Antifoam formulation containing triacylglycerides

Abstract

The present invention relates to (1) A triacylglyceride of formula (I), (2) filler, (3) an organic polysiloxane resin composed of units of general formula (II); As desired (4) a water-insoluble organic compound different from triacylglyceride (1), and As desired (5) an alkaline or acidic catalyst or a reaction product of said catalyst with components (1) to (4), The present invention relates to an antifoam formulation (A) comprising: [Formula 1] JPEG2025507878000010.jpg7466 (wherein R may be the same or different, and each R is a saturated or unsaturated C5-C 13 It is a hydrocarbon group. R 2 e (R 3 O) f SiO (4-e-f) / 2 (II) (In the formula, R 2 are the same or different and are a hydrogen atom or an optionally substituted monovalent hydrocarbon group having 1 to 30 carbon atoms bonded through a SiC bond, R 3 may be the same or different and are a hydrogen atom or an optionally substituted monovalent hydrocarbon group having 1 to 4 carbon atoms, e is 0, 1, 2 or 3; f is 0, 1, 2 or 3, provided that e+f is 3 or less, and e+f is 2 in less than 50% of all units of formula (II) in said organopolysiloxane resin.

Description

[Technical Field]

[0001] The present invention relates to antifoam formulations containing triacylglycerides and their use as antifoam agents, particularly in aqueous surfactant systems. [Background technology]

[0002] Many liquid systems, especially aqueous systems, contain surface-active compounds as desirable or undesirable components and can cause foaming problems when in strong contact with more or less gaseous substances, such as when sparging wastewater, when agitating liquids, during distillation, washing or coloring processes, or during dispensing procedures.

[0003] This foam can be controlled mechanically or by the addition of antifoam agents. The most effective antifoam formulations, especially for detergents, are silicone-based.

[0004] There is a certain demand for defoamer formulations that contain small amounts of organopolysiloxanes or that are free of organopolysiloxanes. U.S. Patent No. 5,693,256 A and European Patent No. 1,703,958 B1 describe organopolysiloxane-free defoamer formulations that use a water-insoluble organic liquid together with a hydrophobic filler and siloxane resin instead of organopolysiloxanes. The water-insoluble organic liquid used in these patents can be vegetable oil, in addition to isoparaffin oil, fatty acid ester, or mineral oil. Rapeseed oil and peanut oil are listed as vegetable oils. Vegetable oils are triacylglycerides in which three fatty acid groups are all bonded to a glycerol group via ester bonds. Rapeseed oil is a triacylglyceride, and its fatty acid groups are mainly oleic acid, linoleic acid, linolenic acid, and palmitic acid, i.e., C16 or C18 fatty acid groups. The same is true for peanut oil, whose fatty acid groups are also mainly composed of oleic, linoleic and palmitic acid groups, i.e. C16 or C18 fatty acid groups. The defoamer formulations described in U.S. Pat. No. 5,693,256 A and European Patent No. 1,703,958 B1 are primarily used for foam control in the wash cycle of laundry washing machines, in addition to defoaming or breaking down foam in black liquor in cutting oil treatment.

[0005] Antifoam formulations based on rapeseed oil or peanut oil work very well in the applications described. Summary of the Invention [Problem to be solved by the invention]

[0006] However, in the course of improving antifoam formulations, it was discovered that in applications where cationic surfactants are used or where diffusion plays an important role, such as the wash cycle of a laundry process, foam control compositions based on triacylglycerides having primarily C16 or C18 fatty acid groups, such as the aforementioned rapeseed oil or peanut oil, are very weakly or ineffective.

[0007] It was an object to provide an antifoam formulation which does not have the aforementioned drawbacks. This object is achieved by the present invention. [Means for solving the problem]

[0008] Therefore, the present invention provides (1) a triacylglyceride of formula (I), (2) filler, (3) an organic polysiloxane resin composed of units of general formula (II); As desired (4) a water-insoluble organic compound different from the triacylglyceride (1), and As desired (5) an alkaline or acidic catalyst or a reaction product of the catalyst with components (1) to (4); The present invention provides an antifoam formulation (A) comprising: [ka] (In the formula, R may be the same or different, and may be a saturated or unsaturated C5-C 13 It is a hydrocarbon group. R 2 e (R 3 O) f SiO (4-e-f) / 2 (II) (In the formula, R 2 may be the same or different and are hydrogen atoms or optionally substituted monovalent hydrocarbon groups having 1 to 30 carbon atoms bonded by SiC bonds, R 3 may be the same or different and are a hydrogen atom or an optionally substituted monovalent hydrocarbon group having 1 to 4 carbon atoms, e is 0, 1, 2 or 3; f is 0, 1, 2 or 3, provided that e+f is 3 or less, and that e+f is 2 in less than 50% of all units of formula (II) in the organopolysiloxane resin. [Effects of the Invention]

[0009] Surprisingly, it has been found that antifoam formulations based on triacylglycerides with fatty acid groups containing less than 16 carbon atoms are very effective, especially in the aforementioned applications where cationic surfactants are used, as well as in applications where diffusion plays an important role, such as the wash cycle of a laundry process. DETAILED DESCRIPTION OF THE INVENTION

[0010] The defoamer formulation (A) is 100 parts by weight of triacylglyceride (1), In either case, 1 part by weight or more, preferably 1.5 parts by weight or more, particularly preferably 2 parts by weight or more, and 25 parts by weight or less, preferably 20 parts by weight or less, particularly preferably 15 parts by weight or less of filler (2) per 100 parts by weight of (1); In either case, an organic polysiloxane resin (3) is used in an amount of 1 part by weight or more, preferably 1.5 parts by weight or more, particularly preferably 2 parts by weight or more, and 25 parts by weight or less, preferably 20 parts by weight or less, particularly preferably 15 parts by weight or less, per 100 parts by weight of (1); In either case, a water-insoluble organic compound (4) in an amount of 0 to 25 parts by weight, preferably 17 parts by weight or less, particularly preferably 10 parts by weight or less, per 100 parts by weight of (1), and In either case, 0 part by weight or more, preferably 0.05 part by weight or more, particularly preferably 0.1 part by weight or more, and 2 parts by weight or less, preferably 1 part by weight or less, particularly preferably 0.5 parts by weight or less of an alkaline or acidic catalyst (5) or a reaction product of the catalyst with components (1) to (4) per 100 parts by weight of (1); It is preferred that the compound contains:

[0011] Examples of the hydrocarbon group R include alkyl or alkylene groups such as pentyl, pentenyl, hexyl, hexenyl, heptyl, heptenyl, octyl, octenyl, nonyl, nonenyl, decyl, decenyl, undecyl, undecenyl, dodecyl, dodecenyl, tridecyl, and tridecenyl groups. Alkyl groups are preferred. Particularly preferred R groups are pentyl, heptyl, nonyl and undecyl groups.

[0012] The triacylglyceride (1) used in the antifoam formulation (A) is preferably a triglyceride having medium-chain fatty acids. Medium-chain fatty acids include caproic acid (C6:0), caprylic acid (C8:0), capric acid (C10:0), and lauric acid (C12:0). In the term (C6:0), "C6" indicates the number of carbon atoms, and "0" indicates the number of double bonds. The triacylglycerides (1) used in the antifoam formulation (A) are obtained industrially by hydrolysis of coconut oil and palm kernel oil, followed by fractionation of the medium chain fatty acids, and finally re-esterification with glycerol.

[0013] The triacylglyceride (1) may be a triglyceride having predominantly only one fatty acid, such as glyceryl tricaprylate (INCI name), or a triglyceride having a mixture of fatty acids, such as caprylic / capric triglyceride (INCI name).

[0014] The triacylglyceride (1) may further contain a small amount (as an impurity), preferably 0 to 10% by weight, particularly 0 to 5% by weight, of a fatty acid group having a chain length of more than 14 carbon atoms, such as a stearyl group, a palmityl group, a linolyl group, or a linoleyl group.

[0015] The triacylglycerides (1) also include so-called MCT oils (medium-chain triglycerides), which are commercially available, for example, as palm-based MCT oil (Gustavhees) or as CremerCOOR® MCT C8, CremerCOOR® MCT 60-40 or CremerCOOR® MCT 30-70 (Kremer Oleo).

[0016] R 2 is preferably a hydrocarbon group having 1 to 30 carbon atoms. Hydrocarbon group R 2Examples of the alkyl groups include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, and tert-pentyl; hexyl groups such as n-hexyl; heptyl groups such as n-heptyl; octyl groups such as n-octyl and isooctyl (e.g., 2,2,4-trimethylpentyl and 2-ethylhexyl); nonyl groups such as n-nonyl; decyl groups such as n-decyl; and dodecyl groups such as n-dodecyl. tetradecyl groups such as n-tetradecyl groups; hexadecyl groups such as n-hexadecyl groups, and octadecyl groups such as n-octadecyl groups; cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl, and 4-ethylcyclohexyl groups; aryl groups such as phenyl, naphthyl, anthryl, and phenanthryl groups; alkaryl groups such as o-, m-, p-tolyl, xylyl, and ethylphenyl groups; and aralkyl groups such as benzyl and α- and β-phenylethyl groups. Hydrocarbon group R 2 may contain ether or polyether groups.

[0017] base R 2 is preferably a methyl group, an ethyl group, or a phenyl group.

[0018] base R 3 Examples of the alkyl group include a hydrogen atom and an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.

[0019] base R 3 is preferably a hydrogen atom, a methyl group, or an ethyl group.

[0020] The BET surface area of ​​the filler (2) used in the defoaming agent formulation of the present invention is 20 to 1000 m 2 The particle size of the filler (2) is preferably less than 10 μm, and the aggregate size of the filler (2) is preferably less than 100 μm.

[0021] Examples of the filler (2) include silicon dioxide (silica), titanium dioxide, aluminum oxide, metal soap, quartz powder, PTFE powder, fatty acid amides such as ethylene bisstearamide, and finely dispersed hydrophobic polyurethane.

[0022] Silica, especially those with a BET surface area of ​​50 to 800 m 2 / g of silica is preferred as filler (2). These silicas may be fumed silica or precipitated silica. Both pretreated silica (i.e., hydrophobic silica) and hydrophilic silica can be used as filler (2). Commercially available hydrophobic silicas that can be used in the present invention include hexamethyldisilazane-treated silica with a BET surface area of ​​140 m 2 HDK® H2000, a fumed silica with a BET surface area of ​​90 m² / g (commercially available from Wacker Chemie, Germany), and a polydimethylsiloxane-treated silica with a BET surface area of ​​90 m² 2 / g of precipitated silica (commercially available from Evonik GmbH, Germany, under the name "Sipernat D10").

[0023] Component (3) used in the defoamer formulations of the present invention is preferably a silicone resin comprised of units of formula (II), wherein e+f is 2 for less than 30%, preferably less than 5%, of the units of formula (II) in the resin.

[0024] The organic polysiloxane resin (3) composed of units of formula (II) is Formula SiO2 (Q units) and formula R 2 3SiO 1 / 2 (M units) Preferably, the MQ resin is composed of units of R 2 is as defined above. In this case, the molar ratio of M units to Q units is preferably in the range of 0.5 to 2.0, more preferably in the range of 0.6 to 1.0. The MQ resin may contain, in addition to M units and Q units, a small amount of R units, if desired. 2 SiO 3 / 2 or (R 3 O)SiO3 / 2 (T) Unit or R 2 2SiO 2 / 2 The (D) unit may be contained in an amount of preferably 0.01 to 20 mol %, more preferably 0.01 to 5 mol %, based on the total of all siloxane units, and R 3 is as defined above. These MQ resins may contain up to 10% by weight of free Si-bonded hydroxyl or alkoxy groups, such as methoxy or ethoxy groups.

[0025] These organopolysiloxane resins (3) preferably have a viscosity of more than 1000 mPa·s at 25°C and 101.425 kPa or are solid. The weight average molecular weight of these resins, measured by gel permeation chromatography (based on polystyrene standards), is preferably 200 to 200,000 g / mol, in particular 1,000 to 20,000 g / mol.

[0026] If desired, a water-insoluble organic compound (4) can be used in the defoamer formulation of the present invention. In the context of the present invention, the term "water-insoluble" is understood to mean a solubility in water at 25° C. and a pressure of 101.425 kPa of less than or equal to 3% by weight.

[0027] The optional component (4) is preferably a water-insoluble organic compound having a boiling point of more than 100°C at atmospheric pressure, i.e., 900 to 1100 hPa, and is particularly selected from esters such as hydrocarbons, polyisobutylene, and fatty acid esters with monoalcohols.

[0028] Hydrocarbons include isoparaffins (e.g., available from ExxonMobil under the trade names Isopar® E, Isopar® G, Isopar® H, Isopar® J, Isopar® L, Isopar® M, Isopar® N, Isopar® P, and Isopar® V), dearomatized hydrocarbons (e.g., available from ExxonMobil under the trade names Exxsol® D40, Exxsol® 60, Exxsol® D95, Exxsol® D100, and Exxsol® D130), or white oils. Dearomatized hydrocarbons are particularly preferred. Examples of polyisobutylene include products commercially available under the trade names Indopol (registered trademark) (Ineos) or Oppanol (registered trademark) (BASF). -1 Polyisobutylene having a kinematic viscosity measured at a shear rate of 20 to 500 cSt is particularly preferred. Examples of esters, particularly fatty acid esters with monoalcohols, include methyl laurate, isopropyl laurate, octyl laurate, octyl stearate, octyl oleate, dodecyl palmitate, and isopropyl myristate.

[0029] Optional alkaline catalysts (5) include alkali metal hydroxides and alkaline earth metal hydroxides such as NaOH, KOH, CsOH, LiOH, and Ca(OH)2. Acidic catalysts (5) include hydrochloric acid, sulfuric acid, and phosphonitrile chloride. The reaction product of (5) with components (1) to (4) is, for example, a product of silica and an alkali metal hydroxide, which is preferred as filler (2), such as potassium silicate or sodium silicate. The metered addition of the catalyst can be carried out in typical organic solvents such as alcohols (methanol, ethanol, isopropanol, etc.) or esters (ethyl acetate, etc.).

[0030] Each of the components (2) to (5) used in the antifoaming agent formulation (A) of the present invention may be a single component or a mixture of two or more components.

[0031] The viscosity of the antifoaming agent formulation (A) of the present invention is preferably 50 to 100,000 mPa·s, particularly preferably 100 to 10,000 mPa·s, and in particular 200 to 5,000 mPa·s at 25°C and 101.425 kPa.

[0032] The antifoam formulation (A) of the present invention can be prepared by known methods, such as by mixing all components under high shear in a colloid mill, dissolver, or rotor-stator homogenizer. The mixing step can be carried out under reduced pressure to prevent the inclusion of air present in highly dispersed fillers. If necessary, the filler can be hydrophobized in situ. Alternatively, component (1) may be added first, optionally heated, and then components (2), (3), optionally (4), and optionally (5) may be added successively. It is preferred to add component (3) in the form of a solution dissolved in component (4) or a part of component (4).

[0033] The present invention further comprises: the defoamer formulation (A) of the present invention, emulsifier (B), optionally a thickener (C), and Water (W) The present invention provides an emulsion (E) of a defoamer formulation comprising:

[0034] To produce the antifoam emulsion (E) of the present invention, a typical emulsifier (B) known to those skilled in the art, such as an emulsifier for producing a silicone emulsion (such as a nonionic emulsifier, an anionic emulsifier, or a cationic emulsifier), can be used. It is preferred to use an emulsifier mixture in which one or more non-ionic emulsifiers are present.

[0035] The nonionic emulsifier (B-1) used includes, but is not limited to, the following: 1. Alkyl polyglycol ethers, preferably those having 3 to 30 EO units and alkyl groups having 8 to 20 carbon atoms. 2. Carboxylic acid polyglycol esters, particularly fatty acid polyglycol esters, preferably those having more than 6 EO units and a carboxylic acid group having 8 to 20 carbon atoms. 3. Ethoxylated sorbitan fatty acid esters or non-ethoxylated sorbitan fatty acid esters. 4. Ethoxylated castor oil or its hydrogenated derivatives. 5. Polyglycerol carboxylic acid ester. 6. General formula R * -OZ o alkyl polyglycosides of the formula (wherein R * is a linear or branched saturated or unsaturated alkyl group having an average of 8 to 24 carbon atoms, and Z o is an oligoglycoside group having an average of o=1 to 10 hexose or pentose units or mixtures thereof). 7. Alkylaryl polyglycol ethers, preferably those having 5 to 30 EO units and 8 to 20 carbon atoms in the alkyl and aryl groups. 8. Ethylene oxide / propylene oxide (EO / PO) block copolymers, preferably those having 8 to 30 EO or PO units. Polyvinyl alcohol still containing 9.5% to 50%, preferably 8% to 20%, of vinyl acetate units and having a degree of polymerization of 500 to 3000. 10. Addition products of alkylamines having an alkyl group having 8 to 22 carbon atoms and ethylene oxide or propylene oxide. 11. Natural substances and their derivatives, such as lecithin, lanolin, saponin, cellulose, cellulose alkyl ethers, and carboxyalkyl cellulose, each of which has an alkyl group containing four or fewer carbon atoms. 12. Linear organic (poly)siloxanes containing polar groups (especially those containing O, N, C, S, P, Si elements), especially alkoxy groups with up to 24 carbon atoms and / or EO and / or PO groups with up to 40 carbon atoms.

[0036] Preferred nonionic emulsifiers (B-1) include the following: 1. Alkyl polyglycol ethers, preferably those having 3 to 30 EO units and an alkyl group having 8 to 20 carbon 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 names). 2. Carboxylic acid polyglycol esters, in particular fatty acid polyglycol esters, preferably those having more than 6 EO units and a carboxylic acid group having from 8 to 20 carbon atoms, such as PEG-20 stearate, PEG-20 laurate, PEG-7 olivine, PEG-8 oleate, PEG-8 laurate HLB PEG-6 stearate, PEG-20 stearate or PEG-100 stearate (according to their INCI names). 3. Ethoxylated or non-ethoxylated sorbitan fatty acid esters, such as sorbitan laurate, polysorbate 20, polysorbate 60, polysorbate 80 or polysorbate 85 (according to their INCI names). 4. Ethoxylated castor oil or its hydrogenated derivatives, such as PEG 200 castor oil or PEG-60 hydrogenated castor oil (according to INCI names). 5. Polyglycerol carboxylic acid esters, such as polyglyceryl-10 oleate, polyglyceryl-10 laurate or polyglyceryl-10 stearate. 6. General formula R * -OZ o alkyl polyglycosides of the formula (wherein R * is a linear or branched saturated or unsaturated alkyl group having an average of 8 to 24 carbon atoms, and Z ois an oligoglycoside radical having an average of o=1 to 10 hexose or pentose units or mixtures thereof), such as Glucopon 215, Glucopon 225, Glucopon 600 (trade name).

[0037] Examples of the anionic emulsifier (B-2) include, but are not limited to, the following: 1. Alkyl sulfates, especially those having a chain length of 8 to 18 carbon atoms, alkyl ether sulfates and alkaryl ether sulfates having 8 to 18 carbon atoms in the hydrophobic group and 1 to 30 ethylene oxide (EO) and / or propylene oxide (PO) units. 2. Sulfonates, particularly alkylsulfonates having 8 to 18 carbon atoms and alkylarylsulfonates having 8 to 18 carbon atoms. 3. Alkali metal and ammonium salts of carboxylic acids having 8 to 20 carbon atoms in the alkyl, aryl, alkaryl or aralkyl group, in particular alkali metal and ammonium salts of fatty acids, preferably those having a carboxylic acid group having 8 to 20 carbon atoms.

[0038] The anionic emulsifier (B-2) is preferably an alkali metal salt or ammonium salt of a carboxylic acid having 8 to 20 carbon atoms in the alkyl group, aryl group, alkaryl group, or aralkyl group. Particularly preferred anionic emulsifiers are alkali metal salts or ammonium salts of fatty acids, preferably those having a carboxylic acid group having 8 to 20 carbon atoms, such as sodium salts, potassium salts, and triethanolammonium salts of lauric acid, myristic acid, palmitic acid, stearic acid, or oleic acid.

[0039] Examples of the cationic emulsifier (B-3) include, but are not limited to, the following: 1. Salts of primary, secondary, and tertiary aliphatic amines having 8 to 24 carbon atoms with acetic acid, sulfuric acid, hydrochloric acid, and phosphoric acid. 2. Alkylpyridinium salts, alkylimidazolinium salts and alkyloxazolinium salts, especially those in which the alkyl chain has 18 or fewer carbon atoms, specifically halides, sulfates, phosphates and acetates. 3. Quaternary alkylammonium salts and alkylbenzeneammonium salts, especially those in which the alkyl group has 6 to 24 carbon atoms, in particular the halides, sulfates, phosphates and acetates.

[0040] Additionally, compounds known as thickeners (C) may be added, such as polyacrylic acid, polyacrylates, cellulose ethers such as carboxymethyl cellulose and hydroxyethyl cellulose, polyurethanes, natural thickeners such as xanthan gum, preservatives, and other common additives known to those skilled in the art.

[0041] The continuous phase of the defoamer emulsion (E) of the present invention is preferably water, but it is also possible to produce the defoamer emulsion (E) of the present invention by forming the continuous phase with component (1) or, if desired, (4). The antifoam emulsion may be a multiple emulsion.

[0042] Methods for preparing the antifoam emulsion (E) are known and are typically prepared by simply mixing all of the ingredients, followed by homogenization, if desired, using a jet disperser, rotor-stator homogenizer, colloid mill, or high-pressure homogenizer.

[0043] The defoamer emulsion (E) of the present invention is 5 to 50% by weight of the defoamer formulation (A) of the present invention, 1 to 20% by weight of an emulsifier (B); 0 to 5 wt. % of a thickener (C), and 25 to 94% by weight of water (W) Preferably, the emulsion is an oil-in-water emulsion comprising:

[0044] The compositions of the present invention can also be formulated as free-flowing powders (P). Powders are preferred, for example, for use in powder detergents. Starting from the antifoam formulation (A) of the present invention, the powders are produced by methods known to those skilled in the art, such as spray drying or build-up granulation, using additives known to those skilled in the art.

[0045] The present invention further comprises: the defoamer formulation (A) of the present invention, and Support material (T) The present invention provides a powder (P) comprising:

[0046] The powder (P) of the present invention preferably contains 2 to 20% by weight of the antifoaming agent blend (A) of the present invention.

[0047] The support material (T) used may be, for example, zeolites, sodium sulfate, sodium bicarbonate, sodium carbonate, cellulose derivatives, urea and urea derivatives, and sugars.

[0048] The powder (P) of the present invention comprises 80 to 98% by weight of a support material (T). Further constituents of the powder of the present invention include waxes or organic polymers, as described, for example, in EP 887097 A and EP 1060778 A.

[0049] The defoamer formulations (A) of the present invention and their emulsions (E) or powders (P) can be used wherever defoamer formulations based on organosilicon compounds have been used up to now.

[0050] The present invention has particular application to foam control in aqueous surfactant systems for use in detergent and cleaning compositions, for foam control in wastewater plants, textile dyeing processes, natural gas scrubbing, polymer dispersions, and for defoaming aqueous media occurring in pulp production.

[0051] Therefore, the present invention further provides a method for preventing defoaming and / or foaming in a medium by mixing the defoamer formulation (A) of the present invention or its emulsion (E) or powder (P) with the medium.

[0052] The use of the defoamer formulation (A) of the present invention is preferred for defoaming and / or preventing foaming of cationic surfactant systems or in applications where diffusion plays an important role.

[0053] The antifoam formulations of the present invention can also be used in care products such as detergent and cleaning compositions and fabric softeners, and the antifoam formulations (A) of the present invention can be used in bulk or in the form of emulsions (E) or powders (P).

[0054] The present invention therefore further provides detergents, cleaning compositions and laundry care compositions comprising the inventive defoamer formulation (A) or the inventive defoamer formulation in the form of an emulsion (E) or powder (P).

[0055] The defoamer formulations of the present invention can be added directly to the foaming medium as a powder or emulsion, or dissolved in a suitable solvent such as toluene, xylene, methyl ethyl ketone, or tert-butanol. The amount required to achieve the desired defoaming effect depends, for example, on the type of medium, its temperature, and the turbulence that occurs. [Example]

[0056] In the following examples, all parts and percentages are by weight unless otherwise stated. The following examples are conducted at ambient atmospheric pressure (i.e., about 1000 hPa) and at room temperature (i.e., about 20° C.) or at a temperature established by combining the reactants at room temperature without additional heating or cooling, unless otherwise stated.

[0057] Dynamic viscosity was measured according to DIN EN ISO 3219:1994 and DIN 53019 using an Anton Paar "MCR 302" rheometer and a 2° cone-plate system (cone CP50-2). The instrument was calibrated with standard oil 10,000 obtained from the Physik-Technika Institute in Germany. The measurement temperature was 25.00°C ± 0.05°C, and the measurement time was 3 minutes. The viscosity specification (reported in mPa·s) represents the arithmetic mean of three independently measured values. The measurement error for dynamic viscosity is 1.5%. The shear rate gradient as a function of viscosity was selected, and the shear rate gradient was specified separately for each viscosity specification.

[0058] The kinematic viscosity is measured by means of a Schott ViscoSystem® AVS 350 viscosity measuring system using an Ubbelohde viscometer tube (e.g. from Windaus or VWR) with a constant according to DIN 51562 Part 1 or ISO / DIS 3105 (including its calibration). The measurement is carried out at a temperature of 25.0°C (±0.1°C). The viscosity specification (mm 2 The kinematic viscosity (reported in / s) represents the arithmetic mean of three independently measured individual values. The measurement error of the kinematic viscosity is 1.05%. Depending on the measurement range, different viscometer tubes with corresponding directional constants are used.

[0059] [Table 1]

[0060] Details of the measurement range, corresponding capillary numbers and constants are in accordance with VWR Laboratory Catalog, 2011-2013, p. 645.8.

[0061] Example 1: Preparation of antifoam formulations (A1), (VA2) and (VA3), antifoam emulsions (E1) and (VE2), and antifoam powder (P1):

[0062] A) Antifoam formulation A1: 89 parts by weight of MCT oil (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% by weight and a content of fatty acids with 16 or more carbon atoms of at most 1.0% by weight), 6 parts by weight of precipitated silica (available from Evonik under the name Sipernat® D 10), 2.5 parts by weight of a hydrocarbon mixture with a boiling point range of 235-270°C (available from Staub, Nuremberg, Germany under the name Exxsol D 100 S), and 40 mol% of CH3SiO4 with a weight-average molar mass of 7900 g / mol (based on polystyrene standard). 1 / 2- , 50 mol% SiO 4 / 2- , 8 mol% C2H5OSiO 3 / 2- and 2 mol% HOSiO 3 / 2- It consists of units of ( 29 The antifoam formulation A1 was prepared by homogenizing 2.5 parts by weight of silicone resin that was solid at room temperature (based on Si NMR and IR analysis) with a dissolver at 800 rpm for 10 minutes. The viscosity was 305 mPa·s (at 25°C and a shear rate of 10 s). -1 ) is obtained a low-viscosity defoamer formulation A1.

[0063] B) Antifoam formulation VA2 not according to the invention: A defoamer formulation VA2 not according to the invention was prepared by homogenizing 85 parts by weight of soybean oil (commercially available from Gustavheess under the name Hydrogenated Soybean Oil Ph.Eur., containing 9-13% by weight of palmitic acid, 17-30% by weight of oleic acid and isomers, 48-58% by weight of linoleic acid, 5-11% by weight of linolenic acid, and 0.1% by weight or less of fatty acids less than C14) with 5 parts by weight of the precipitated silica of Example 1a), 5 parts by weight of the hydrocarbon mixture of Example 1a), and 5 parts by weight of the solid silicone resin of Example 1a) in a dissolver at 800 rpm for 10 minutes. The viscosity of the formulation was 840 mPa·s (at 25°C and a shear rate of 10 s). -1 ) to obtain a low viscosity antifoam formulation VA2.

[0064] c) Antifoam formulation VA3 not according to the invention: Antifoam formulation VA3, not according to the invention, was prepared in a similar manner to the preparation of antifoam formulation VA2. Instead of soybean oil, palm oil (commercially available from Gustavheess under the name Hydrogenated Palm Oil Ph.Eur., containing approximately 35% by weight of palmitic acid, approximately 46% by weight of oleic acid, approximately 13.5% by weight of linoleic acid, 3.5% by weight of stearic acid, and up to 2.5% by weight of fatty acids below C14) was used as the main component. The viscosity of the antifoam formulation VA3 was 300,000 mPa·s (at 25°C and a shear rate of 0.5 s). -1 ) antifoam formulation VA3 is obtained.

[0065] d) Antifoam emulsion E1: Antifoam emulsion E1 is prepared by mixing 10 parts by weight of an emulsifier mixture containing ethoxylated isotridecyl alcohol (HLB value 11.2), ethoxylated stearyl alcohol (HLB value 9.7), pentaerythrityl distearate, and ammonium lauryl sulfate with 20 parts by weight of antifoam formulation A1 and 70 parts by weight of water using an Ultra-Turrax. Finally, 0.3 parts by weight of a disinfectant mixture consisting of benzisothiazolinone and chloromethylisothiazolinone is added. The viscosity is 220 mPa·s (at 25°C and a shear rate of 10 s). -1 ) a milky white emulsion is obtained.

[0066] e) Defoamer formulation VE2 not according to the invention: A non-inventive antifoam emulsion VE2 was prepared in the same manner as in the preparation of antifoam formulation E1, except that antifoam formulation VA2 was used instead of antifoam formulation A1. The viscosity was 50 mPa·s (at 25°C and a shear rate of 10 s). -1 ) a milky white emulsion is obtained.

[0067] f) Antifoam powder P1: 56.3 g of sodium bicarbonate, 56.3 g of sodium sulfate, and 15.0 g of natural cellulose (e.g., Arbocel UFC M8, available from Rettenmeyer & Söhne) are first placed in a glass beaker and vigorously mixed with each other using a blade stirrer. While vigorously stirring, 22.5 g of antifoam formulation A1 are slowly added. A white, free-flowing powder is obtained.

[0068] Example 2: Performance testing of antifoam agents in washing machines

[0069] A predetermined amount of antifoam formulation A1 (see Table 1) was added to 130 g of WFK laundry powder ECE-2. The laundry powder was then placed in a drum washing machine (Miele Novotronic W918, without fuzzy logic) along with 3500 g of clean cotton laundry. The wash program was then started. The program was run at 40°C with a water hardness of 3°GH. The foam height was recorded over a 55-minute period. The foam scores measured over the entire period were used to determine an average foam score (ranging from 0% for no measured foam to 100% for excessive foaming). The lower the average foam score, the more effective the antifoam formulation was over the entire period.

[0070] [Table 2]

[0071] Antifoam formulation A1 provides excellent antifoaming throughout the entire wash cycle.

[0072] Example 3: Testing the performance of defoamers against surfactant residues in the wash cycle

[0073] Add 5.0 L of tap water (16°GH) to an 8 L plastic bowl. Add 20 g of WFK ECE-2 laundry powder detergent and disperse by hand. Place a terry cloth towel (100% cotton, 45 x 45 cm, approximately 100 g, approximately 490 g / m²) in the bowl. 2(and pre-washed twice in the washing machine) into the washing solution, dip several times, wring and leave to soak. Remove the terry cloth towels and wring them out to a total weight of 350g. A cleaning solution (in a separate 8 L plastic bowl) is prepared consisting of 5 L of tap water (16°GH) and 15 g of cationic surfactant solution. The cationic surfactant solution is an 11.1 wt % aqueous solution of Stepantex® VK 90 (a 9:1 mixture of methylbis[ethyl(tallow fatty acid)]-2-hydroxyethylammonium methyl sulfate and isopropanol, commercially available from Stepan). A predetermined amount of antifoam formulation or emulsion is added depending on the experiment (see Table 2). A wet terry cloth towel is placed in the cleaning solution, removed and squeezed out to create a lather. This procedure is repeated three times. Finally, a photograph is taken after 30 seconds to assess the lather that has formed on the surface of the cleaning solution.

[0074] [Table 3]

[0075] [Table 4]

[0076] The cationic surfactant formulation K2 containing the antifoam formulation A1 shows superior defoaming performance compared to the blank value K1 (without the antifoam formulation). This also applies to the cationic surfactant formulation K3 containing the emulsion E1 (which also contains A1). In contrast, the (not according to the invention) antifoam emulsion VE2 (based on triacylglycerides with fatty acid groups greater than C14 as the main component) does not show any defoaming effect.

[0077] Example 4: Testing the antifoam performance of aqueous cationic surfactant solutions

[0078] 20 mL of cationic surfactant solution is placed in a 50 mL BRAND® PP centrifuge tube. Methylbis[ethyl(tallow fatty acid)]-2-hydroxyethylammonium methyl sulfate (commercially available from Stepan under the name Stepantex® VK 90, 9:1 mixture with isopropanol) is used as the surfactant. The amount of cationic surfactant varies according to the values ​​in Table 4. The antifoam formulation is added to the cationic surfactant solution, and the solution is stirred to uniformly distribute the antifoam formulation. The cationic surfactant solution is sheared for 1 minute at 20,000 rpm using an Ultra-Turrax disperser (Ultra-Turrax T 25 from IKA-Labortechnik equipped with S 25 N-10 G dispersing blades). The foam height is measured 60 seconds after the disperser is removed.

[0079] [Table 5]

[0080] Antifoam formulation A1 exhibits superior antifoam effectiveness across the entire concentration range of the cationic surfactant solution compared to antifoam formulation VA3.

[0081] Example 5: Testing the antifoaming performance of the antifoam powder P1 of the present invention in the washing process in a dishwasher:

[0082] To 20 g of antifoam-free dishwasher detergent powder (containing sodium citrate dihydrate, sodium carbonate, sodium sulfate, sodium bicarbonate, sodium percarbonate, tetrasodium etidronate, and ceteareth-25), a predetermined amount of antifoam powder P1 was added (see Table 5). The detergent powder was then placed in the wash compartment of a Bauknecht GSF 50204 dishwasher. A wash program was then started without ceramics. The program was run at a temperature of 40°C and a water hardness of 16°GH. The foam height was measured by the spray pressure. The spray pressure indicates the foam generation during the wash process. When only water is pumped, the spray pressure is approximately 300 mbar. As the spray pressure decreases, the water / foam mixture is pumped. The lower the spray pressure, the more foam there is in the dishwasher. The minimum spray pressure is recorded.

[0083] [Table 6]

[0084] Antifoam powder P1 (containing antifoam formulation A1) has a very good effect on controlling foam during the washing process in a dishwasher.

Claims

1. (1) 100 parts by weight of a triacylglyceride of formula (I), (2) a filler in an amount of 1 part by weight or more and 25 parts by weight or less per 100 parts by weight of (1); (3) 1 part by weight or more and 25 parts by weight or less of an organic polysiloxane resin composed of units of general formula (II) relative to 100 parts by weight of (1); (4) 0 to 25 parts by weight of a water-insoluble organic compound different from the triacylglyceride (1) relative to 100 parts by weight of (1), and (5) 0 to 2 parts by weight of an alkaline or acidic catalyst or a reaction product of the catalyst with components (1) to (4) per 100 parts by weight of (1); An antifoam formulation (A) comprising: 【Chemistry 1】 (wherein R may be the same or different, and may be saturated or unsaturated C ５ ~C １３ It is a hydrocarbon group.) R ２ ｅ (R ３ O) ｆ SiO （４－ｅ－ｆ）／２ (-I) (In the formula, R ２ may be the same or different and are hydrogen atoms or monovalent hydrocarbon groups having 1 to 30 carbon atoms bonded by SiC bonds, R ３ may be the same or different and are a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, e is 0, 1, 2 or 3; f is 0, 1, 2 or 3, provided that e+f is 3 or less, and that e+f is 2 in less than 50% of all units of formula (II) in the organopolysiloxane resin.

2. 2. The defoamer formulation (A) of claim 1, wherein the defoamer formulation is a triglyceride having medium chain fatty acids selected from caproic acid (C6:0), caprylic acid (C8:0), capric acid (C10:0) and lauric acid (C12:0), wherein in the terms (C6:0), (C8:0), (C10:0) and (C12:0), "C6", "C8", "C10" and "C12" respectively represent the number of carbon atoms and "0" represents the number of double bonds.

3. 3. The defoamer formulation according to claim 1, wherein silica is used as filler (2).

4. The organic polysiloxane resin (3) used is Formula SiO ２ (Q units) and Formula R ２ ３ SiO １／２ (M units) It is an MQ resin composed of units the molar ratio of M units to Q units is in the range of 0.5 to 2.0; The MQ resin contains, in addition to the M and Q units, a small amount of R ２ SiO ３／２ Or (R ３ O) SiO ３／２ (T) unit or R ２ ２ SiO ２／２ The (D) unit may be contained in an amount of only 0.01 to 20 mol % based on the sum of all siloxane units, 3. The defoamer formulation (A) of claim 1 or 2, wherein the MQ resin may contain up to 10 wt. % of free Si-bonded hydroxyl or alkoxy groups. (In the formula, R ２ and R ３ is as defined in claim 1.

5. The defoamer formulation (A) according to claim 1 or 2, wherein the water-insoluble organic compound (4) used is different from the triacylglyceride (1) and has a boiling point of more than 100 ° C. at 900 to 1100 hPa.

6. The defoamer formulation (A) according to claim 1, an emulsifier (B), and Water (W) An emulsion of an antifoam formulation (E) comprising:

7. The defoamer formulation (A) according to claim 1 and Support material (T) A powder (P) comprising:

8. 8. A detergent, cleaning composition or laundry care composition comprising an antifoam formulation (A) according to claim 1 or an emulsion of an antifoam formulation (E) according to claim 6 or a powder (P) according to claim 7.

9. A method for preventing defoaming and / or foaming in a medium by mixing the defoamer formulation (A) according to claim 1, the emulsion of the defoamer formulation (E) according to claim 6, or the powder (P) according to claim 7 with the medium.

10. 10. Use of the defoamer formulation (A) according to claim 1 or the emulsion of the defoamer formulation (E) according to claim 6 or the powder (P) according to claim 7 for defoaming and / or preventing foaming in a cationic surfactant system or in the wash cycle of a laundry process.

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