 200,000 g / mol, in particular from 1,000 to 200,000 g / mol.

[0099] Organopolysiloxanes (Ad) which are different from the polysiloxanes (Aa) can optionally be used in the defoamer preparation (A).

[0100] Preferably, the organopolysiloxanes (Ad) are those of formula (IXX)

[0101] R 5 R 1 2SiO-(SiR 1 2O) z -SiR 1 2R 5 (IXX),

[0102] in

[0103] R 1 and R 5 With the definitions given above,

[0104] On average, z is greater than 5, preferably greater than 10, and less than 500, preferably less than 200, particularly preferably less than 100.

[0105] Water-insoluble organic compounds (Ae) may optionally be used in the defoamer preparation (A).

[0106] In the context of the present invention, the term "water-insoluble" is understood to mean a solubility in water at 25°C and a pressure of 101.425 kPa of at most 3% by weight.

[0107] The optionally used component (Ae) is preferably a water-insoluble organic compound having a boiling point of more than 100° C. at the pressure of the ambient atmosphere, i.e. at 900 to 1100 hPa, and a melting point of less than 35° C., in particular those selected from mineral oils, natural oils, isoparaffins, polyisobutenes, residues from oxoalcohol synthesis, esters of low molecular weight synthetic carboxylic acids, such as pentane-1,3-diol diisobutyrate, fatty acid esters, such as octyl stearate, octyl oleate, isopropyl laurate, methyl laurate or isopropyl myristate, fatty alcohols which are liquid at temperatures of more than 35° C., ethers of low molecular weight alcohols, phthalates and esters of phosphoric acid.

[0108] Examples of basic catalysts (Af) are alkali metal hydroxides and alkaline earth metal hydroxides, such as NaOH, KOH, CsOH, LiOH and Ca(OH) 2. Examples of acidic catalysts (Af) are hydrochloric acid, sulfuric acid and phosphazene chloride.

[0109] Reaction products of (Af) with components (Aa) to (Ad) are, for example, products of silicon dioxide, preferably as filler (Ab), with alkali metal hydroxides such as potassium silicate or sodium silicate.

[0110] The metered addition of the catalyst can be carried out in typical organic solvents such as alcohols (eg methanol, ethanol, isopropanol) or esters (eg ethyl acetate).

[0111] Components (Aa) to (Af) used in the defoamer preparation (A) may each be one type of such component or a mixture of at least two types of the corresponding components.

[0112] The antifoam preparation (A) has a viscosity of preferably 100 to 2 000 000 mPa·s, more preferably 500 to 80 000 mPa·s, particularly preferably 1 000 to 15 000 mPa·s, in each case at 25° C. and 101.425 kPa.

[0113] The defoamer preparation (A) according to the invention can be produced by known methods, such as by mixing all the components, for example using high shear forces in a colloid mill, a dissolver or a rotor-stator homogenizer. The mixing process can be carried out under reduced pressure to prevent the inclusion of air, which is present, for example, in highly dispersed fillers. If necessary, the filler can then be hydrophobized in situ.

[0114] It is also possible first to initially charge and optionally heat component (Aa) and then successively add components (Ab), (Ac), optionally (Ad), optionally (Ae) and optionally (Af).

[0115] In a preferred embodiment, component (Ac) is added in dissolved form as a solution in component (Ad) or (Ae) or part of component (Ad) or (Ae).

[0116] The waxy additive (B) used is an organic material having a melting point of 35° C. to 85° C., and its main component is a monoester of glycerol and fatty acid (also called 1-monoacylglycerol).

[0117] In particular, these are monoesters of glycerol and aliphatic fatty acids having a carbon chain containing 12 to 20 carbon atoms. This includes the products in their racemic and optically active forms.

[0118] Examples of such monoesters are glyceryl monolaurate, glyceryl monomyristate, glyceryl monopalmitate and glyceryl monostearate. A particularly preferred example of a monoester is glyceryl monostearate.

[0119] The waxy additive (B) used may be an organic material having a melting point of 35° C. to 85° C., thus producing a mixture of several components, the main components of which are glycerol and monoesters of fatty acids.

[0120] Therefore, industrial products of 1-monoglycerol are usually mixtures of 1-monoglycerol and diglycerol with different monoglycerol contents. In addition, these industrial products may also contain small proportions of triglycerols, free glycerol and also free fatty acids.

[0121] In the case of glyceryl monostearate, it is predominantly a mixture of glyceryl monostearate, glyceryl distearate and possibly glyceryl monopalmitate with small proportions of glyceryl tristearate and either free glycerol (in the case of non-emulsifying or non-self-emulsifying monostearate) or also a certain amount of soap (in the case of self-emulsifying monostearate).

[0122] The waxy additive (B) used may also be an organic material having a melting point in the range from 35° C. to 85° C. and wherein additional waxy organic material has been deliberately added to the monoglyceride and fatty acid as main components.

[0123] This additional waxy organic material (not being an ester of fatty acids and glycerol) has a melting point in the range from 35°C to 85°C.

[0124] Examples of further waxy materials are semisynthetic waxes such as amide waxes (eg stearamide, behenamide, erucamide, oleamide), alcohol waxes or ketone waxes or synthetic waxes such as polyolefin waxes or waxy hydrocarbons (eg hard paraffin having a melting point of from 50 to 62° C.).

[0125] Regardless of whether as a result of production or whether additional waxy materials are used, in the total mixture of the wax component (B) used, the content of 1-monoglycerol is preferably greater than or equal to 30% by weight, more preferably greater than or equal to 50% by weight and in particular greater than or equal to 70% by weight, and the content of triglycerol is preferably less than 5% by weight.

[0126] Essential for the defoamer powder according to the invention is a combination of a waxy additive (B) and at least one polycarboxylate binder (C) having a pH of 3 or less when dissolved or dispersed in water.

[0127] It has been found that this combination is essential for good storage stability of the defoamer powders according to the invention in detergent powders.

[0128] The polycarboxylate binders (C) are water-soluble or water-dispersible polymers, homopolymers, copolymers or their salts. They contain at least 60% by weight of segments of the general formula:

[0129] (CR 8 2-CR 8 2) n (V),

[0130] in

[0131] n takes a value between 10 and 100,000, preferably between 20 and 10,000, particularly preferably between 30 and 1,000,

[0132] R 8 is selected from hydrogen, an (optionally substituted) hydrocarbon group having 1 to 30 carbon atoms, a carboxyl group or a salt thereof, and a group having the following general formula

[0133] -C(O)-OR 9 (VI)

[0134] -C(O)-N(R 10 )2 (VII),

[0135] in

[0136] R 9 is an optionally functionalized hydrocarbon group having 1 to 30 carbon atoms, and

[0137] R 10 is hydrogen or a group R 9 or R 11 -SO3X,

[0138] in

[0139] R 11 is a divalent alkylene group having 1 to 12 carbon atoms, and

[0140] X is a hydrogen atom or a cation,

[0141] The proviso is that at least 5 mol %, preferably at least 10 mol %, in particular at least 15 mol % of the radicals R 8It is an acidic group selected from a carboxyl group or a salt thereof and a sulfonyl group-containing group or a salt thereof (preferably selected from a carboxyl group and a salt thereof).

[0142] Group R 8 Can be the same or different.

[0143] Group R 8 Examples are a hydrogen atom, a monovalent (optionally substituted) alkyl, aryl, aralkyl and alicyclic hydrocarbon radicals, 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 also (sulfonyl)naphthyl, a carboxyl group or a radical of the formula (VI) and (VII).

[0144] Preferred groups R 8 is a hydrogen atom, a methyl group, an ethyl group, a (sulfonyl)phenyl group, a carboxyl group or a group of the formula (VI) and (VII).

[0145] Group R 9 The monovalent alkyl, aryl, aralkyl and alicyclic hydrocarbon groups may be the same or different.

[0146] Group R 9 Examples of are methyl, ethyl, n-butyl, isobutyl, tert-butyl, 2-ethylhexyl, lauryl, stearyl, benzyl, isopropyl, neopentyl, cyclohexyl, 2-hydroxyethyl and 2-hydroxypropyl.

[0147] Group R 10 may be the same or different and are hydrogen or a group R 9 or R 11 -SO3X.

[0148] Divalent alkylene group R 11 Examples are methylene, 1,2-ethylene, 1,3-propylene, 1,2-propylene or (2-methyl-)1,2-propylene.

[0149] Examples of X are hydrogen atoms or cations such as sodium, potassium, calcium, magnesium, lithium or ammonium cations, for example derived from ammonia, monoethanolamine, diethanolamine, triethanolamine or isopropylamine.

[0150] Examples of preferred segments corresponding to general formula (V) are:

[0151] (CH2-C(CH3)R 12 ) n (XIII)

[0152] (CH2-C(C2H5)R 12 ) n (XV)

[0153] (CH2-CHR 12 ) n (XVI)

[0154] (CHR 12 -CHR 12 ) n (XVII)

[0155] Where R 12 Select from the following group

[0156] -C(O)-OH(XVIII),

[0157] as well as

[0158] -C(O)-NR 10 2(VII),

[0159] Where R 10 has the definition given thereto above.

[0160] The carboxyl group (XVIII) and the sulfonyl group may also be partially neutralized by a base, preferably a base having a singly positively charged cation, such as an alkali metal cation or an ammonium cation, however it is still necessary to satisfy the condition that the binder (C) has a pH of 3 or less when dissolved in water.

[0161] Examples of monomers that produce these structures are 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).

[0162] Also useful as monomers are maleic anhydride or maleimide. In this case, the anhydride or imide groups preferably incorporated react completely or partially with water, alcohols, amines or ammonia solutions to form carboxyl, ester and / or amide groups.

[0163] Preferred examples of monomers that yield 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 maleimide.

[0164] Particularly preferred examples of monomers that produce these structures are acrylic acid, maleic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and maleic anhydride.

[0165] Copolymerization with relatively small amounts of monomeric materials not containing any carboxylic acid, namely methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, neopentyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, butane-1,4-diol monoacrylate, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate, acrylamide, methacrylamide, vinyl methyl, vinyl methyl ether, styrene and ethylene is not detrimental to the use of polycarboxylates in the foam control agent according to the present invention. Depending on the type of polycarboxylate, the level can be kept low or the level can be up to about 40% by weight of the total polymer or copolymer.

[0166] Such and similar compounds (C) which can be used in the context of the present invention are known and commercially available; for example, PA80S and PA110S (BASF, Germany), acrylic acid-maleic acid copolymer having a pH of about 1 (e.g. CP12S (BASF, Germany)), and a modified polyacrylic acid polymer having a pH of about 1.5 (e.g. CP10S and 13S (also BASF, Germany) or AR-540 (Nouryon, a copolymer of acrylic acid and sulfonated monomers).

[0167] The defoamer powder according to the invention preferably contains a carrier material (D) which is not a basic carrier material. Basic carrier materials are those which produce a basic pH (ie a pH greater than or equal to 11) when dissolved or dispersed in water.

[0168] This is determined from a 0.02 wt% solution or a 5 wt% slurry.

[0169] It has been found that the storage stability of the defoamer powders according to the invention in detergent powders is significantly improved when predominantly non-alkaline carrier materials are used.

[0170] The carrier materials (D) present in the defoamer powders according to the invention may each be one type of such component or a mixture of at least two types of corresponding components.

[0171] In case only one type of component is used as support material, this should be a non-basic support material.

[0172] In the case of using several components as support material, the non-alkaline support material should be the main component. This is the case when the proportion of the non-alkaline support material is greater than 50% by weight, preferably greater than 60% by weight, particularly preferably greater than 75% by weight of the total amount of support material (D).

[0173] Examples of non-alkaline carrier materials are phosphates, for example powdered or granulated sodium tripolyphosphate, sodium sulfate, sodium bicarbonate, sodium citrate, sodium acetate or cellulose derivatives, such as sodium carboxymethylcellulose.

[0174] Examples of basic support materials which can be used in amounts of less than 50% by weight, preferably less than 40% by weight, particularly preferably less than 25% by weight, are sodium carbonate, zeolites (eg zeolite A or zeolite X), aluminosilicates or silicates (eg magnesium silicate).

[0175] Particularly preferred are those carrier materials which have good water solubility, such as sodium sulfate, sodium bicarbonate, sodium citrate, sodium acetate and cellulose derivatives such as sodium carboxymethylcellulose.

[0176] In the context of the present invention, good water solubility is present when the solubility in water at 25°C and a pressure of 101.425 kPa is at least 3 wt%.

[0177] In case only one type of component is used as support material, this should be a readily water-soluble support material.

[0178] In the case where several components are used as carrier material, the readily water-soluble carrier material should be the main component. This is the case when the proportion of readily water-soluble carrier material is greater than 50% by weight, preferably greater than 60% by weight, particularly preferably greater than 75% by weight of the total amount of carrier material (D).

[0179] It has been found that the water solubility or water dispersibility of the defoamer powder according to the invention is significantly improved when a water-soluble carrier material is used as the main component.

[0180] Examples of readily water-soluble carrier materials are phosphates, for example powdered or granulated sodium tripolyphosphate, sodium sulfate, sodium bicarbonate, sodium citrate, sodium acetate or cellulose derivatives, such as sodium carboxymethylcellulose.

[0181] Examples of sparingly water-soluble support materials which can be used in amounts of less than 50% by weight, preferably less than 40% by weight, particularly preferably less than 25% by weight, are zeolites, such as zeolite A or zeolite X, aluminosilicates or silicates, such as magnesium silicate.

[0182] The present invention further provides a method for producing a defoamer powder, comprising:

[0183] preparing a premix of the defoamer preparation (A), the waxy additive (B) and the binder (C), preferably in the form of a dispersion, in particular an aqueous dispersion, and

[0184] This premix is ​​mixed with a powdered carrier material.

[0185] The premix is ​​preferably obtained by dispersing an emulsion or dispersion of the defoamer preparation (A) and the waxy additive (B), preferably aqueous, in a solution or dispersion of the binder (C), preferably aqueous.

[0186] The defoamer powder according to the invention can be produced, for example, by mixing a premix of the defoamer preparation (A) and the waxy additive (B) with the pulverulent carrier material (D) and subsequently or simultaneously incorporating a solution or dispersion of the binder (C).

[0187] Alternatively, it is also possible to prepare an emulsion or dispersion of a premix of the defoamer preparation (A) and the waxy additive (B) in a solution or dispersion of the binder (C) in a known manner and subsequently bind it to the pulverulent carrier material (D).

[0188] This production process uses advantageously an emulsion or dispersion of a premix of the defoamer preparation (A) and the waxy additive (B) in a solution or dispersion of the binder (C).

[0189] If desired, the pulverulent composition obtained after mixing can also be dried in order to finally obtain a free-flowing powder. Drying can be carried out directly in the mixer or subsequently in a separate dryer of known design, such as a belt dryer, spray dryer, screw dryer, paddle dryer or adsorption dryer. Drying is preferably carried out at a temperature of 60° C. to 150° C.

[0190] For the production of the defoamer powder according to the invention, various known mixers can be used, which preferably can be heated and / or evacuated to enable drying in the same unit.

[0191] Examples of suitable mixers are plowshare mixers, Z mixers, screw extruders or planetary mixers.The technically relevant residual water content of the defoamer powder according to the invention is below 10% by weight, preferably below 5% by weight.

[0192] Preferably, the defoamer powders according to the invention are used in cleaners and cleaning compositions.

[0193] However, they can be used wherever it is intended to control or prevent foam. An example of this is powdered crop protection products, in particular those containing relatively large amounts of surface-active compounds. Alternatively, the defoamer powders according to the invention can advantageously be used in chemical processes or wastewater treatment.

[0194] The metered addition of the defoamer powder according to the invention can be achieved, for example, by simple mixing with the detergent. This is advantageously done at the point in time when the detergent is mixed with other components, such as enzymes, bleaches. However, the defoamer powder according to the invention can also be metered directly into the foaming medium.

[0195] The defoamer powder according to the invention is preferably used in solid media comprising surfactants which lead to foam formation when used in an aqueous environment, more preferably in detergents and cleaning compositions, especially in solid (powdered or granular) detergents and cleaning compositions.

[0196] The present invention therefore provides a detergent or cleaning composition comprising the defoamer powder according to the invention.

[0197] The viscosity of the individual components, in particular component (Aa), was determined according to DIN 53019-1 (2008-09) (principle and measurement geometry), DIN 53019-2 (2001-2) (calibration of the viscometer and determination of the uncertainty of the measurement) and DIN 53019-3 (2008-09) (error of measurement and correction) or according to DIN EN ISO 3219 (1994) (Plastics - polymers / resins in liquid state or as emulsions or dispersions - determination of viscosity using a rotational viscometer with a defined shear rate) using an MCR 300 cone / plate viscometer (Paar-Physika) at 25 ° C and the shear rate as indicated accordingly.

[0198] The viscosity of the defoamer preparation (A) was determined in accordance with DIN EN ISO 3219 using an MCR 300 cone / plate viscometer (Paar-Physika) at 25° C. and a shear rate of 50 / s.

[0199] The amount of monoglycerol or triglycerol in commercially available monoglycerol was determined by liquid chromatography (HPLC) using a Phenomenex Luna 5 μm C5 100· (250 x 4.6 mm) HPLC column. The mobile phase used was a mixture of 0.05% aqueous trifluoroacetic acid and THF, with a gradient of 30% THF-100% THF running at a flow rate of 1.0 ml / min and a column temperature of 30°C. Detection was performed with the aid of an evaporative light scattering detector (ELSD) (1.4 SLM-30° neb-30°C evap-50% light source intensity).

[0200] 10 mg of sample were dissolved in 10 ml THF, mixed with 1 ml water and made up to a total of 10 ml with further THF. Calibration was performed against chemically pure mono- or triglycerides.

[0201] In the following examples, all figures for parts and percentages are based on weight unless otherwise stated. Unless otherwise stated, the following examples were carried out under ambient atmospheric pressure, i.e. at about 1000 hPa, and at room temperature, i.e. at about 20° C., or at the temperature established when the reactants were combined at room temperature without additional heating or cooling.

[0202] Example 1: Production of defoamer preparation (A):

[0203] Production of Defoamer Preparation (A1):

[0204] 82.3 parts by weight of trimethylsiloxy-terminated methyloctylsiloxane having 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 300 mPa·s 2 / g of BET surface area of ​​fumed silica (known as Wacker Chemie AG Munich T30 available), 5 parts of a hydrocarbon mixture having a boiling range of 235°C to 270°C (available from Staub & Co Nurmemberg D 100 is commercially available from Germany), is solid at room temperature and consists of the following units (according to 29 Si NMR and IR analysis) composed of 5 parts of silicone resin: (CH3)3SiO 1 / 2 -40mol%,50mol%SiO 4 / 2 -, 8 mol% C2H5OSiO 3 / 2 - and 2 mol% HOSiO 3 / 2 -, this resin has a weight average molar mass of 7900 g / mol (based on polystyrene standards), and 0.7 parts of a 20 wt% solution of KOH in glycerol are mixed in a dissolver and heated to 110° C. for 4 hours. A defoamer formulation with a viscosity of 3500 mPa·s (2.5 rpm, 25° C.) is obtained.

[0205] Production of Defoamer Preparation (A2):

[0206] The method for producing the defoamer preparation (A1) was repeated, wherein 82.3 parts by weight of trimethylsiloxy-terminated dodecylmethylsiloxane having an average chain length of 55 and a viscosity of 1100 mPa·s (measured at 25° C. and a shear rate of 10 / s) was used as the organopolysiloxane (Aa). A defoamer preparation (A2) having a viscosity of 28 700 mPa·s (2.5 rpm, 25° C.) was obtained.

[0207] Production of defoamer preparation (A3):

[0208] 85 parts of a trimethylsiloxy-terminated dimethylsiloxy-(α-methylstyryl)siloxy-methyloctylsiloxy copolymer having an average chain length of 60, a ratio of dimethylsiloxy units to (α-methylstyryl)siloxy units to methyloctylsiloxy units of 10:9:1, and a viscosity of 1500 mPa·s (measured at 25° C. and a shear rate of 10 / s), 5 parts of fumed silica as defoamer preparation (A1), 5 parts of a hydrocarbon mixture as defoamer preparation (A1), 5 parts of a silicone resin as defoamer preparation (A1), and 0.7 parts of a 20 wt % methanolic KOH solution were mixed in a dissolver and heated to 110° C. for 4 hours. A defoamer preparation having a viscosity of 9500 mPa·s (2.5 rpm, 25° C.) was obtained.

[0209] Example 2: Production of defoamer powder according to the present invention:

[0210] Production of Defoamer Powder (P1):

[0211] 10 parts of the antifoam formulation (A1) and 1.25 parts of glyceryl monostearate (available from Faci under the trade name GMS90, with a tristearate content of less than 1% by weight (according to HPLC analysis)) were mixed together at a temperature of 50° C. The obtained mixture was dispersed in 2.5 parts of a polyacrylic acid solution (50% by weight polyacrylic acid solution, as CP 10S commercially available from BASF). A white, creamy, flowable dispersion is obtained. The obtained dispersion is added to a mixture of 72.5 parts of sodium sulfate and 15 parts of zeolite 4A under high shear. After drying to constant weight at 80° C., a defoamer powder (P1) according to the invention is obtained.

[0212] Production of defoamer powder (P2):

[0213] Analogously to the description of the antifoam powder (P1), a dispersion was prepared from 3.75 parts of glyceryl monostearate GMS90, 2.5 parts of Sokalan CP 10S and 10 parts of the antifoam formulation (A1). This dispersion was added to a mixture of 70 parts of sodium sulfate and 15 parts of zeolite 4A and finally dried to obtain an antifoam powder (P2).

[0214] Production of Defoamer Powder (P3):

[0215] Analogously to the description of the antifoam powder (P1), a dispersion was prepared from 1.25 parts of glycerol monostearate GMS90, 7.5 parts of Sokalan CP 10S and 10 parts of the antifoam formulation (A1). This dispersion was added to a mixture of 70 parts of sodium sulfate and 15 parts of zeolite 4A and finally dried to obtain an antifoam powder (P3).

[0216] Production of defoamer powder (P4):

[0217] Analogously to the description of the antifoam powder (P1), a dispersion was prepared from 3.75 parts of glyceryl monostearate GMS90, 7.5 parts of Sokalan CP 10S and 10 parts of the antifoam formulation (A1). This dispersion was added to a mixture of 70 parts of sodium sulfate and 15 parts of zeolite 4A and finally dried to obtain an antifoam powder (P4).

[0218] Production of defoamer powder (P5):

[0219] Similar to the description of the antifoam powder (P1), a dispersion was prepared from 1.9 parts of glyceryl monostearate GMS90, 1.9 parts of paraffin (melting range: 56 to 58° C.), 8.0 parts of Sokalan CP 10S and 10 parts of the antifoam formulation (A1). This dispersion was added to a mixture of 67 parts of sodium sulfate and 15 parts of zeolite 4A and finally dried to obtain an antifoam powder (P5).

[0220] Production of Defoamer Powder (P6):

[0221] Analogously to the description of the antifoam powder (P1), a dispersion was prepared from 3.8 parts of glyceryl monostearate GMS90, 8.0 parts of Sokalan CP10S and 10 parts of the antifoam formulation (A3). This dispersion was added to a mixture of 66 parts of sodium sulfate and 15 parts of zeolite 4A and finally dried to obtain an antifoam powder (P6).

[0222] Production of Defoamer Powder (P7):

[0223] Analogously to the description of the antifoam powder (P1), a dispersion was prepared from 3.8 parts of glyceryl monostearate GMS90, 8.0 parts of Sokalan CP10S and 10 parts of the antifoam formulation (A2). This dispersion was added to a mixture of 66 parts of sodium sulfate and 15 parts of zeolite 4A and finally dried to obtain an antifoam powder (P7).

[0224] Example 3: Production of defoamer powder not of the present invention:

[0225] Production of Defoamer Powder (VP1):

[0226] 3.8 parts of glyceryl monostearate GMS90 and 10 parts of antifoam preparation (A1) were mixed with each other at 50° C., and the warm mixture was added to a mixture of 70 parts of sodium sulfate and 15 parts of zeolite 4A to obtain an antifoam powder (VP1) (not according to the invention).

[0227] Production of Defoamer Powder (VP2):

[0228] Analogously to the description for the defoamer powder (P1), 3.8 parts of glyceryl monostearate GMS90, 11.1 parts of polyacrylic acid with a pH of 8.5 (45 wt. % polyacrylic acid solution, as A dispersion was prepared from 10 parts of a defoamer formulation (A1) and 10 parts of CP 10 commercially available from BASF. This dispersion was added to a mixture of 66 parts of sodium sulfate and 15 parts of zeolite 4A and finally dried to give a defoamer powder (VP2) (not according to the invention).

[0229] Production of Defoamer Powder (VP3):

[0230] Analogously to the description for the defoamer powder (P1), 3.8 parts of glyceryl monostearate GMS90, 8.0 parts of an acrylic acid-maleic acid copolymer having a pH of 8.0 (40 wt. % acrylic acid-maleic acid copolymer solution, as CP 5, commercially available from BASF) and 10 parts of defoamer preparation (A1). This dispersion is added to a mixture of 67 parts of sodium sulfate and 15 parts of zeolite 4A and finally dried to give a (not inventive) defoamer powder (VP3).

[0231] Production of Defoamer Powder (VP4):

[0232] Analogously to the description of the defoamer powder (P1), a dispersion was prepared from 3.8 parts of Steareth-4, 8.0 parts of Sokalan CP 10S and 10 parts of the defoamer formulation (A1). This dispersion was added to a mixture of 66 parts of sodium sulfate and 15 parts of zeolite 4A and finally dried to give a defoamer powder (VP4) (not according to the invention).

[0233] Production of Defoamer Powder (VP5):

[0234] Analogously to the description of the defoamer powder (P1), a dispersion was prepared from 10.0 parts of Sokalan CP 10S and 10 parts of the defoamer formulation (A1). This dispersion was added to a mixture of 70 parts of sodium sulfate and 15 parts of zeolite 4A and finally dried to give a defoamer powder (VP5) (not according to the invention).

[0235] Production of Defoamer Powder (VP6):

[0236] A mixture of 3.8 parts of glyceryl monostearate GMS90 and 10 parts of antifoam preparation (A1) was added with 8.0 parts of Sokalan CP 10S on sodium carbonate and final drying of an antifoam powder (not according to the invention) (VP6) was obtained.

[0237] Production of Defoamer Powder (VP7):

[0238] 10 parts of the defoamer preparation (A1) are dispersed in 8.0 parts of Sokalan CP 10S. This dispersion is added to 85 parts of zeolite 4A and finally dried to give a defoamer powder (VP7) (not according to the invention).

[0239] Production of Defoamer Powder (VP8):

[0240] 10 parts of the antifoam preparation (A3) are mixed with 3.8 parts of glyceryl monostearate GMS 90 and the mixture is dispersed in 8.0 parts of Sokalan CP 10S. This dispersion is added to 82 parts of corn starch and finally dried to give an antifoam powder (not according to the invention) (VP8).

[0241] Embodiment 4:

[0242] Defoamer effectiveness testing in washing machines

[0243] 0.5% by weight of defoamer powder was added to 130 g of washing powder ECE-2 from WFK. The washing powder was then placed in a drum washing machine (model: Miele Novotronik W918, without fuzzy logic) together with 3500 g of clean cotton laundry. The washing program was then started. The program was run at a temperature of 40° C. and a water hardness of 3° GH. The foam height was recorded over a period of 55 minutes. The average foam score was determined from the foam scores determined over the entire period (0% no measurable foam to 100% excessive foaming). The lower the score, the more effective the defoamer powder was over the entire period.

[0244] The storage test in detergent powder ECE-2 was carried out as follows:

[0245] 0.5 wt% of defoamer powder was added to 130 g of washing powder and mixed thoroughly. The mixture was placed in a PE bag with a film thickness of 50 μm, the PE bag was closed and stored in a climate chamber at 35° C. / 70% humidity for 4, 8 or 12 weeks. After storage, the contents of the bag were checked in a drum washing machine as described above to check foam control.

[0246] Each foam score determination is the average of several individual measurements.

[0247] Table 1:

[0248] Defoamer effect of 0.05% of defoamer powder according to the invention in washing powder ECE-2 with and without storage:

[0249] Defoamer powder Average foam score without storage Average foam score after 12 weeks of storage p1 ++ ++ p2 ++ ++ p3 ++ ++ p4 ++ ++ p5 ++ ++

[0250] 0–10% foam: ++

[0251] 11–20% Foam: +

[0252] 21%–40% Foam: o

[0253] 41–60% Foam:-

[0254] >60% foam:--

[0255] All the defoamer powders according to the invention had an excellent defoamer effect in the washing powder ECE-2. Even after storage for 12 weeks, the defoamer powders still showed an excellent defoamer effect.

[0256] Table 2:

[0257] Defoaming effect of 0.05% of the defoamer powder VP1 not according to the invention in the washing powder ECE-2 with and without storage:

[0258] Defoamer powder Average foam score without storage Average foam score after 12 weeks of storage VP1 ++ --

[0259] The (non-inventive) antifoam powder (VP1) did show excellent antifoam efficacy without storage without the use of polyacrylic acid (as described in EP 0 210 731, EP 1 534 403 and EP 1 528 954). However, the antifoam efficacy completely degraded after 12 weeks of storage.

[0260] Therefore, a combination of acidic polyacrylic acid and glycerol monostearate (as used in the antifoam powders P1 to P5 according to the invention) is necessary to achieve very good storage stability.

[0261] Table 3:

[0262] Defoamer effect of 0.05% of the defoamer powders VP2 and VP3 not according to the invention in the washing powder ECE-2 with and without storage:

[0263] Defoamer powder Average foam score without storage Average foam score after 8 weeks storage VP2 ++ -- VP3 ++ --

[0264] Without the use of acidic polyacrylic acid, there was also excellent defoamer effectiveness without storage. However, the defoamer effectiveness had completely degraded after 8 weeks.

[0265] In contrast, if acidic polyacrylic acid is used (as in the defoamer powders P1 to P5 according to the invention), excellent storage stability is achieved.

[0266] Table 4:

[0267] Defoamer effect of 0.05% of defoamer powders VP4 and VP5 not according to the invention in washing powder ECE-2 with and without storage:

[0268] Defoamer powder Average foam score without storage Average foam score after 12 weeks of storage VP4 + -- VP5 + --

[0269] In the case of using stearyl polyether instead of glyceryl monostearate (VP4), or if glyceryl monostearate is omitted completely (VP5), a slightly worse efficacy is already exhibited without storage. After 12 weeks of storage, the defoamer efficacy decreases significantly.

[0270] In contrast, if glyceryl monostearate is used (as in the antifoam powders P1 to P5 according to the invention), excellent efficacy without storage and outstanding storage stability are achieved.

[0271] Table 5:

[0272] Defoamer effect of 0.05% of defoamer powder VP6 not according to the invention in washing powder ECE-2 with and without storage:

[0273] Defoamer powder Average foam score without storage Average foam score after 4 weeks storage VP6 o --

[0274] In the case of using only an alkaline carrier and not adding the polycarboxylate binder and defoamer formulation in the form of an aqueous premix, there is a weak defoamer effect without storage. In addition, the defoamer effect significantly degrades after 8 weeks of storage.

[0275] In contrast, if the alkaline carrier is not a major component (as in the defoamer powders P1 to P5 according to the invention, with about 18% by weight, based on the total amount of the carrier material) and if the polycarboxylate binder is added to the carrier material together with the defoamer formulation as an aqueous premix (as in the defoamer powders P1 to P5 according to the invention), there is an excellent efficacy without storage, and even after 12 weeks of storage the defoamer efficacy is still present.

[0276] Example 5: Dispersibility of defoamer powder:

[0277] First, 150 g of water was placed in a 250 ml glass bottle. The defoamer powder was added and stirred with a spatula. Visual evaluation was performed after 10 and 60 seconds.

[0278] Table 6:

[0279] Solubility / dispersibility of 0.1 wt. % defoamer powder in water after 10 and 60 seconds:

[0280] Defoamer powder Visual evaluation after 10 seconds Visual evaluation after 60 seconds P7 Clear solution with little precipitation Clear solution, sediment mostly dissolved VP7 Turbid solution, precipitate Turbidity increases again VP8 Low turbidity of solution, precipitation The turbidity of the solution increases again

[0281] In the case of using only zeolite or only starch as carrier material (VP7 and VP8), there is low solubility. In both cases, the result is a turbid solution that becomes more turbid over time.

[0282] In the case where a water-soluble support material (sodium sulfate) was used as the main component (P7), the result was a clear solution. The sediment that appeared at the beginning (but was smaller than in the case of VP7 or VP8) mostly dissolved over time.

[0283] The use of a water-soluble carrier material as the main component of the defoamer powder according to the invention clearly represents an advantage over the prior art.

Claims

1. A defoamer powder comprising (A) 100 parts by weight of a defoamer preparation, the preparation comprising (Aa) polysiloxane containing units of formula (I) R 1 R 2 SiO 2 / 2 (I), in, R 1 may be the same or different and are monovalent, optionally branched, SiC-bonded hydrocarbon radicals having 1 to 5 carbon atoms, R 2 may be the same or different and are monovalent, optionally branched, SiC-bonded hydrocarbon groups having 6 to 30 carbon atoms, (Ab) filler, (Ac) an organopolysiloxane resin composed of units of the following general formula: R 3 a (R 4 O) b SiO (4-a-b) / 2 (II) in, R 3 may be the same or different and are monovalent, optionally substituted, SiC-bonded hydrocarbon groups having 1 to 30 carbon atoms, R 4 may be identical or different and are a hydrogen atom or a monovalent, optionally substituted hydrocarbon group having 1 to 4 carbon atoms, a is 0, 1, 2, or 3, and b is 0, 1, 2, or 3, Provided that the sum of a+b is ≤3, and in less than 50% of all units of formula (II) in the organopolysiloxane resin, the sum of a+b=2, (Ad) optionally another organopolysiloxane composed of units of formula (III) and (IV) R 1 2SiO 2 / 2 (III), R 5 R 1 2SiO 1 / 2 (IV), in, R 1 With the definition as above, R 5 can be the same or different and can be R 1 OR 6 ,in R 6 is a hydrogen atom or a monovalent, optionally substituted, hydrocarbon group having 1 to 25 carbon atoms, (Ae) optionally a water-insoluble organic compound, (Af) optional basic or acidic catalyst or its reaction product with components (Aa) to (Ad) (B) based on 100 parts by weight of the defoamer preparation (A), 10 to 45 parts by weight of a waxy additive, wherein the waxy additive comprises a monoester (B') of glycerol and a fatty acid; It does not contain additives containing polysiloxane, and It contains less than 5% by weight of triesters of glycerol and fatty acids (B"), (C) based on 100 parts by weight of the defoamer preparation (A), 10 to 50 parts by weight of a polycarboxylate binder, the binder having a pH of 3 or less when dissolved in water, (D) based on 100 parts by weight of the defoamer preparation (A), 120 to 5000 parts by weight of at least one pulverulent carrier material, provided 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 powder according to claim 1, characterized in that The polysiloxane (Aa) is an organopolysiloxane of the following formula: R 5 R 1 2SiO-(SiR 1 2O) x -(SiR 1 R 2 O) y -SiR 1 2R 5 (VIII), in R 1 , R 2 and R 5 having the meaning given thereto in claim 1, x is greater than or equal to 0 and less than 200 on average, and On average, y is greater than 5 and less than 200.

3. The defoamer powder according to claim 1 or 2, characterized in that Silica was used as filler (Ab).

4. The defoamer powder according to claim 1, 2 or 3, characterized in that The organopolysiloxane resin (Ac) used is an MQ resin composed of units of the following formula: SiO2 (Q unit) and R 3 3SiO 1 / 2 (M unit), The molar ratio of the M unit to the Q unit is in the range of 0.5 to 2.

0. In addition to the M unit and the Q unit, the MQ resin may also contain a small amount of R 3 SiO 3 / 2 or (R 4 O)SiO 3 / 2 (T) unit or R 3 2SiO 2 / 2 (D) units in an amount of 0.01 to 20 mol% based on the sum of all siloxane units, and the MQ resin may contain up to 10 wt% of free Si-bonded hydroxyl or alkoxy groups, such as methoxy or ethoxy groups, Where R 3 and R 4 It has the definition given to it in claim 1.

5. The defoamer powder according to any one of claims 1 to 4, characterized in that The waxy additive (B) contains, in the total mixture of the waxy component (B) used, 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 monoesters of glycerol and fatty acids and less than 5% by weight of triglycerols.

6. The defoamer powder according to any one of claims 1 to 5, characterized in that The monoester of glycerol and a fatty acid is glyceryl monolaurate, glyceryl monomyristate, glyceryl monopalmitate or glyceryl monostearate.

7. The defoamer powder according to any one of claims 1 to 6, characterized in that The polycarboxylate binder (C) is a water-soluble or water-dispersible homopolymer, copolymer or salt thereof, which contains at least 60% by weight of the following general formula fragment: (CR 8 2-CR 8 2) n (V), in The value of n is between 10 and 100,000, preferably between 20 and 10,000, particularly preferably between 30 and 1,000, R 8 is selected from hydrogen, an (optionally substituted) hydrocarbon group having 1 to 30 carbon atoms, a carboxyl group or a salt thereof, and a group having the following general formula -C(O)-OR 9 (WE), -C(O)-N(R 10 )2(VII), in R 9 is an optionally functionalized hydrocarbon group having 1 to 30 carbon atoms, and R 10 is hydrogen or a group R 9 or R 11 -SO3X, in R 11 is a divalent alkylene group having 1 to 12 carbon atoms, and X is a hydrogen atom or a cation, The proviso is that at least 5 mol %, preferably at least 10 mol %, in particular at least 15 mol % of the radicals R 8 The acidic group is selected from a carboxyl group or a salt thereof and a sulfonyl group-containing group or a salt thereof, preferably a carboxyl group and a salt thereof.

8. The defoamer powder according to any one of claims 1 to 7, characterized in that The polycarboxylate binder (C) is a homopolymer or copolymer of a monomer selected from the group consisting 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 powder according to any one 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 carboxymethylcellulose are used as pulverulent carrier materials in an amount of more than 50% by weight.

10. A method for producing a defoamer powder according to any one of claims 1 to 9, characterized in that preparing a premix of the defoamer preparation (A), the waxy additive (B) and the binder (C), preferably in the form of a dispersion, and The premix is ​​mixed with the powdered carrier material.

11. The method according to claim 10, characterized in that The premix is ​​mixed in the form of an aqueous dispersion with the pulverulent carrier material.

12. The method according to claim 10 or 11, characterized in that: The antifoam powder is then dried.

13. A cleaning agent or cleaning composition comprising the defoamer powder according to any one of claims 1 to 9 or the defoamer powder produced according to claim 10.