Defoaming composition for detergent

Abstract

Detergent defoaming agent composition (A) (Aa) Formula (I): R 1 R 2 SiO 2 / 2 , wherein R 1 is a monovalent, optionally branched, SiC-bonded hydrocarbon group having 1 to 5 carbon atoms, and R 2 is a monovalent, optionally branched, SiC-bonded hydrocarbon group having 6 to 30 carbon atoms, a polysiloxane containing units, (Ab) a filler, (Ac) General formula (II): R 3 a (R 4 O) b SiO (4-a-b) / 2 , wherein R 3 is a monovalent, optionally substituted, SiC-bonded hydrocarbon group having 1 to 30 carbon atoms, and R 4 is a hydrogen atom or a monovalent, optionally substituted, hydrocarbon group having 1 to 4 carbon atoms, a is 0, 1, 2 or 3, b is 0, 1, 2 or 3, provided that the sum of a + b is ≦ 3, and in less than 50% of all the units of formula (II), the sum of a + b = 2, an organopolysiloxane resin composed of units, optionally further organopolysiloxane (Ad), optionally a water-insoluble organic compound (Ae), and optionally a catalyst (Af) 100 parts by mass of a defoaming agent, (B) not containing a polysiloxane-containing additive, and containing less than 5% by mass of a triester (B'') of glycerol and a fatty acid, 10 to 45 parts by mass of a wax-like additive containing a monoester (B') of glycerol and a fatty acid, (C) 10 to 50 parts by mass of a polycarboxylate binder having a pH of 3 or less when dissolved in water, (D) at least one powdered carrier material, provided that the carrier material contains less than 50% by mass of an alkaline carrier material, 120 to 5000 parts by mass of a powdered carrier material, to describe a novel defoaming agent powder.

Description

Technical Field

[0001] The present invention relates to an antifoaming agent powder containing a waxy non-silicone-containing component, a polycarboxylate binder, and a powdery water-soluble carrier material in addition to an antifoaming agent formulation, a method for producing the same, and its use for defoaming a medium, preferably an aqueous medium, particularly for defoaming an aqueous surfactant formulation.

Background Art

[0002] In many liquid systems, particularly aqueous systems, when they contain surfactant compounds as desirable or undesirable components, when these systems come into intense contact with gaseous substances more or less, for example, in wastewater sparging, intense agitation of liquids, distillation, washing, dyeing processes, filling operations, etc., the formation of foam may cause problems.

[0003] This foam can be controlled by mechanical means or by the addition of an antifoaming agent. In this case, it has been found that antifoaming agents based on siloxanes are particularly useful. Antifoaming agents based on siloxanes are produced, for example, according to US Patent No. 3383327, by heating hydrophilic silica in polydimethylsiloxane. Polyorganosiloxanes having pendant relatively long-chain n-alkyl groups are also described in US Patent Application Publication No. 2009 / 0137446 as main components for producing effective antifoaming agents.

[0004] When using solid products such as detergents, cleaning compositions, agricultural products, pharmaceutical preparations, etc., mainly powdery antifoaming agents are used. In this case, it is advantageous to make the antifoaming agent, which usually exists as an oily and viscous liquid, into a powder by adsorbing it on a solid carrier material. When used in cleaning powders, it is particularly advantageous if the carrier material used does not interfere with the cleaning process or is the detergent component itself. A common characteristic of most of the antifoaming agent powders obtained by simply coating the antifoaming agent on the carrier material is that they quickly lose their efficacy when stored, particularly in the presence of alkaline compounds.

[0005] To address this drawback, various solutions have been proposed. One possible solution is the encapsulation or coating of the carrier material aimed at improving the fixing of the antifoaming agent. For this purpose, European Patent Application Publication No. 0995473 proposes the use of an acidic polycarboxylate combined with a polyether-functionalized polysiloxane on zeolite of the carrier material.

[0006] European Patent Application Publication No. 0210731 describes the use of a monoester of glycerol as a waxy additive. When the described monoester of glycerol is used in excess with respect to the antifoaming agent based on polydimethylsiloxane, storage stability can be shown.

[0007] International Publication No. 2004 / 018073 describes an antifoaming agent based on a polyorganosiloxane pendant-functionalized with an α-methylstyryl group supported on sodium carbonate, starch or zeolite, and a glycerol triester such as glycerol tristearate is always used as an additive. The additive has a positive effect on the efficacy of the antifoaming agent powder when used for controlling the foam of the washing powder. There is no description about storage stability.

[0008] International Publication No. 2004 / 018074 describes an antifoaming agent powder in which a waxy glycerol triester is similarly used as an additive. The glycerol triester is sprayed onto a carrier together with the antifoaming agent, particularly onto sodium carbonate or starch, in partial combination with highly polar additives such as glycerol monoesters, alkylphenols, aliphatic alcohols or fatty acids. The amount of the additive is at least 50% by mass based on the antifoaming agent. It was also possible here to demonstrate that it has a positive effect on the efficacy of the antifoaming agent powder when used for controlling the foam of the washing powder. Similarly, there is no description about storage stability.

Prior Art Documents

Patent Documents

[0009] [Patent Document 1] U.S. Patent No. 3,383,327 [Patent Document 2] U.S. Patent Application Publication No. 2009 / 0137446 [Patent Document 3] European Patent Application Publication No. 0995473 [Patent Document 4] International Publication No. 2004 / 018073 [Patent Document 5] International Publication No. 2004 / 018074 [Summary of the Invention] [Problems to be Solved by the Invention]

[0010] The disadvantages of the described solutions are, in some cases, the large amount of additional organic additives required, the lack of storage stability in the solid surfactant matrix, and the suboptimal water solubility or water dispersibility.

[0011] Accordingly, an object of the present invention was to provide an antifoaming agent powder that contains only a small amount of additional components in addition to the antifoaming agent formulation and the carrier material, and has excellent storage stability and excellent water solubility or dispersibility. In particular, it is desirable that the produced antifoaming agent powder can be used in detergents and cleaning compositions. [Means for Solving the Problems]

[0012] The present invention relates to an antifoaming agent powder, (A) 100 parts by mass of an antifoaming agent formulation, (Aa) Formula (I) R 1 R 2 SiO 2 / 2 (I) (In the formula, R 1 is the same or different and is a monovalent, optionally branched, SiC-bonded hydrocarbon group having 1 to 5 carbon atoms, R 2is a monovalent, optionally branched, SiC-bonded hydrocarbon group having 6 to 30 carbon atoms, which may be the same or different. A polysiloxane containing the unit of (Ab) filler (Ac) General formula (II) R 3 a (R 4 O) b SiO (4-a-b) / 2 (II) (In the formula, R 3 is a monovalent, optionally substituted, SiC-bonded hydrocarbon group having 1 to 30 carbon atoms, which may be the same or different; R 4 is a hydrogen atom or a monovalent, optionally substituted, hydrocarbon group having 1 to 4 carbon atoms, which may be the same or different; a is 0, 1, 2 or 3; b is 0, 1, 2 or 3; provided that the sum of a + b is ≦ 3, and in less than 50% of all the units of formula (II) in the organopolysiloxane resin, the sum of a + b is = 2. An organopolysiloxane resin composed of the units of Optionally (Ad) Formulas (III) and (IV) R 1 2SiO 2 / 2 (III) R 5 R 1 2SiO 1 / 2 (IV) (In the formula, R 1 has the above definition; R 5 may be the same or different, and may be R 1 or -OR 6 wherein R 6 is a hydrogen atom or a monovalent, optionally substituted, hydrocarbon group having 1 to 25 carbon atoms. A further organopolysiloxane composed of the units of Optionally (Ae) A water-insoluble organic compound, optionally (Af) an alkaline or acidic catalyst, or a reaction product thereof with components (Aa)-(Ad), A defoamer formulation comprising (B) a waxy additive in an amount of 10 to 45 parts by mass based on 100 parts by mass of the defoamer formulation (A), comprising a monoester (B’) of glycerol and a fatty acid, not containing a polysiloxane-containing additive, containing less than 5% by mass of a triester (B’’) of glycerol and a fatty acid, a waxy additive, (C) a polycarboxylate binder in an amount of 10 to 50 parts by mass based on 100 parts by mass of the defoamer formulation (A), having a pH of 3 or less when dissolved in water, (D) at least one powdered carrier material in an amount of 120 to 5000 parts by mass based on 100 parts by mass of the defoamer formulation (A), provided that the carrier material contains less than 50% by mass of an alkaline carrier material, preferably less than 40% by mass of an alkaline carrier material, more preferably less than 25% by mass of an alkaline carrier material A defoamer powder is provided.

[0013] The term "defoamer powders" should be understood to mean both pulverulent and granulated products.

Advantages of the Invention

[0014] Now, surprisingly, defoamer powders having such a composition have been found to have significantly improved storage stability in washing powders, while at the same time using less additional chemicals and having significantly improved water solubility or water dispersibility in washing liquids, as compared to the prior art.

Modes for Carrying Out the Invention

[0015] The antifoaming agent powder according to the present invention preferably contains, in each case, based on 100 parts by mass of the antifoaming agent formulation (A), 10 to 42 parts by mass of the wax-like additive (B), 10 to 47 parts by mass of the polycarbonate binder (C), and 200 to 2000 parts by mass of the powdery carrier material (D), and particularly preferably contains, in each case, based on 100 parts by mass of the antifoaming agent formulation (A), 13 to 40 parts by mass of the wax-like additive (B), 13 to 45 parts by mass of the polycarboxylate binder (C), and 300 to 1200 parts by mass of the powdery carrier material (D).

[0016] The antifoaming agent powder according to the present invention preferably consists essentially of components (A), (B), (C), and (D).

[0017] Preferably, the antifoaming agent (A) consists of components (Aa), (Ab), (Ac), and optionally components (Ad), (Ae), and (Af).

[0018] Preferably, the antifoaming agent (A) contains the following. (1) At least 55% by mass, preferably at least 65% by mass, particularly preferably at least 75% by mass, and preferably at most 97% by mass, more preferably at most 90% by mass, particularly preferably at most 85% by mass of polysiloxane (Aa), (2) At least 1% by mass, preferably at least 2% by mass, particularly preferably at least 3% by mass, and preferably at most 15% by mass, more preferably at most 12% by mass, particularly preferably at most 10% by mass of the filler (Ab), (3) At least 1% by mass, preferably at least 2% by mass, particularly preferably at least 3% by mass, and preferably at most 15% by mass, more preferably at most 12% by mass, particularly preferably at most 10% by mass of the organopolysiloxane resin (Ac) composed of units of formula (II) (4) At least 0% by mass, and preferably at most 15% by mass, more preferably at most 10% by mass, particularly preferably at most 7.5% by mass of the organopolysiloxane (Ad) composed of units of formula (III) and (IV), (5) At least 0% by mass, and preferably at most 15% by mass, more preferably at most 10% by mass, particularly preferably at most 7.5% by mass, of a water-insoluble organic compound (Ae), and (6) At least 0% by mass, preferably at least 0.05% by mass, particularly preferably at least 0.1% by mass, and preferably at most 1% by mass, more preferably at most 0.5% by mass, particularly preferably at most 0.3% by mass, of an alkaline or acidic catalyst (Af) or a reaction product thereof with components (Aa) to (Ad).

[0019] Preferably, the organopolysiloxane (Aa) used in the defoaming agent composition (A) is of the formula (VIII) R 5 R 1 2SiO-(SiR 1 2O) x -(SiR 1 R 2 O) y -SiR 1 2R 5 (VIII) (wherein, R 1 , R 2 and R 5 have the above definitions, x is 0 or more and less than an average of 200, preferably less than 100, particularly preferably less than 50, y is greater than 5 on average, preferably greater than 10, and less than 200, preferably less than 100, particularly preferably less than 50.) is an organopolysiloxane.

[0020] The organopolysiloxane (Aa) may additionally contain branches by containing units of the formulas (IX) and (X). SiO 4 / 2 (IX) R 1 SiO 3 / 2 or R 2 SiO 3 / 2 or R 5 SiO 3 / 2(X) R 1 LSiO 2 / 2 or R 2 LSiO 2 / 2 or R 5 LSiO 2 / 2 (XI) (In the formula, R 1 , R 2 and R 5 have the definitions given above, L is a divalent structure that connects two organopolysiloxane chains to each other. L may be an alkylene group such as an ethylene group, a propylene group, a butylene group, a hexylene group, an octylene group, preferably a hexylene group or an octylene group, a divalent aromatic group such as a 1,2-bisethylene benzene group, a 1,4-bisethylene benzene group or a 1,8-bisethylene naphthalene group, a cycloalkylene group such as a 1,4-bisethylene cyclohexane group or a divalent organosiloxane chain.)

[0021] Examples of the hydrocarbon group R 1 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 groups; and cycloalkyl groups such as a cyclopentyl group.

[0022] R 1 Preferred examples are methyl and ethyl groups. A particularly preferred example is a methyl group.

[0023] Hydrocarbon group R 2Examples include an alkyl group such as a hexyl group like an n - hexyl group, a heptyl group like an n - heptyl group, an octyl group such as an n - octyl group, an isooctyl group such as 2,2,4 - trimethylpentyl or 2 - ethylhexyl group, a nonyl group like an n - nonyl group, a decyl group like an n - decyl group, a dodecyl group like an n - dodecyl group, a tetradecyl group like an n - tetradecyl group, a hexadecyl group like an n - hexadecyl group, an octadecyl group like an n - octadecyl group; a cycloalkyl group such as cyclohexyl, cycloheptyl, methylcyclohexyl, 4 - ethylcyclohexyl group; an aryl group such as phenyl, naphthyl, anthryl, phenanthryl group; an alkaryl group such as o -, m -, p - tolyl group, xylyl group, ethylphenyl group; and an aralkyl group such as benzyl group, 2 - phenylpropyl group, α - and β - phenylethyl group.

[0024] R 2 Preferred examples include an n - octyl group, an n - decyl group, an n - dodecyl group, an n - tetradecyl group, an n - hexadecyl group, an n - octadecyl group, a phenyl group, a benzyl group and a 2 - phenylpropyl group. Particularly preferred examples are an n - octyl group, an n - dodecyl group, a phenyl group and a 2 - phenylpropyl group.

[0025] R 5 Examples, preferred examples, and particularly preferred examples of R 1 or the group of the formula - OR 6 are examples, preferred examples, and particularly preferred examples.

[0026] R 6Examples include 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 group, hexyl groups such as n-hexyl group, heptyl groups such as n-heptyl group, octyl groups such as n-octyl group, and isooctyl groups such as 2,2,4-trimethylpentyl and 2-ethylhexyl group, nonyl groups such as n-nonyl group, decyl groups such as n-decyl group, dodecyl groups such as n-dodecyl group, tetradecyl groups such as n-tetradecyl group, hexadecyl groups such as n-hexadecyl group, octadecyl groups such as n-octadecyl group; and cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl and 4-ethylcyclohexyl group.

[0027] R 6 Preferred examples of R are a hydrogen atom, or methyl and ethyl groups. Particularly preferred examples are a hydrogen atom or a methyl group.

[0028] Preferably, the filler (Ab) used in the defoaming agent composition (A) has a BET surface area of 20 to 1000 m 2 / g. Preferably, the filler (Ab) has a particle size of less than 10 μm and a weak agglomerate size of less than 100 μm.

[0029] Examples of the filler (Ab) include silicon dioxide (silica), titanium dioxide, aluminum oxide, metal soaps, ground quartz, PTFE powder, fatty acid amides such as ethylene bisstearic acid amide, and finely divided hydrophobic polyurethane.

[0030] Preferably used as the filler (Ab) is silicon dioxide (silica), titanium dioxide or aluminum oxide having a BET surface area of 20 to 1000 m 2 / g. Preferably, these fillers have a particle size of less than 10 μm and a weak agglomerate size of less than 100 μm.

[0031] Preferably, the filler (Ab) is silica, particularly having a BET surface area of 50 to 800 m 2 / g. These silicas may be fumed silica or precipitated silica. Both pretreated silica, i.e., hydrophobic silica and hydrophilic silica, can be used as the filler (Ab). Examples of commercially available hydrophobic silicas that can be used according to the present invention are fumed hexamethyldisilazane-treated silica having a BET surface area of 140 m 2 / g, HDK(R) H2000 (commercially available from Wacker Chemie AG, Germany), and precipitated polydimethylsiloxane-treated silica having a BET surface area of 90 m 2 / g (commercially available from Evonik, Germany under the name "Sipernat(R) D10").

[0032] The hydrophilic silica may be hydrophobized in situ if it is advantageous for the desired efficacy of the defoamer formulation. Many processes for the hydrophobization of silica are known. The in situ hydrophobization of 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 a catalyst (Af) and a hydrophobizing agent, such as a short-chain OH-terminated polydimethylsiloxane, silane or silazane.

[0033] The component (Ac) used in the defoamer formulation (A) is preferably a silicone resin composed of units of formula (II), in which case, preferably less than 30%, more preferably less than 5% of the units in the resin, the sum of a + b is equal to 2.

[0034] Preferably, R 3 is a hydrocarbon group having 1 to 30 carbon atoms. The hydrocarbon group R 3Examples include 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 group, heptyl groups such as n-heptyl group, octyl groups such as n-octyl group, isooctyl groups such as 2,2,4-trimethylpentyl and 2-ethylhexyl groups, nonyl groups such as n-nonyl group, decyl groups such as n-decyl group, dodecyl groups such as n-dodecyl group, tetradecyl groups such as n-tetradecyl group, hexadecyl groups such as n-hexadecyl group, octadecyl groups such as n-octadecyl group, etc.; cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl, 4-ethylcyclohexyl group, etc.; aryl groups such as phenyl, naphthyl, anthryl, phenanthryl group, etc.; alkaryl groups such as o-, m-, p-tolyl groups, xylyl group and ethylphenyl group, etc.; and aralkyl groups such as benzyl group, 2-phenylpropyl group and α- and β-phenylethyl groups, etc. Group R 3 Preferred examples are methyl, ethyl and phenyl groups. Group R 3 Particularly preferred example is the methyl group.

[0035] Group R 4 Examples are a hydrogen atom, and alkyl groups such as methyl, ethyl, n-propyl, isopropyl and n-butyl groups. Group R 4 is preferably a hydrogen atom, or a methyl or ethyl group.

[0036] Preferably, the organopolysiloxane resin (Ac) composed of units of formula (II) is the formula SiO2(IX) and R 3 3SiO 1 / 2 (XII) (wherein R 3 has the definition given above.) is an MQ resin composed of units of The molar ratio of the M unit to the Q unit 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 unit and the Q unit, the MQ resin may optionally and in small amounts also contain R 3 SiO 3 / 2 or (R 4 O)SiO 3 / 2 (T) units or R 3 2SiO 2 / 2 (D) units, based on the total of all siloxane units, may preferably be included in an amount of from 0.01 to 20 mol%, more preferably from 0.01 to 5 mol%, where 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 groups or alkoxy groups such as methoxy or ethoxy groups.

[0037] Preferably, these organopolysiloxane resins (Ac) have a viscosity exceeding 1000 mPa·s or are solids at 25 °C and 101.425 kPa. The weight average molecular weight measured by gel permeation chromatography (based on polystyrene standards) of these resins is preferably from 200 to 200,000 g / mol, particularly from 1000 to 20,000 g / mol.

[0038] An organopolysiloxane (Ad) different from the polysiloxane (Aa) can optionally be used in the defoamer formulation (A). Preferably, the organopolysiloxane (Ad) has the formula (IXX) R 5 R 1 2SiO-(SiR 1 2O) z -SiR 1 2R 5 (IXX) (wherein R 1 and R 5 have the definitions given above, and z is on average greater than 5, preferably greater than 10, and less than 500, preferably less than 200, particularly preferably less than 100.) is an organopolysiloxane.

[0039] The water-insoluble organic compound (Ae) can be optionally used in the antifoaming agent composition (A). In the context of the present invention, the term "water-insoluble" should be understood to mean having a solubility in water at 25 °C and a pressure of 101.425 kPa of at most 3% by mass.

[0040] The optionally used component (Ae) is preferably a water-insoluble organic compound having a boiling point exceeding 100 °C and a melting point below 35 °C at the pressure of the ambient atmosphere, i.e., 900 to 1100 hPa, and is particularly selected from mineral oils, natural oils, isoparaffins, polyisobutylenes, residues from the synthesis of oxo alcohols, 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, aliphatic alcohols that are liquid at temperatures higher than 35 °C, ethers of low molecular weight alcohols, esters of phthalates and phosphates.

[0041] Examples of the alkali catalyst (Af) are alkali metal hydroxides and alkaline earth metal hydroxides such as NaOH, KOH, CsOH, LiOH and Ca(OH)2. Examples of the acidic catalyst (Af) are hydrochloric acid, sulfuric acid and phosphonitrilic chloride. The reaction product of (Af) and components (Aa) to (Ad) is, for example, a product of silica, which is preferable as the filler (Ab), and an alkali metal hydroxide such as potassium silicate or sodium silicate. The quantitative addition of the catalyst can be carried out in a typical organic solvent such as an alcohol (methanol, ethanol, isopropanol, etc.) or an ester (ethyl acetate, etc.).

[0042] The components (Aa) to (Af) used in the antifoaming agent complex (A) may each be one type of component, or may be a mixture of at least two individual components.

[0043] In any case, the antifoaming agent complex (A) has a viscosity of preferably 100 to 2000000 mPa·s, more preferably 500 to 80000 mPa·s, and particularly preferably 1000 to 15000 mPa·s at 25°C and 101.425 kPa.

[0044] The antifoaming agent complex (A) according to the present invention can be produced by known methods such as mixing all components using high shear force with a colloid mill, a dissolver, or a rotor - stator homogenizer. The mixing step may be carried out under reduced pressure, for example, to prevent the incorporation of air present in the highly dispersed filler. If necessary, the filler may subsequently be hydrophobized in situ. It is also possible to first charge component (Aa), optionally heat it, and then continuously add components (Ab), (Ac), optionally (Ad), optionally (Ae), and optionally (Af). In a preferred embodiment, component (Ac) is added in a form dissolved as a solution in component (Ad) or (Ae), or in a part of component (Ad) or (Ae).

[0045] The waxy additive (B) used is an organic substance having a melting point in the range from 35°C to 85°C, and its main component is a monoester of glycerol and a fatty acid (also called 1 - monoacylglycerol).

[0046] In particular, these are monoesters of glycerol and aliphatic fatty acids having a carbon chain containing 12 to 20 carbon atoms. This includes racemic and optically active products. Examples of such monoesters include glycerol monolaurate, glycerol monomyristate, glycerol monopalmitate, and glycerol monostearate. A particularly preferred example of the monoester is glycerol monostearate.

[0047] The waxy additive (B) used may be an organic substance having a melting point in the range of 35°C to 85°C and being a mixture of a plurality of components mainly composed of a monoester of glycerol and a fatty acid as a result of production. Therefore, industrial products of 1-monoacylglycerol are generally mixtures of 1-monoacylglycerol and diacylglycerol with different monoacylglycerol contents. Furthermore, these industrial products may contain small amounts of triacylglycerol, free glycerol, and free fatty acids.

[0048] In the case of glycerol monostearate, most of it is a mixture of glycerol monostearate and glycerol distearate, and glycerol monopalmitate and a small amount of glycerol tristearate may also be present, as well as free glycerol (in the case of non-emulsifying or non-self-emulsifying glycerol monostearate) or a certain amount of soap (in the case of self-emulsifying glyceryl monostearate). In the case of glycerol monostearate, most of it can be a mixture of glycerol monostearate and glycerol distearate.

[0049] Also, the waxy additive (B) used may be an organic substance having a melting point in the range of 35°C to 85°C and being an organic substance in which an additional waxy organic substance is intentionally added to the monoester of glycerol and a fatty acid as the main component. This additional waxy organic substance is not an ester of a fatty acid and glycerol and has a melting point in the range of 35°C to 85°C. Examples of additional waxy substances include amide waxes (e.g., stearic acid amide, behenic acid amide, erucic acid amide, oleic acid amide), semi-synthetic waxes such as alcohol waxes or ketone waxes, or synthetic waxes such as polyolefin waxes or waxy hydrocarbons (e.g., hard paraffin having a melting point from 50°C to 62°C).

[0050] Regardless of whether it is a result of production or whether additional waxy substances are used, the content of 1-monoacylglycerol is preferably 30% by mass or more, more preferably 50% by mass or more, particularly preferably 70% by mass or more in the total mixture of the waxy component (B) used, and the content of triacylglycerol is preferably less than 5% by mass.

[0051] What is essential for the antifoaming agent powder according to the present 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. This combination has been found to be essential for storing the antifoaming agent powder according to the present invention stably in the cleaning powder.

[0052] The polycarboxylate binder (C) is a water-soluble or water-dispersible polymer, homopolymer, copolymer or their salts. These are represented by the general formula (V) (CR 8 2-CR 8 2) n (V), (wherein n assumes a value of 10 to 100000, preferably 20 to 10000, particularly preferably 30 to 1000, R 8 is hydrogen, an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, a carboxyl group or its salt, and the general formula -C(O)-O-R 9 (VI), -C(O)-N(R 10 )2(VII), (wherein R 9 is an optionally functionalized hydrocarbon group having 1 to 30 carbon atoms, R 10 is hydrogen, group R 9 or R 11 -SO3X (wherein, R 11 is a divalent alkylene group having 1 to 12 carbon atoms, X is a hydrogen atom or a cation.) is any of.) selected from the groups of, provided that at least 5 mol%, preferably at least 10 mol%, particularly at least 15 mol% of the group R 8 is an acidic group selected from carboxyl groups or their salts and sulfonyl groups or their salts, preferably selected from carboxyl groups and their salts.) contains at least 60% by mass of the segment of.)

[0053] Groups R 8 may be the same or different.) Examples of the group R 8 include a hydrogen atom, a monovalent (optionally substituted) alkyl, aryl, aralkyl and cycloaliphatic hydrocarbon group, for example, methyl, ethyl, heptyl, octyl, 2-ethylhexyl, decyl, isodecyl, dodecyl, lauryl, myristyl, stearyl, phenyl, (4-sulfonyl)phenyl or (2-sulfonyl)phenyl such as (sulfonyl)phenyl, 1-naphthyl, and (sulfonyl)naphthyl group, a carboxyl group, or groups of formula (VI) and (VII).

[0054] Preferred group R 8 is a hydrogen atom, a methyl group, an ethyl group, a (sulfonyl)phenyl group, a carboxyl group, or groups of formula (VI) and (VII).

[0055] Group R 9are monovalent alkyl, aryl, aralkyl, and cycloaliphatic hydrocarbon groups which may be the same or different.

[0056] Group R 9 Examples thereof include methyl, ethyl, n-butyl, isobutyl, tert-butyl, 2-ethylhexyl, lauryl, stearyl, benzyl, isopropyl, neopentyl, cyclohexyl, 2-hydroxyethyl, and 2-hydroxypropyl groups.

[0057] Group R 10 may be the same or different and may be hydrogen, group R 9 or R 11 -SO3X.

[0058] The divalent alkylene group R 11 Examples thereof include a methylene group, 1,2-ethylene group, 1,3-propylene group, 1,2-propylene group, or (2-methyl-)1,2-propylene group. Examples of X include a hydrogen atom, or a cation such as a sodium, potassium, calcium, magnesium, lithium cation, or an ammonium cation derived from, for example, ammonia, monoethanolamine, diethanolamine, triethanolamine, or isopropylamine.

[0059] Examples of preferred segments corresponding to general formula (V) are as follows: (CH2-C(CH3)R 12 ) n (XIII) (CH2-C(C2H5)R 12 ) n (XV) (CH2-CHR 12 ) n (XVI) (CHR 12 -CHR 12 ) n (XVII) (wherein R 12 is the following group -C(O)-O-H (XVIII), and -C(O)-NR 10 2(VII) (wherein R 10 has the definition given above.) is selected from.)

[0060] The carboxyl group (XVIII) and the sulfonyl group can also be partially neutralized by a base, preferably a base having a monovalent positive charge such as an alkali metal cation or an ammonium cation, and still, it is necessary to satisfy the condition that the pH is 3 or less when the binder (C) is dissolved in water.)

[0061] Examples of monomers that bring about 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, 2-acrylamido-2-methylpropanesulfonic acid (AMPS).

[0062] Maleic anhydride or maleimide can be used as the monomer. In this case, the incorporated anhydride group or imide group preferably reacts completely or partially with water, alcohol, amine or ammonia solution to form a carboxyl group, an ester group and / or an amide group.)

[0063] Preferred examples of monomers that bring about 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.)

[0064] Particularly preferred examples of monomers that bring about these structures are acrylic acid, maleic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and maleic anhydride.)

[0065] A relatively small amount of monomer materials that do not contain carboxylic acids, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl 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, 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 copolymerization with ethylene are not harmful to the use of polycarboxylate in the foaming control agent according to the present invention. Depending on the type of polycarboxylate, this content can be kept low or up to about 40% by mass of the total polymer or copolymer.

[0066] Such compounds and similar compounds (C) that can be used in the context of the present invention are known and commercially available. For example, Sokalan(R) PA80S and Sokalan(R) PA110S (manufactured by BASF, Germany) with a pH of about 1.5, acrylic-maleic acid copolymers, such as Sokalan(R) CP12S (manufactured by BASF, Germany) with a pH of about 1, and modified polyacrylic acid polymers, such as Sokalan(R) CP10S and 13S (also manufactured by BASF, Germany) with a pH of about 1.5, or Aquatreat(R) AR-540 (manufactured by Nouryon, a copolymer of acrylic acid and sulfonated monomers) can be mentioned.

[0067] The antifoaming agent powder according to the present invention preferably contains a carrier material (D) that is not an alkaline carrier material. An alkaline carrier material is one that provides an alkaline pH, i.e., a pH of 11 or higher, when dissolved or dispersed in water. This is determined from a 0.02 mass% solution or a 5 mass% slurry. The storage stability of the antifoaming agent powder according to the present invention in the cleaning powder has been found to be significantly improved mainly when a non-alkaline carrier material is used. The carrier material (D) present in the antifoaming agent powder according to the present invention may be each a single component or a mixture of at least two individual components.

[0068] When only one type of component is used as the carrier material, this should be a non-alkaline carrier material. When several types of components are used as the carrier material, the non-alkaline carrier material should be the main component. This is the case when the proportion of the non-alkaline carrier material is greater than 50 mass%, preferably greater than 60 mass%, particularly preferably greater than 75 mass% with respect to the total amount of the carrier material (D).

[0069] Examples of non-alkaline carrier materials include phosphates such as powdered or granular sodium tripolyphosphate, sodium sulfate, sodium hydrogen carbonate, sodium citrate, sodium acetate, or cellulose derivatives such as sodium carboxymethyl cellulose.

[0070] Examples of alkaline carrier materials that can be used in an amount of less than 50 mass%, preferably less than 40 mass%, particularly preferably less than 25 mass% include sodium carbonate, zeolites such as zeolite A or zeolite X, aluminosilicates or silicates such as magnesium silicate.

[0071] Particularly preferably, it is a carrier material having good water solubility, such as sodium sulfate, sodium hydrogen carbonate, sodium citrate, sodium acetate, and cellulose derivatives such as sodium carboxymethyl cellulose. In the context of the present invention, good water solubility exists when the solubility in water at 25 °C and a pressure of 101.425 kPa is at least 3% by mass.

[0072] When using only one type of component as the carrier material, it should be an easily water-soluble carrier material. When using a plurality of components as the carrier material, the easily water-soluble carrier material should be the main component. The proportion of the easily water-soluble carrier material is greater than 50% by mass, preferably greater than 60% by mass, particularly preferably greater than 75% by mass, based on the total amount of the carrier material (D). It has been found that when using a water-soluble carrier material as the main component, the water solubility or water dispersibility of the antifoaming agent powder according to the present invention is significantly improved.

[0073] Examples of easily water-soluble carrier materials are phosphates such as powdered or granular sodium tripolyphosphate, sodium sulfate, sodium hydrogen carbonate, sodium citrate, sodium acetate, or cellulose derivatives such as sodium carboxymethyl cellulose.

[0074] Examples of sparingly water-soluble carrier materials that can be used in an amount less than 50% by mass, preferably less than 40% by mass, particularly preferably less than 25% by mass, are zeolites such as zeolite A or zeolite X, aluminosilicates or silicates such as magnesium silicate.

[0075] The present invention further provides a method for producing an antifoaming agent powder. In this method, a premix of the antifoaming agent formulation (A), the waxy additive (B), and the binder (C), preferably in the form of a dispersion, particularly an aqueous dispersion, is produced, and this premix is mixed with a powdered carrier material.

[0076] The premix is preferably obtained by dispersing an emulsion or dispersion of an antifoaming agent formulation (A) and a wax-like additive (B), preferably aqueous, in a solution or dispersion of a binder (C), preferably aqueous.

[0077] The antifoaming agent powder according to the present invention can be produced, for example, by mixing a premix of an antifoaming agent formulation (A) and a wax-like additive (B) with a powdery carrier material (D) and then or simultaneously incorporating a solution or dispersion of a binder (C). Alternatively, an emulsion or dispersion of a premix of an antifoaming agent formulation (A) and a wax-like additive (B) can be produced in a solution or dispersion of a binder (C) by a known method, and then this can be incorporated into a powdery carrier material (D). This production method using an emulsion or dispersion in which the antifoaming agent formulation (A) and the wax-like additive (B) are premixed in a solution or dispersion of the binder (C) is preferred.

[0078] If necessary, the powdery composition obtained after mixing can also be dried so that a free-flowing powder is finally obtained. Drying can be carried out directly in a mixer or, subsequently, in a separate dryer of a 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.

[0079] To produce the antifoaming agent powder according to the present invention, various known mixers that can be heated and / or evacuated so as to be dried preferably within the same unit can be used. Examples of suitable mixers are a plowshare mixer, Z mixer, screw extruder or planetary mixer. The technical residual moisture content of the antifoaming agent powder according to the present invention is 10% by mass or less, preferably 5% by mass or less.

[0080] Preferably, the antifoaming agent powder according to the present invention is used in detergents and cleaning compositions. However, if it is intended to control or prevent foaming, it can be used anywhere. An example is powdery crop protection products, especially those containing a relatively large amount of surfactant compounds. Alternatively, the defoaming agent powder according to the invention can be advantageously used in chemical processes or waste water treatment. The metered addition of the defoaming agent powder according to the invention can be carried out, for example, by simple mixing with detergents. This is advantageously carried out at the time when the detergent is mixed with further components such as enzymes, bleaching agents, etc. However, it is also possible to meter the defoaming agent powder according to the invention directly into the foaming medium.

[0081] The defoaming agent powder according to the invention is preferably used in a surfactant-containing solid medium that causes foaming when used in an aqueous environment, more preferably in detergents and cleaning compositions, especially in solid (powdery or granular) detergents and cleaning compositions.

[0082] Accordingly, the present invention provides a detergent or cleaning composition comprising the defoaming agent powder according to the invention.

[0083] The viscosity of the individual components, especially component (Aa), is measured at 25 °C and the appropriately indicated shear rate using an MCR 300 cone / plate viscometer (manufactured by Paar-Physika) in accordance with DIN 53019-1 (2008-09) (principles and measuring geometries), DIN 53019-2 (2001-2) (calibration of viscometers and determination of measurement uncertainties) and DIN 53019-3 (2008-09) (measurement errors and corrections), or in accordance with DIN EN ISO 3219 (1994) (Plastics - Determination of viscosity using a rotational viscometer with defined shear rate for polymers / resins in the liquid state or as emulsions or dispersions). The viscosity of the defoaming agent formulation (A) is measured at 25 °C and a shear rate of 50 / s using an MCR 300 cone / plate viscometer (manufactured by Paar-Physika) in accordance with DIN EN ISO 3219.

[0084] The amount of monoacylglycerol or triacylglycerol in commercially available monoacylglycerol is measured by high performance liquid chromatography (HPLC) using a Luna 5μm C5 100Å (250mm×4.6mm) HPLC column manufactured by Phenomenex. The mobile phase used is a mixture of 0.05% aqueous trifluoroacetic acid solution and THF, and a gradient of 30% THF to 100% THF is carried out at a flow rate of 1.0 ml / min and a column temperature of 30°C. Detection is performed with an evaporative light scattering detector (ELSD) (1.4 SLM - 30°C neb - 30°C evap - 50% light source intensity). Dissolve 10 mg of the sample in 10 ml of THF, mix with 1 ml of water, and further add THF to make a total of 10 ml. Calibration is performed for chemically pure monoacylglycerol or triacylglycerol.

[0085] In the following examples, all numerical values of parts and percentages are by mass, unless otherwise specified. Unless otherwise specified, the following examples are carried out at the pressure of the ambient atmosphere, i.e., about 1000 hPa, at room temperature, i.e., about 20°C, or at the temperature established by the combination of reactants at room temperature without additional heating or cooling.

[0086] Example 1: Production of antifoaming agent formulation (A): Production of antifoaming agent formulation (A1): 82.3 parts by mass of 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 by mass of fumed silica with a BET specific surface area of 300 m 2 / g (available under the name HDK(R) T30 from Wacker Chemie AG Munich), 5 parts by mass of a hydrocarbon mixture having a boiling point in the range of 235 - 270°C (commercially available under the name Exxsol D 100 S from Staub & Co, Nuremberg, Germany), which is solid at room temperature and has the following units ( 29 by Si NMR and IR analysis): (CH3)3SiO 1 / 2 - 40 mol%, SiO 4 / 2 - 50 mol%, C2H5OSiO 3 / 2-8 mol% and HOSiO 3 / 2 5 parts by mass of a silicone resin consisting of -2 mol% and having a weight average molar mass of 7900 g / mol (based on polystyrene standard), and 0.7 parts by mass of a 20% by mass solution of KOH in glycerol were mixed in a dissolver and heated to 110 °C for 4 hours. An antifoaming agent formulation having a viscosity of 35500 mPa·s (2.5 rpm, 25 °C) was obtained.

[0087] Production of antifoaming agent formulation (A2): The production method of the antifoaming agent formulation (A1) was repeated, and as the organopolysiloxane (Aa), 82.3 parts by mass 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. An antifoaming agent formulation (A2) having a viscosity of 28700 mPa·s (2.5 rpm, 25 °C) was obtained.

[0088] Production of antifoaming agent formulation (A3): 85 parts by mass of trimethylsiloxy-terminated dimethylsiloxy-(α-methylstyryl)methylsiloxy-methyloctylsiloxy copolymer having an average chain length of 60, a ratio of dimethylsiloxy units:(α-methylstyryl)methylsiloxy units:methyloctylsiloxy of 10:9:1, and a viscosity of 1500 mPa·s (measured at 25 °C and a shear rate of 10 / s), 5 parts by mass of fumed silica for the antifoaming agent formulation (A1), 5 parts by mass of a hydrocarbon mixture for the antifoaming agent formulation (A1), 5 parts by mass of a silicone resin for the antifoaming agent formulation (A1), and 0.7 parts by mass of a 20% by mass methanol KOH solution were mixed in a dissolver and heated to 110 °C for 4 hours. An antifoaming agent formulation having a viscosity of 9500 mPa·s (2.5 rpm, 25 °C) was obtained.

[0089] Example 2: Production of the antifoaming agent powder according to the present invention: Production of antifoaming agent powder (P1): 10 parts of the defoaming agent complex (A1) were mixed with 1.25 parts of glycerol monostearate (available from Faci under the name GMS90 and having a content of glycerol tristearate of less than 1% by mass (by HPLC analysis)) at a temperature of 50°C. The resulting mixture was dispersed in 2.5 parts of a polyacrylic acid solution at pH 2.5 heated to 50°C (a 50% by mass solution of polyacrylic acid commercially available from BASF as Sokalan(R) CP 10 S). As a result, a white creamy and fluid dispersion was obtained. The obtained dispersion was added to a mixture of 72.5 parts of sodium sulfate and 15 parts of zeolite 4A under high shear. After drying to a constant weight at 80°C, the defoaming agent powder (P1) according to the present invention was obtained.

[0090] Production of defoaming agent powder (P2): In the same manner as the description of the defoaming agent powder (P1), a dispersion was prepared from 3.75 parts of glycerol monostearate GMS90, 2.5 parts of Sokalan CP 10 S, and 10 parts of the defoaming agent complex (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 the defoaming agent powder (P2).

[0091] Production of defoaming agent powder (P3): In the same manner as the description of the defoaming agent powder (P1), a dispersion was prepared from 1.25 parts of glycerol monostearate GMS90, 7.5 parts of Sokalan CP 10 S, and 10 parts of the defoaming agent complex (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 the defoaming agent powder (P3).

[0092] Production of defoaming agent powder (P4): In the same manner as the description of the defoaming agent powder (P1), a dispersion was prepared from 3.75 parts of glycerol monostearate GMS90, 7.5 parts of Sokalan CP 10 S, and 10 parts of the defoaming agent complex (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 the defoaming agent powder (P4).

[0093] Manufacture of defoaming agent powder (P5): Similar to the description of the defoaming agent powder (P1), a dispersion was prepared from 1.9 parts of glycerol monostearate GMS90, 1.9 parts of paraffin (melting point range: 56 - 58 °C), 8.0 parts of Sokalan CP 10 S, and 10 parts of defoaming agent 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 the defoaming agent powder (P5).

[0094] Manufacture of defoaming agent powder (P6): Similar to the description of the defoaming agent powder (P1), a dispersion was prepared from 3.8 parts of glycerol monostearate GMS90, 8.0 parts of Sokalan CP 10 S, and 10 parts of defoaming agent 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 the defoaming agent powder (P6).

[0095] Manufacture of defoaming agent powder (P7): Similar to the description of the defoaming agent powder (P1), a dispersion was prepared from 3.8 parts of glycerol monostearate GMS90, 8.0 parts of Sokalan CP 10 S, and 10 parts of defoaming agent 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 the defoaming agent powder (P7).

[0096] Example 3: Manufacture of defoaming agent powder of non - invention: Manufacture of defoaming agent powder (VP1): 3.8 parts of glycerol monostearate GMS90 and 10 parts of defoaming agent formulation (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, resulting in the defoaming agent powder (VP1) (of non - invention).

[0097] Manufacture of defoaming agent powder (VP2): Similar to the description of the antifoaming agent powder (P1), a dispersion was prepared from 3.8 parts of glycerol monostearate GMS90, 11.1 parts of polyacrylic acid with a pH of 8.5 (a 45% by mass solution of polyacrylic acid commercially available from BASF as Sokalan(R) CP 10), and 10 parts of the antifoaming agent 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 obtain an antifoaming agent powder (VP2) (not of the invention).

[0098] Production of antifoaming agent powder (VP3): Similar to the description of the antifoaming agent powder (P1), a dispersion was 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 (a 40% by mass solution of an acrylic acid - maleic acid copolymer commercially available from BASF as Sokalan(R) CP 5), and 10 parts of the antifoaming agent 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 antifoaming agent powder (VP3) (not of the invention).

[0099] Production of antifoaming agent powder (VP4): Similar to the description of the antifoaming agent powder (P1), a dispersion was prepared from 3.8 parts of Steareth - 4, 8.0 parts of Sokalan CP 10 S, and 10 parts of the antifoaming agent 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 obtain an antifoaming agent powder (VP4) (not of the invention).

[0100] Production of antifoaming agent powder (VP5): Similar to the description of the antifoaming agent powder (P1), a dispersion was prepared from 10.0 parts of Sokalan CP 10 S and 10 parts of the antifoaming agent 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 antifoaming agent powder (VP5) (not of the invention).

[0101] Production of antifoaming agent powder (VP6): A mixture of 3.8 parts of glycerol monostearate GMS90 and 10 parts of defoamer formulation (A1) was combined with 8.0 parts of Sokalan CP 10 S on parts of sodium carbonate and finally dried to obtain a defoamer powder (VP6) of the non-invention.

[0102] Production of defoamer powder (VP7): 10 parts of defoamer formulation (A1) was dispersed in 8.0 parts of Sokalan CP 10 S. This dispersion was added to 85 parts of zeolite 4A and finally dried to obtain a defoamer powder (VP7) of the non-invention.

[0103] Production of defoamer powder (VP8): 10 parts of defoamer formulation (A3) was mixed with 3.8 parts of glycerol monostearate GMS 90, and this mixture was dispersed in 8.0 parts of Sokalan CP 10 S. This dispersion was added to 82 parts of corn starch and finally dried to obtain a defoamer powder (VP8) of the non-invention.

[0104] Example 4: Defoaming efficacy test in a washing machine 0.5% by mass of defoamer powder was added to 130 g of washing powder ECE-2 manufactured by WFK. This washing powder was 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 started. The program was run at a temperature of 40 °C and a water hardness of 3 °GH. The foam height was recorded over 55 minutes. The average foam score was determined from the foam scores confirmed over the entire time (from 0% non-measurable foam to 100% over-foam). The lower this score, the more effective the defoamer powder is over the entire time.

[0105] The storage test in washing powder ECE-2 was conducted as follows: 0.5% by mass of the antifoaming agent powder was added to 130 g of the cleaning powder and mixed well. The mixture was put into a PE bag with a film thickness of 50 μm, the PE bag was closed, and stored in a thermostatic chamber at 35 °C / 70% humidity for 4, 8, and 12 weeks. After storage, the contents of the bag were tested in a drum washing machine as described above to confirm foam control. The determination of each foam score is the average value of a plurality of individual measurements.

[0106] Table 1: Defoaming effect when 0.05% of the antifoaming agent powder according to the present invention was stored in the cleaning powder ECE-2 and when not stored:

[0107]

Table 1

[0108] All the antifoaming agent powders according to the present invention have excellent defoaming effects in the cleaning powder ECE-2. Even after storage for 12 weeks, the antifoaming agent powder still shows excellent defoaming effects.

[0109] Table 2: Defoaming effect when 0.05% of the non-invention antifoaming agent powder VP1 was stored in the cleaning powder ECE-2 and when not stored:

[0110]

Table 2

[0111] When polyacrylic acid is not used (described in European Patent Application Publication No. 0210731, European Patent No. 1534403, and European Patent No. 1528954), the (non-invention) antifoaming agent powder (VP1) shows excellent defoaming effects when not stored. However, the defoaming effect is completely lost after storage for 12 weeks. Therefore, the combination of acidic polyacrylic acid and glycerol monostearate (used in the antifoaming agent powders P1 - P5 according to the present invention) is necessary to achieve very good storage stability.

[0112] Table 3: Defoaming effect when 0.05% of non-invention antifoaming agent powders VP2 and VP3 are stored in the cleaning powder ECE-2 and when not stored:

[0113]

Table 3

[0114] Even when acidic polyacrylic acid is not used, there is an excellent defoaming effect when not stored. However, the defoaming effect has completely broken down after 8 weeks. In contrast, when acidic polyacrylic acid is used (like the antifoaming agent powders P1 - P5 according to the present invention), excellent storage stability is achieved.

[0115] Table 4: Defoaming effect when 0.05% of non-invention antifoaming agent powders VP4 and VP5 are stored in the cleaning powder ECE-2 and when not stored:

[0116]

Table 4

[0117] When stearyl polyether is used instead of glycerol monostearate (VP4), or when glycerol monostearate is completely removed (VP5), a slightly worse effect is already shown when not stored. The defoaming effect significantly decreases after 12 weeks of storage. In contrast, when glycerol monostearate is used (like the antifoaming agent powders P1 - P5 according to the present invention), both the excellent effect when not stored and excellent storage stability are achieved.

[0118] Table 5: Defoaming effect when 0.05% of non-inventive defoaming agent powder VP6 is stored in washing powder ECE-2 and when not stored:

[0119]

Table 5

[0120] When only an alkaline carrier is used and the polycarboxylate and defoaming agent formulation are not added in the form of an aqueous premix, the defoaming effect when not stored becomes weak. Furthermore, after 8 weeks of storage, the defoaming effect is significantly impaired. In contrast, when the alkaline carrier is not the main component (such as the defoaming agent powders P1 - P5 according to the invention having about 18% by mass based on the total amount of the carrier material), and the polycarboxylate binder is added to the carrier material as an aqueous premix together with the defoaming agent formulation (such as the defoaming agent powders P1 - P5 according to the invention), there is an excellent effect even when not stored, and the defoaming effect still exists even after 12 weeks of storage.

[0121] Example 5: Dispersibility of defoaming agent powder First, 150 g of water was placed in a 250 ml glass bottle. The defoaming agent powder was added thereto and stirred with a spatula. Visual evaluations were performed after 10 seconds and 60 seconds.

[0122] Table 6: Solubility / dispersibility in water of 0.1% by mass of defoaming agent powder after 10 seconds and 60 seconds:

[0123]

Table 6

[0124] When only zeolite or only starch is used as the carrier material (VP7 and VP8), the solubility is low. In both cases, a turbid solution is obtained, which becomes more turbid over time. When a water-soluble carrier material (sodium sulfate) is used as the main component (P7), the result is a clear solution. The initially formed precipitate (although less than in the case of VP7 or VP8) mostly dissolves over time. Using a water-soluble carrier material as the main component of the antifoaming agent powder according to the present invention clearly shows advantages over the prior art.

Claims

1. An antifoaming agent powder, comprising: (A) 100 parts by mass of an antifoaming agent formulation, including: (Aa) a polysiloxane containing the unit of formula (I): R １ R ２ SiO ２／２ (I) (wherein: R １ may be the same or different and is a monovalent, optionally branched SiC-bonded hydrocarbon group having 1 to 5 carbon atoms, R ２ may be the same or different and is a monovalent, optionally branched SiC-bonded hydrocarbon group having 6 to 30 carbon atoms.) ), (Ab) a filler, (Ac) an organopolysiloxane resin composed of units of general formula (II): R ３ ａ (R ４ O) ｂ SiO （４－ａ－ｂ）／２ (II) (wherein: ), R ３ which may be the same or different and is a monovalent, optionally substituted SiC-bonded hydrocarbon group having 1 to 30 carbon atoms, R ４ may be the same or different and is a hydrogen atom or a monovalent, optionally substituted hydrocarbon group having 1 to 4 carbon atoms, a is 0, 1, 2 or 3; b is 0, 1, 2 or 3; provided that the sum of a + b is ≦ 3, and in less than 50% of all the units of formula (II) in the organopolysiloxane resin, the sum of a + b is = 2.), (Ad) optionally, a further organopolysiloxane composed 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 above definition and R ５ may be the same or different, and R １ or -OR ６ may also be, where 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) optionally, an alkaline or acidic catalyst, or a reaction product thereof with components (Aa)-(Ad), an antifoaming agent formulation; (B) 10 - 45 parts by mass of a wax-like additive based on 100 parts by mass of the antifoaming agent formulation (A), including a monoester (B') of glycerol and a fatty acid, not containing a polysiloxane-containing additive, containing less than 5% by mass of a triester (B'') of glycerol and a fatty acid, a wax-like additive; (C) 10 - 50 parts by mass of a polycarboxylate binder based on 100 parts by mass of the antifoaming agent formulation (A), a polycarboxylate binder having a pH of 3 or less when dissolved in water; (D) 120 - 5000 parts by mass of at least one powdered carrier material based on 100 parts by mass of the antifoaming agent formulation (A), provided that the carrier material contains less than 50% by mass of an alkaline carrier material, preferably less than 40% by mass of an alkaline carrier material, more preferably less than 25% by mass of an alkaline carrier material, an antifoaming agent powder.

2. The antifoaming agent powder according to claim 1, wherein the polysiloxane (Aa) is an organopolysiloxane 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: R １ , R ２ and R ５ have the definitions in claim 1, x is 0 or more and less than 200 on average; y is greater than 5 and less than 200 on average.).

3. The antifoaming agent powder according to claim 1 or 2, wherein silica is used as the filler (Ab).

4. The antifoaming agent powder according to any one of claims 1 - 3, wherein the organopolysiloxane resin (Ac) used is an MQ resin composed of units of the formula: SiO ２ (Q unit) and R ３ ３ SiO １／２ (M unit) (In the formula, the molar ratio of the M unit to the Q unit is in the range of 0.5 to 2.0, and the MQ resin, in addition to the M unit and the Q unit, contains a small amount of R ３ SiO ３／２ or (R ４ O)SiO ３／２ (T) unit or R ３ ２ SiO ２／２ (D) unit may be included in an amount of 0.01 to 20 mol% based on the total of all siloxane units, and the MQ resin may also contain up to 10% by mass of free Si-bonded hydroxyl groups or alkoxy groups such as methoxy groups or ethoxy groups. R ３ and R ４ has the definition in claim 1.)

5. The wax-like additive (B) contains, in the total mixture of the wax-like components (B) used, 30% by mass or more, preferably 50% by mass or more, particularly 70% by mass or more, of monoesters of glycerol and fatty acids, and contains less than 5% by mass of triacylglycerols. The defoaming agent powder according to any one of claims 1 to 4.

6. The defoaming agent powder according to any one of claims 1 to 5, wherein the monoester of glycerol and fatty acid is glycerol monolaurate, glycerol monomyristate, glycerol monopalmitate or glycerol monostearate.

7. The carboxylate binder (C) is represented by the general formula (V) (CR ８ ２ -CR ８ ２ ) ｎ (V), (wherein, n has a value of 10 to 100,000, preferably 20 to 10,000, particularly preferably 30 to 1,000, R ８ is hydrogen, an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, a carboxyl group or a salt thereof, and a general formula -C(O)-O-R ９ (VI), -C(O)-N(R １０ ) ２ (VII), (wherein, R ９ is an optionally functionalized hydrocarbon group having 1 to 30 carbon atoms, R １０ is hydrogen, group R ９ or R １１ -SO ３ X (wherein, R １１ is a divalent alkylene group having 1 to 12 carbon atoms, X is a hydrogen atom or a cation. ) Any of the following. ) Selected from the groups of However, the group R ８ at least 5 mol%, preferably at least 10 mol%, particularly at least 15 mol% thereof is an acidic group selected from a carboxyl group or a salt thereof, and a sulfonyl group or a salt thereof, preferably selected from a carboxyl group and a salt thereof.) A water-soluble or water-dispersible homopolymer, copolymer or salt thereof containing at least 60% by mass of the segment of

8. The defoaming agent powder according to any one of claims 1 to 7, wherein the carboxylate 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. A non-alkaline carrier material such as phosphate, sodium sulfate, sodium hydrogen carbonate, sodium citrate, sodium acetate, or a cellulose derivative such as sodium carboxymethylcellulose is used in a range of more than 50% by mass as the powdery carrier material. The defoaming agent powder according to any one of claims 1 to 8.

10. A method for producing the defoaming agent powder according to any one of claims 1 to 9, A premix of the defoaming agent formulation (A), the wax-like additive (B) and the binder (C) is produced, preferably in the form of a dispersion, The method of mixing the premix with the powdery carrier material.

11. The method according to claim 10, wherein the premix is mixed with the powdery carrier material in the form of a water-washed dispersion.

12. The method according to claim 10 or 11, wherein the defoaming agent powder is then dried.

13. A detergent or cleaning composition comprising the antifoaming agent powder according to any one of Claims 1 to 9 or the antifoaming agent powder produced by the method according to Claim 10.

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