DEFOAMING FORMULATIONS CONTAINING TRIACYLGLYCERIDES

Description

[0001] The invention relates to defoamer formulations containing triacylglycerides and their use as defoamers, in particular in aqueous surfactant systems.

[0002] In many liquid, particularly aqueous systems that contain surface-active compounds as desired or undesired components, problems can arise due to foam formation when these systems are brought into more or less intensive contact with gaseous substances, for example during the gassing of waste water, the intensive stirring of liquids, during distillation, washing or dyeing processes or during filling operations.

[0003] This foam can be controlled mechanically or by adding defoamers. The most successful defoamer formulations, especially for detergents, are based on silicones.

[0004] There is a certain demand for defoamer formulations that contain a reduced amount of organopolysiloxane or are free of organopolysiloxanes. US Pat. No. 5,693,256 A and EP 1 703 958 B1 describe organopolysiloxane-free defoamer formulations in which, instead of the organopolysiloxanes, a water-insoluble organic liquid is used together with hydrophobic fillers and a siloxane resin. The water-insoluble organic liquid used in these patents can be isoparaffin oil, fatty acid ester, or mineral oil, or even a vegetable oil. Rapeseed oil and peanut oil are described as vegetable oils. Vegetable oils are triacylglycerides in which three fatty acid residues are bonded together to a glycerol residue via ester bonds.Rapeseed oil is a triacylglyceride whose fatty acid residues are predominantly oleic, linoleic, linolenic, and palmitic acid residues, thus C16 or C18 fatty acid residues. The same applies to peanut oil, which consists predominantly of oleic, linoleic, and palmitic acid residues, thus also C16 or C18 fatty acid residues.

[0005] In US 5 693 256 A and in EP 1 703 958 B1, the defoamer formulations described are used, in addition to black liquor defoaming or foam destruction in cutting oil processes, primarily for foam control during the washing cycle in the washing machine for washing laundry.

[0006] Document US2007 / 276056 discloses a defoamer formulation with a mixture of glycerol di- or triesters having at least 14 C atoms.

[0007] In the applications described, the defoamer formulations based on rapeseed oil or peanut oil show quite good effectiveness.

[0008] However, in the course of the improvement process of such defoamer formulations, it became apparent that in applications where cationic surfactants are used or in applications where spreading plays a significant role, for example in the rinsing cycle of the washing process, the foam control agents based on triacylglycerides with predominantly C16 or C18 fatty acid residues, such as the described rapeseed oil or peanut oil, show a very weak or no effect.

[0009] The task was to provide defoamer formulations that do not have the disadvantages mentioned above.

[0010] The problem is solved by the invention.

[0011] The invention therefore relates to defoamer formulations (A) containing

[0012] (1) Triacylglycerides of the formula wherein R can be the same or different and denotes a saturated or unsaturated C 5 -C 13 hydrocarbon radical, (2) fillers, (3) organopolysiloxane resins comprising units of the general formula R 2< e (R 3< O) f SiO (4-ef) / 2 (II), wherein R 2< can be the same or different and denotes a hydrogen atom or a monovalent, optionally substituted, SiC-bonded hydrocarbon radical having 1 to 30 C atoms, R 3< can be the same or different and denotes a hydrogen atom or a monovalent, optionally substituted, hydrocarbon radical having 1 to 4 C atoms, e is 0, 1, 2 or 3 and f is 0, 1, 2 or 3, with the proviso that the sum e+f is less than or equal to 3 and in less than 50% of all units of the formula (II) in the organopolysiloxane resin the sum e+f is equal to 2, optionally (4) water-insoluble organic compounds other than the triacylglycerides (1),and optionally (5) alkaline or acidic catalysts or their reaction products with components (1) to (4).

[0013] Surprisingly, it was found that defoamer formulations based on triacylglycerides with fatty acid residues containing fewer than 16 carbon atoms exhibit very good performance. This is particularly true for the described applications in which cationic surfactants are used, or for applications in which spreading plays a significant role, such as in the rinse cycle of the washing process.

[0014] The defoamer formulations (A) preferably contain 100 parts by weight of triacylglycerides (1) and at least 1 part by weight, preferably at least 1.5 parts by weight, particularly preferably at least 2 parts by weight, and at most 25 parts by weight, preferably at most 20 parts by weight, particularly preferably at most 15 parts by weight of fillers (2), in each case based on 100 parts by weight of (1), at least 1 part by weight, preferably at least 1.5 parts by weight, particularly preferably at least 2 parts by weight, and at most 25 parts by weight, preferably at most 20 parts by weight, particularly preferably at most 15 parts by weight of organopolysiloxane resins (3), in each case based on 100 parts by weight of (1), at least 0 parts by weight and at most 25 parts by weight, preferably at most 17 parts by weight, particularly preferably at most 10 parts by weight of water-insoluble organic compounds (4), in each case based on 100 Parts by weight (1), at least 0 parts by weight, preferably at least 0.05 parts by weight, particularly preferably at least 0.1 part by weight, and at most 2 parts by weight, preferably at most 1 part by weight, particularly preferably at most 0.5 parts by weight.-parts of alkaline or acidic catalysts (5) or its reaction products with components (1) to (4), each based on 100 parts by weight of (1). .

[0015] Examples of hydrocarbon radicals R are alkyl or alkylene radicals, such as pentyl, pentenyl, hexyl, hexenyl, heptyl, heptenyl, octyl, octenyl, nonyl, nonenyl, decyl, decenyl, undecyl, undecenyl, dodecyl, dodecenyl, tridecyl, and tridecenyl. Alkyl radicals are preferred. Particularly preferred examples of R are pentyl, heptyl, nonyl, and undecyl.

[0016] The triacylglycerides (1) used in the defoamer formulation (A) are preferably triglycerides containing medium-chain fatty acids. Medium-chain fatty acids include caproic (C 6:0), caprylic (C 8:0), capric (C 10:0), and lauric acid (C 12:0). In the nomenclature (C 6:0), "C 6" represents the number of carbon atoms and "0" the number of double bonds.

[0017] The triacylglycerides (1) used in the defoamer formulation (A) are obtained industrially by hydrolysis of coconut fat and palm kernel oil, subsequent fractionation of the medium-chain fatty acids and finally re-esterification with glycerol.

[0018] Triacylglycerides (1) can be triglycerides with predominantly only one type of fatty acid, such as caprylic triglyceride (INCI nomenclature) or those with a mixture of fatty acids, such as caprylic / capric triglyceride (INCI nomenclature).

[0019] Triacylglycerides (1) may also contain, to a small extent (as an impurity), preferably 0 to 10% by weight, in particular 0 to 5% by weight, further fatty acid residues which are longer in chain than 14 carbon atoms, e.g. the stearyl, palmityl, linoleyl or linoleyl residue.

[0020] Triacylglycerides (1) also include so-called MCT oils (medium chain triglycerides). Such oils are commercially available, for example, as coconut-based MCT oil (from Gustavhees) or as CremerCOOR ®< MCT C8, CremerCOOR ®< MCT 60-40, or CremerCOOR ®< MCT 30-70 (from Cremer Oleo Division).

[0021] Preferably, R 2< represents a hydrocarbon radical having 1 to 30 carbon atoms.

[0022] Examples of hydrocarbon radicals R 2< are alkyl radicals such as methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, iso-butyl, tert-butyl, n-pentyl, isopentyl, neo-pentyl, tert-pentyl, hexyl radicals such as n-hexyl, heptyl radicals such as n-heptyl, octyl radicals such as n-octyl and iso-octyl radicals such as 2,2,4-trimethylpentyl and 2-ethylhexyl, nonyl radicals such as n-nonyl, decyl radicals such as n-decyl, dodecyl radicals such as n-dodecyl, tetradecyl radicals such as n-Tetradecyl radicals, hexadecyl radicals, such as the n-hexadecyl radical, and octadecyl radicals, such as the n-octadecyl radical; cycloalkyl radicals, such as the cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl, and 4-ethylcyclohexyl radicals; aryl radicals, such as the phenyl, naphthyl, anthryl, and phenanthryl radicals; alkaryl radicals, such as o-, m-, p-tolyl radicals, xylyl radicals, and ethylphenyl radicals; and aralkyl radicals, such as the benzyl radical and the α- and β-phenylethyl radicals.The hydrocarbon radicals R 2< may contain ether or polyether groups.

[0023] Preferred examples of radicals R 2< are the methyl, ethyl and phenyl radicals.

[0024] Examples of radicals R 3< are the hydrogen atom and alkyl radicals such as methyl, ethyl, n-propyl, iso-propyl and n-butyl.

[0025] Preferably, the radical R 3< is a hydrogen atom or a methyl or ethyl radical.

[0026] The fillers (2) used in the defoamer formulations according to the invention preferably have a BET surface area of ​​20 to 1000 m 2 / g. The fillers (2) preferably have a particle size of less than 10 µm and an agglomerate size of less than 100 µm.

[0027] Examples of fillers (2) are silicon dioxide (silicic acids), titanium dioxide, aluminum oxide, metal soaps, quartz flour, PTFE powder, fatty acid amides, e.g., ethylene bisstearamide, and finely divided hydrophobic polyurethanes.

[0028] Preferred fillers (2) are silicas, especially those with a BET surface area of ​​50 to 800 m² / g. These silicas can be fumed or precipitated silicas. Both pretreated silicas, i.e., hydrophobic silicas, and hydrophilic silicas can be used as fillers (2). Examples of commercially available hydrophobic silicas that can be used according to the invention are HDK® H2000, a fumed silica treated with hexamethyldisilazanes with a BET surface area of ​​140 m² / g (commercially available from Wacker-Chemie GmbH, Germany) and a precipitated silica treated with polydimethylsiloxane with a BET surface area of ​​90 m² / g (commercially available under the name "Sipernat D10" from Evonik AG, Germany).

[0029] The component (3) used in the defoamer formulations according to the invention is preferably a silicone resin comprising units of the formula (II) in which the sum e+f is equal to 2 in less than 30%, preferably in less than 5%, of the units in the resin.

[0030] The organopolysiloxane resins (3) comprising units of the formula (II) are preferably MQ resins comprising units of the formulas SiO 2 (Q units) and R 2< 3 SiO 1 / 2 (M units), where R 2< has the meaning given above.

[0031] The molar ratio of M to Q units is preferably in the range from 0.5 to 2.0, more preferably in the range from 0.6 to 1.0. In addition to the M and Q units, the MQ resins may optionally also contain small amounts of R 2< SiO 3 / 2 or (R 3< O)SiO 3 / 2 (T) units or R 2< 2 SiO 2 / 2 (D) units, in amounts of preferably 0.01 to 20 mol%, more preferably 0.01 to 5 mol%, based on the sum of all siloxane units, where R 3< has the meaning given above. These MQ resins may also contain up to 10 wt.% of free Si-bonded hydroxyl or alkoxy groups, such as methoxy or ethoxy groups.

[0032] These organopolysiloxane resins (3) preferably have a viscosity greater than 1000 mPa s at 25°C and 101.425 kPa or are solids. The weight-average molecular weight (based on a polystyrene standard) of these resins, determined by gel permeation chromatography, is preferably 200 to 200,000 g / mol, in particular 1000 to 20,000 g / mol.

[0033] In the defoamer formulations according to the invention, water-insoluble organic compounds (4) can optionally be used.

[0034] For the purposes 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 a maximum of 3% by weight.

[0035] The optionally used component (4) is preferably a water-insoluble organic compound having a boiling point greater than 100°C at the pressure of the ambient atmosphere, i.e. at 900 to 1100 hPa, in particular those selected from hydrocarbons, polyisobutylenes and esters such as fatty acid esters with monoalcohols.

[0036] Examples of hydrocarbons are isoparaffins (for example available under the trade name Isopar ®< E, Isopar ®< G, Isopar ®< H, Isopar ®< J, Isopar ®< L, Isopar ®< M, Isopar ®< N, Isopar ®< P, Isopar ®< V from ExxonMobil), dearomatized hydrocarbons (for example available under the trade name Exxsol ®< D40, Exxsol ®< 60, Exxsol ®< D95, Exxsol ®< D100, Exxsol ®< D130 from ExxonMobil) or white oils. Dearomatized hydrocarbons are particularly preferred. Examples of polyisobutylenes are products commercially available under the trade name Indopol ®< (Ineos) or Oppanol ®< (BASF). Particularly preferred polyisobutylenes are those having a kinematic viscosity of 20 to 500 cSt measured at a temperature of 100 °C and a shear rate of 10 1 / s. Examples of esters, in particular fatty acid esters with monoalcohols, are methyl laurate, isopropyl laurate, octyl laurate, octyl stearate, octyl oleate, dodecyl palmitate or isopropyl myristate.

[0037] Examples of optionally used alkaline catalysts (5) are alkali and alkaline earth hydroxides, such as NaOH, KOH, CsOH, LiOH and Ca(OH) 2 . Examples of acidic catalysts (5) are hydrochloric acid, sulfuric acid and phosphonitrile chlorides.

[0038] The reaction products of (5) with components (1) to (4) are, for example, the product of the silicic acid preferred as filler (2) with alkali hydroxides, such as potassium silicate or sodium silicate.

[0039] The catalysts can be dosed in typical organic solvents such as alcohols (such as methanol, ethanol, isopropanol) or esters (such as ethyl acetate).

[0040] The components (2) to (5) used in the defoamer formulations (A) according to the invention can each be one type of such a component or a mixture of at least two types of a respective component.

[0041] The defoamer formulations (A) according to the invention have a viscosity of preferably 50 to 100,000 mPa·s, particularly preferably 100 to 10,000 mPa·s, in particular 200 to 5,000 mPa·s, in each case at 25°C and 101.425 kPa.

[0042] The defoamer formulation (A) according to the invention can be prepared by known methods, such as by mixing all components, for example, using high shear forces in colloid mills, dissolvers, or rotor-stator homogenizers. The mixing process can be carried out at reduced pressure to prevent the incorporation of air, which is present, for example, in highly dispersed fillers. Subsequently, if necessary, the fillers can be hydrophobized in situ.

[0043] It is also possible to first add component (1) and heat it if necessary and then successively add components (2), (3), if necessary (4) and if necessary (5).

[0044] In a preferred embodiment, component (3) is added in dissolved form as a solution in component (4) or parts of component (4).

[0045] The invention further relates to emulsions (E) of defoamer formulations comprising the defoamer formulations (A) according to the invention, emulsifiers (B), optionally thickeners (C) and water (W).

[0046] To prepare the defoamer emulsions (E) according to the invention, typical emulsifiers (B) can be used which are known to the person skilled in the art, for example, for the preparation of silicone emulsions, such as, for example, nonionic, anionic or cationic emulsifiers.

[0047] Emulsifier mixtures are preferably used, which should contain at least one non-ionic emulsifier.

[0048] (Non-limiting) examples of non-ionic emulsifiers (B-1) used are: 1. Alkyl polyglycol ethers, preferably those with 3 to 30 EO units and alkyl radicals of 8 to 20 C atoms. 2. Carboxylic acid polyglycol esters, in particular fatty acid polyglycol esters, preferably those with more than 6 EO units and carboxylic acid radicals of 8 to 20 C atoms. 3. Ethoxylated or non-ethoxylated sorbitan fatty acid esters. 4. Ethoxylated castor oil or hydrogenated variants. 5. Polyglycerol carboxylic acid esters. 6. Alkyl polyglycosides of the general formula R*-OZ O , wherein R* is a linear or branched, saturated or unsaturated alkyl radical with an average of 8-24 C atoms and Z O is an oligoglycoside radical with an average of 1-10 hexose or pentose units or mixtures thereof. 7. Alkylaryl polyglycol ethers, preferably those with 5 to 30 EO units and 8 to 20 carbon atoms in the alkyl and aryl radicals. 8. Ethylene oxide / propylene oxide (EO / PO) block copolymers, preferably those with 8 to 30 EO or PO units. 9.Polyvinyl alcohol containing 5 to 50%, preferably 8 to 20%, vinyl acetate units, with a degree of polymerization of 500 to 3000. 10. Addition products of alkylamines containing alkyl radicals of 8 to 22 carbon atoms with ethylene oxide or propylene oxide. 11. Natural substances and their derivatives, such as lecithin, lanolin, saponins, cellulose; cellulose alkyl ethers and carboxyalkylcelluloses, whose alkyl groups each have up to 4 carbon atoms. 12. Linear organo(poly)siloxanes containing polar groups, in particular containing the elements O, N, C, S, P, Si, especially those containing alkoxy groups with up to 24 carbon atoms and / or up to 40 EO and / or PO groups.

[0049] Preferred non-ionic emulsifiers (B-1) are 1. Alkyl polyglycol ethers, preferably those with 3 to 30 EO units and alkyl radicals of 8 to 20 C atoms such as Ceteareth-20, Oleth-10, Oleth-20, Laureth-3, Laureth-4, Laureth-20, Laureth-23, Trideceth-5, Trideceth-6, Trideceth-8, Trideceth-10, Trideceth-12, Trideceth-16, Trideceth-20, Steareth-20 or Steareth-21 (according to INCI name). 2. Carboxylic acid polyglycol esters, especially fatty acid polyglycol esters, preferably those with more than 6 EO units and carboxylic acid residues of 8 to 20 C atoms, such as PEG-20 stearate, PEG-20 laurate, PEG-7 olivate, PEG-8 oleate, PEG-8 laurate HLB, PEG-6 stearate, PEG-20 stearate or PEG-100 stearate (according to INCI name). 3. Ethoxylated or non-ethoxylated sorbitan fatty acid esters, such as sorbitan laurate, polysorbate 20, polysorbate 60, polysorbate 80 or polysorbate 85 (according to INCI name). 4. Ethoxylated castor oil or hydrogenated variants, such as(Name according to INCI nomenclature) PEG 200 Castor Oil or PEG-60 hydrogenated Castor Oil. 5. Polyglycerolcarboxylic acid esters, such as polyglycerol-10 oleate, polyglycerol-10 laurate or polyglycerol-10 stearate. 6. Alkyl polyglycosides of the general formula R*-OZ O , where R* is a linear or branched, saturated or unsaturated alkyl radical with an average of 8-24 C atoms and Z O is an oligoglycoside radical with an average of 1-10 hexose or pentose units or mixtures thereof, such as Glucopon 215, Glucopon 225, Glucopon 600 (name according to trade name).

[0050] (Non-limiting) examples of anionic emulsifiers (B-2) are: 1. Alkyl sulfates, particularly those with a chain length of 8 to 18 carbon atoms, alkyl and alkaryl ether sulfates with 8 to 18 carbon atoms in the hydrophobic radical and 1 to 30 ethylene oxide (EO) or propylene oxide (PO) units. 2. Sulfonates, particularly alkylsulfonates with 8 to 18 carbon atoms, alkylarylsulfonates with 8 to 18 carbon atoms. 3. Alkali and ammonium salts of carboxylic acids with 8 to 20 carbon atoms in the alkyl, aryl, alkaryl, or aralkyl radical, in particular alkali and ammonium salts of fatty acids, preferably those with carboxylic acid radicals of 8 to 20 carbon atoms.

[0051] Preferred anionic emulsifiers (B-2) are alkali and ammonium salts of carboxylic acids having 8 to 20 C atoms in the alkyl, aryl, alkaryl or aralkyl radical, particularly preferred anionic emulsifiers are alkali and ammonium salts of fatty acids, preferably those having carboxylic acid radicals of 8 to 20 C atoms, such as sodium salts, potassium salts, triethanolammonium salts of lauric acid, myristic acid, palmitic acid, stearic acid or oleic acid.

[0052] (Non-limiting) examples of cationic emulsifiers (B-3) are: 1. Salts of primary, secondary, and tertiary fatty amines with 8 to 24 carbon atoms with acetic acid, sulfuric acid, hydrochloric acid, and phosphoric acids. 2. Alkylpyridinium, alkylimidazolinium, and alkyloxazolinium salts, especially those whose alkyl chains have up to 18 carbon atoms, especially the halides, sulfates, phosphates, and acetates. 3. Quaternary alkyl and alkylbenzeneammonium salts, especially those whose alkyl groups have 6 to 24 carbon atoms, especially the halides, sulfates, phosphates, and acetates.

[0053] Furthermore, compounds known as thickeners (C), such as polyacrylic acid, polyacrylates, cellulose ethers such as carboxymethylcellulose and hydroxyethylcellulose, polyurethanes, natural thickeners such as xanthan gum, as well as preservatives and other customary additives known to the person skilled in the art, can be added.

[0054] The continuous phase of the defoamer emulsions (E) according to the invention is preferably water. However, defoamer emulsions (E) according to the invention can also be prepared in which the continuous phase is formed by components (1) or, if appropriate, (4).

[0055] These can also be multiple emulsions.

[0056] Processes for the preparation of defoamer emulsions (E) are known. Typically, they are prepared by simply stirring all components and, if necessary, subsequent homogenization using jet dispersers, rotor-stator homogenizers, colloid mills, or high-pressure homogenizers.

[0057] The defoamer emulsions (E) according to the invention are preferably oil-in-water emulsions containing 5 to 50% by weight of the defoamer formulation (A) according to the invention, 1 to 20 wt% emulsifiers (B), 0 to 5 wt% thickeners (C) and 25 to 94 wt% water (W).

[0058] The compositions according to the invention can also be formulated as free-flowing powders (P). These are preferred, for example, for use in powdered detergents. These powders are produced from the defoamer formulation (A) according to the invention by processes known to those skilled in the art, such as spray drying or granulation, and with additives known to those skilled in the art.

[0059] The invention further relates to powders (P) comprising the defoamer formulation (A) according to the invention and carrier materials (T).

[0060] The powders (P) according to the invention preferably contain 2 to 20% by weight of the defoamer formulation (A) according to the invention.

[0061] Examples of carriers (T) used include zeolites, sodium sulfate, sodium bicarbonate, sodium carbonate, cellulose derivatives, urea and urea derivatives, and sugar.

[0062] The powders (P) according to the invention contain 80 to 98 wt. % carrier materials (T). Further constituents of the powders according to the invention can be, for example, waxes or organic polymers, as described, for example, in EP-A 887097 and EP-A 1060778.

[0063] The defoamer formulations (A) according to the invention as well as their emulsions (E) or powders (P) can be used wherever defoamer formulations based on organosilicon compounds have been used to date.

[0064] This applies in particular to the control of foam in aqueous surfactant systems, for use in detergents and cleaning agents, for the control of foam in wastewater treatment plants, in textile dyeing processes, in natural gas scrubbing, in polymer dispersions, and for the defoaming of aqueous media arising in pulp production.

[0065] A further subject of the present invention is therefore a process for defoaming and / or preventing the foaming of media by mixing the defoamer formulations (A) according to the invention or their emulsions (E) or powders (P) with the media.

[0066] The defoamer formulations (A) according to the invention are preferably used for defoaming and / or preventing the foaming of cationic surfactant systems or in applications in which spreading plays an important role.

[0067] The defoamer formulations according to the invention can furthermore be used in washing and cleaning agents and care products, such as fabric softeners, wherein the defoamer formulations (A) according to the invention can be used in bulk or in the form of emulsions (E) or powders (P).

[0068] The present invention therefore further provides washing, cleaning and washing care compositions comprising the defoamer formulations (A) according to the invention or the defoamer formulations according to the invention in the form of emulsions (E) or in the form of powders (P).

[0069] The defoamer formulation according to the invention can be added directly to the foaming media, dissolved in suitable solvents such as toluene, xylene, methyl ethyl ketone, or tert-butanol, as a powder or as an emulsion. The amount required to achieve the desired defoamer effect depends, for example, on the type of medium, the temperature, and the turbulence encountered.

[0070] In the following examples, all parts and percentages are by weight unless otherwise stated. Unless otherwise stated, the following examples are carried out at ambient atmospheric pressure, i.e., approximately 1000 hPa, and at room temperature, i.e., approximately 20°C, or a temperature that occurs when the reactants are combined at room temperature without additional heating or cooling.

[0071] Dynamic viscosities were measured on an Anton Paar MCR 302 rheometer according to DIN EN ISO 3219:1994 and DIN 53019, using a cone-and-plate system (CP50-2 cone) with an opening angle of 2°. The instrument was calibrated with Normalöl 10000 from the Physikalisch-Technische Bundesanstalt (PTB). The measurement temperature was 25.00°C + / - 0.05°C, and the measurement time was 3 minutes. The viscosity data (given in mPa s) represents the arithmetic mean of three independently performed individual measurements. The measurement uncertainty of the dynamic viscosity is 1.5%. The shear rate gradient was selected depending on the viscosity and is reported separately for each viscosity data.

[0072] Kinematic viscosities are determined using a ViscoSystem ® AVS 350 viscosity measuring system from Schott, using Ubbelohde viscometer tubes with constants (e.g., from Windaus or VWR) according to DIN 51562 Part 1 or ISO / DIS 3105 (including their calibration). Measurements are performed at a temperature of 25.0°C (+- 0.1°C). The viscosity value (given in mm² / s) represents the arithmetic mean of three independently performed individual measurements. The measurement uncertainty of the kinematic viscosity is 1.05%. Depending on the measuring range, different viscometer tubes with corresponding reference constants are used: Measuring range Capillary No. Directional constant 0.5 - 3 mm 2 < / s 0c 0,003 K 0.8 - 5 mm 2 < / s 0a 0,005 K 1.2 - 10 mm 2 < / s I 0,01 K 3 - 30 mm 2 < / s Ic 0,03 K 10 - 100 mm 2 < / s II 0,10 K 30 - 300 mm 2 < / s IIc 0,30 K 100 - 1000 mm 2 < / s III 1 K 300 - 3000 mm 2 < / s IIIc 3 K 1000 - 10000 mm 2 < / s IV 10 K

[0073] Specification of the measuring range, the corresponding capillary number, and the constant according to the VWR laboratory catalog, 2011-2013, p. 645.8. Example 1: Preparation of defoamer formulation (A1), (VA2) and (VA3), defoamer emulsions (E1) and (VE2) and defoamer powder (P1): a) Defoamer formulation A1 :

[0074] To prepare the defoamer formulation A1 89 parts by weight of an MCT oil (commercially available from Gustavheess under the name MCT Oil Type V Ph.Eur. 10.0 with a content of saturated fatty acids with 8 or 10 carbon atoms of at least 95.0 wt.% and max. 1.0 wt.% of ≥ C16 fatty acids), 6 parts by weight of a precipitated silica (commercially available from Evonik under the name Sipernat ®< D 10), 2.5 parts by weight of a hydrocarbon mixture with a boiling range of 235-270°C (commercially available under the name Exxsol D 100 S from Staub & Co. Nuremberg, Germany) and 2.5 parts by weight of a silicone resin which is solid at room temperature and consists of the following units (according to 29< Si-NMR and IR analysis): 40 mol-% CH 3 SiO 1 / 2 -, 50 mol-% SiO 4 / 2 -, 8 mol-% C 2 H 5 OSiO 3 / 2 -, and 2 mol-% HOSiO 3 / 2 -, with a weight-average molecular weight of 7900 g / mol (based on polystyrene standard), were homogenized with a dissolver for 10 min at 800 rpm. This resulted in a low-viscosity defoamer formulation. A1 with a viscosity of 305 mPa·s (at 25°C and at a shear rate of 10 1 / s). b) non-inventive defoamer formulation VA2:

[0075] For the preparation of the non-inventive defoamer formulation VA2 85 parts by weight of soybean oil (commercially available from Gustavheess under the name Hydrogenated Soybean Oil Ph. Eur. with a content of 9-13 wt.% palmitic acid, 17-30 wt.% oleic acid and isomers, 48-58 wt.% linoleic acid, 5-11 wt.% linolenic acid and a maximum of 0.1 wt.% < C14 fatty acids), 5 parts by weight of the precipitated silica from Example 1a), 5 parts by weight of the hydrocarbon mixture from Example 1a) and 5 parts by weight of the solid silicone resin from Example 1a) were homogenized with a dissolver for 10 minutes at 800 rpm. This results in a low-viscosity defoamer formulation. VA2 with a viscosity of 840 mPa·s (at 25°C and at a shear rate of 10 1 / s). c) non-inventive defoamer formulation VA3:

[0076] The preparation of the non-inventive defoamer formulation VA3 is carried out analogously to the preparation of the defoamer formulation VA2. Palm oil (available from Gustavheess under the name Hydrogenated Palm Oil Ph. Eur. with a content of approximately 35 wt.% palmitic acid, approximately 46 wt.% oleic acid, approximately 13.5 wt.% linoleic acid, 3.5 wt.% stearic acid, and a maximum of 2.5 wt.% < C14 fatty acids) was used as the main component instead of soybean oil. The result is a defoamer formulation. VA3 with a viscosity of 300000 mPa·s (at 25°C and at a shear rate of 0.5 1 / s). d) Defoamer emulsion E1 :

[0077] Defoamer emulsion E1 is prepared by mixing 10 parts by weight of an emulsifier mixture containing an ethoxylated isotridecyl alcohol (HLB value of 11.2), an ethoxylated stearyl alcohol (HLB 9.7), pentaerythritol distearate and ammonium lauryl sulfate with 20 parts by weight of the defoamer formulation A1 and 70 parts by weight of water using an Ultraturrax. Finally, 0.3 parts by weight of a biocide mixture consisting of benzylisothiazolinone and chloromethylisothiazolinone is added. This results in a milky-white emulsion with a viscosity of 220 mPa s (at 25°C and a shear rate of 10 1 / s). e) non-inventive defoamer formulation VE2:

[0078] The preparation of the non-inventive defoamer emulsion VE2 is carried out analogously to the preparation of the defoamer formulation E1, where instead of the defoamer formulation A1 the defoamer formulation VA2 The result is a milky-white emulsion with a viscosity of 50 mPa·s (at 25 °C and a shear rate of 10 1 / s). f) Defoamer powder P1 :

[0079] In a beaker, 56.3 g of sodium bicarbonate, 56.3 g of sodium sulfate, and 15.0 g of a native cellulose, such as Arbocel UFC M8 (available from Rettenmaier & Söhne), are placed and mixed together vigorously using a paddle stirrer. 22.5 g of the defoamer formulation A1 are slowly added with vigorous stirring. A white, free-flowing powder is obtained. Example 2: Tests of defoamer effectiveness in washing machines

[0080] To 130 g of a washing powder ECE-2 from WFK, a certain amount (see Table 1) of defoamer formulation was added A1 The washing powder was then added to a drum washing machine (Miele Novotronik W918 without Fuzzy Logic) along with 3500 g of clean cotton laundry. The wash program was then started. The program ran at a temperature of 40°C and a water hardness of 3°GH. The foam height was recorded over a period of 55 minutes. The average foam score was determined from the foam scores measured over the entire period (0% no foam measurable to 100% overfoaming). The lower this score, the more effective the defoamer formulation over the entire period. Table 1: A1 Defoaming effect of the defoamer formulation in a washing machine: Defoamer formulation Dosage per 100 g washing powder average foam note A1 0,5 g 7%

[0081] The defoamer formulation A1 has an excellent anti-foam effect throughout the entire washing period. Example 3: Testing the effectiveness as a defoamer for surfactant residues in the rinsing cycle

[0082] 5.0 liters of tap water (16°C) are poured into an 8-liter plastic bowl. 20 g of ECE-2 washing powder from WFK are added and dispersed by hand. A terry cloth towel (100% cotton, 45 x 45 cm, approx. 100 g, approx. 490 g / m², pre-washed twice in the washing machine) is placed in the wash solution, immersed several times, squeezed out, and allowed to soak. The terry cloth towel is removed and wrung out to a total weight of 350 g.

[0083] A rinsing solution (in another 8 L plastic bowl) consisting of 5 L of tap water (16°C) and 15 g of a cationic surfactant solution is prepared. The cationic surfactant solution is an 11.1 wt. % aqueous solution of Stepantex®< VK 90 (a 9:1 mixture of methyl bis[ethyl(tallowate)]-2-hydroxyethyl ammonium methyl sulfate with isopropanol; commercially available from Stepan). Depending on the experiment (see Table 2), the specified amounts of defoamer formulation or emulsion are added.

[0084] The wet terry cloth is placed in the rinse solution, removed, and wrung out to generate foam. This procedure is repeated three times. Finally, after 30 seconds, a photograph is taken to evaluate the resulting foam on the surface of the rinse solution. Table 2 : Cationic surfactant formulations: Aqueous cationic surfactant solution Amount of cationic surfactant (*) Amount of defoamer formulation or emulsion K1 11.1% by weight - K2 11.1% by weight 0.025 wt.% A1 K3 11.1% by weight 0.125 wt.% E1 K4 11.1% by weight 0.125 wt.% VE2 (*) Methyl bis[ethyl(tallowate)]-2-hydroxyethyl ammonium methyl sulfate (available from Stepan under the name Stepantex ®< VK 90, 9:1 mixture with isopropanol) Table 3 :Evaluation of defoamer effectiveness: Cationic surfactant solution Defoamer effectiveness K1 - K2 +++ K3 ++ K4 - - no foam reduction (< 30% foam reduction) + slight foam reduction (30-50% foam reduction) ++ good foam reduction (50 - 75% foam reduction) +++ very good foam reduction (> 75% foam reduction)

[0085] Cationic surfactant formulation K2 containing defoamer formulation A1 shows compared to the blank value K1 (without defoamer formulation) has excellent defoamer effectiveness. This also applies to the cationic surfactant formulation K3 containing emulsion E1 (again containing A1). In contrast, the (non-inventive) defoamer emulsion VE2 (based on triacylglycerides with >C14 fatty acid residues as main component) no defoamer effect. Example 4: Testing the defoamer effectiveness in an aqueous cationic surfactant solution

[0086] 20 ml of a cationic surfactant solution is added to a 50 mL BRAND ®< PP centrifuge tube. Methyl bis[ethyl(tallowate)]-2-hydroxyethyl ammonium methyl sulfate (available from Stepan under the name Stepantex ®< VK 90, 9:1 mixture with isopropanol) is used as the cationic surfactant. The amount of cationic surfactant is varied according to the information in Table 4. The defoamer formulation is added to the cationic surfactant solution, and the solution is stirred to evenly distribute the defoamer formulation.

[0087] Using an Ultra Turrax disperser (ULTRA-TURRAX T 25 from IKA-Labortechnik, equipped with an S 25 N-10 G dispersing tool), the cationic surfactant solution is sheared at 20,000 rpm for 1 min. The disperser is removed, and the resulting foam height is determined after 60 seconds. Table 4 : A1 VA3 Defoaming effect of the defoamer formulations and in a cationic surfactant solution: Concentration of the cationic surfactant in the cationic surfactant solution Foam height after 60 seconds defoamer formulation A1 Foam height after 60 seconds defoamer formulation VA3 4 wt.% 3 ml 15 ml 5 wt.% 1 ml 12 ml 6 wt.% 0 ml 11 ml 7 wt.% 1 ml 9 ml 8 wt.% 0 ml 8 ml 9 wt.% 3 ml 9 ml 10 wt.% 4 ml 7 ml (Dosage 0.1 wt.% of the defoamer formulation A1 or VA3 in the cation surfactant solution)

[0088] The defoamer formulation A1 shows a higher performance over the entire concentration range of the cationic surfactant solution compared to the defoamer formulation VA3 better defoamer effect. Example 5: Testing the defoamer effectiveness of the defoamer powder according to the invention P1 during the washing process in the dishwasher:

[0089] To 20 g of a defoamer-free dishwashing powder (containing sodium citrate dihydrate, sodium carbonate, sodium sulfate, sodium bicarbonate, sodium percarbonate, tetrasodium etidronate and ceteareth-25) a certain amount (see Table 5) of the defoamer powder was added P1 The washing powder was then poured into the wash compartment of a dishwasher (type Bauknecht GSF 50204). The wash program was then started without any dishes. The program ran at a temperature of 40°C and a water hardness of 16°GH. The foam height was determined using the spray pressure. The spray pressure indicates the foam development during the wash cycle. If only water is pumped, the spray pressure is approximately 300 mbar. If the spray pressure drops, a water / foam mixture is pumped. The lower the spray pressure drops, the more foam is in the dishwasher. The minimum spray pressure is recorded. Table 5 : P1 Defoaming effect of defoamer formulations in dishwashers: Amount of defoamer powder used Minimum spray pressure (average over 3 measurements note 2 wt.% P1 248 mbar hardly any foaming No defoamer 36 mbar Very strong foaming

[0090] The defoamer powder P1 (containing defoamer formulation A1 ) shows a very good effect in controlling foam during the washing process in the dishwasher.

Claims

1. Defoamer formulations (A) comprising (1) 100 parts by weight of triacylglycerides of the formula where R may be the same or different and is a saturated or unsaturated C5-C13 hydrocarbon radical, (2) at least 1 part by weight and at most 25 parts by weight of fillers, based on 100 parts by weight of (1), (3) at least 1 part by weight and at most 25 parts by weight of organopolysiloxane resins, based on 100 parts by weight of (1), composed of units of the general formula         R2e(R3O)fSiO(4-e-f) / 2     (II), where R2 may be the same or different and is a hydrogen atom or a monovalent, optionally substituted, SiC-bonded hydrocarbon radical having 1 to 30 carbon atoms, R3 may be the same or different and is a hydrogen atom or a monovalent, optionally substituted, hydrocarbon radical having 1 to 4 carbon atoms, e is 0, 1, 2 or 3 and f is 0, 1, 2 or 3, with the proviso that the sum of e+f is less than or equal to 3 and in less than 50% of all units of the formula (II) in the organopolysiloxane resin the sum of e+f is equal to 2, optionally (4) at least 0 parts by weight and at most 25 parts by weight of water-insoluble organic compounds, based on 100 parts by weight of (1), which differ from the triacylglycerides (1), and optionally (5) at least 0 parts by weight and at most 2 parts by weight of alkaline or acidic catalysts or reaction products thereof with the components (1) to (4), based on 100 parts by weight of (1).

2. Defoamer formulations (A) according to Claim 1, characterized in that said formulations are triglycerides comprising medium-chain fatty acids selected from caproic acid (C 6:0), caprylic acid (C 8:0), capric acid (C 10:0) and lauric acid (C 12:0), where in the nomenclature (C 6:0), (C 8:0), (C 10:0) and (C 12:0), "C 6", "C 8", "C 10" and "C 12" is in each case the number of carbon atoms and the "0" signifies the number of double bonds.

3. Defoamer formulations according to Claim 1 or 2, characterized in that silicas are used as fillers (2).

4. Defoamer formulations (A) according to any of Claims 1 to 3, characterized in that the organopolysiloxane resins (3) used are MQ resins composed of units of the formulae         SiO2     (Q units) and         R23SiO1 / 2     (M units), where the molar ratio of M to Q units is in the range from 0.5 to 2.0, the MQ resins may also comprise, in addition to the M and Q units, small amounts of R2SiO3 / 2 or (R3O)SiO3 / 2 (T) units or R22SiO2 / 2 (D) units, in amounts from 0.01 to 20 mol%, based on the sum of all siloxane units, and the MQ resins may comprise up to 10% by weight of free Si-bonded hydroxyl or alkoxy groups, such as methoxy or ethoxy groups, where R2 and R3 are as defined in Claim 1.

5. Defoamer formulations (A) according to any of Claims 1 to 4, characterized in that the water-insoluble organic compounds (4) used, which differ from the triglycerides (1), are those having a boiling point greater than 100°C at 900 to 1100 hPa, preferably those selected from hydrocarbons, polyisobutylenes and fatty acid esters with monoalcohols.

6. Emulsions (E) of defoamer formulations comprising defoamer formulations (A) according to any of Claims 1 to 5, emulsifiers (B), optionally thickeners (C) and water (W).

7. Powder (P) comprising defoamer formulations (A) according to any of Claims 1 to 5 and support materials (T).

8. Detergent, cleaning composition or laundry care composition comprising defoamer formulations (A) according to any of Claims 1 to 5 or emulsions (E) thereof according to Claim 6 or powders (P) thereof according to Claim 7.

9. Process for defoaming and / or for preventing foaming of media by mixing the defoamer formulations (A) according to any of Claims 1 to 5 or emulsions (E) thereof according to Claim 6 or powders (P) thereof according to Claim 7 with the media.

10. Use of the defoamer formulations (A) according to Claim 1 to 5 or emulsions (E) thereof according to Claim 6 or powders (P) thereof according to Claim 7 for defoaming and / or for preventing foaming in cationic surfactant systems or in the rinsing cycle of the washing process.