defoaming agent

Abstract

To provide a defoaming agent excellent in defoaming performance even when stored at a low temperature.SOLUTION: The defoaming agent includes: aluminum carboxylate (A); aromatic carbon (BA)-containing hydrocarbon oil (B); a polyoxyalkylene compound (C) represented by formula (1); and a mixed ester (D) composed of polyoxyethylene glycol fatty acid diesters and polyoxyethylene glycol fatty acid monoesters; wherein the content of (A) is 0.1 to 15 wt.%, the content of (B) is 40 to 94.8 wt.%, the content of (C) is 5 to 30 wt.%, and the content of (D) is 0.1 to 15 wt.% based on the weights of (A), (B), (C), and (D), and the content of (BA) is 1 to 30 atomic percent based on the total number of carbon atoms in (B). R1-(AO)n-OR2 (1) (where R1 is alkyl or alkenyl having 2 to 22 carbon atoms, R2 is acyl having 8 to 31 carbon atoms, AO is oxyalkylene having 2 to 4 carbon atoms, and n is an integer of 10 to 60).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an antifoaming agent.

Background Art

[0002] “An antifoaming agent containing aluminum carboxylate (A) and hydrocarbon oil (B) and not containing an alkaline earth metal carboxylate, wherein (A) is aluminum dicarboxylate (A2), or a mixture of aluminum monocarboxylate (A1) and aluminum dicarboxylate (A2), (A) The content of (A) is 0.1 to 60% by weight and the content of (B) is 40 to 99.9% by weight based on the weights of (A) and (B), and the content of (A1) is 40% or less based on the total weight of (A1) and (A2).” “The antifoaming agent according to any one of claims 1 to 3, further containing a polyoxyalkylene compound (C) represented by the general formula (1).

Chemical Formula

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] Conventional defoaming agents have the problem that their defoaming performance may decrease when added to foaming liquids (paints, inks, etc.) and stored at low temperatures (-5 to 0°C, etc.). In other words, the objective of the present invention is to provide a defoaming agent that exhibits excellent defoaming performance even when stored at low temperatures. [Means for solving the problem]

[0005] The antifoaming agent of the present invention is characterized by containing aluminum carboxylate (A); aromatic carbon (BA)-containing hydrocarbon oil (B); a polyoxyalkylene compound represented by formula (1) (C); and a mixed ester (D) consisting of polyoxyethylene glycol fatty acid diester and polyoxyethylene glycol fatty acid monoester. Based on the weights of aluminum carboxylate (A), hydrocarbon oil (B), polyoxyalkylene compound (C), and mixed ester (D), the content of aluminum carboxylate (A) is 0.1 to 15% by weight, the content of hydrocarbon oil (B) is 40 to 94.8% by weight, the content of polyoxyalkylene compound (C) is 5 to 30% by weight, and the content of mixed ester (D) is 0.1 to 15% by weight. The content of aromatic carbons (BA) is 1 to 30 percent based on the total number of carbon atoms in hydrocarbon oil (B).

[0006] R1-(AO)n-OR2 (1)

[0007] R1 represents an alkyl or alkenyl group with 2 to 22 carbon atoms, R2 represents an acyl group with 8 to 31 carbon atoms, AO represents an oxyalkylene group with 2 to 4 carbon atoms, and n represents an integer between 10 and 60. [Effects of the Invention]

[0008] The defoaming agent of the present invention exhibits excellent defoaming performance even when added to foaming liquids (paints, inks, etc.) and stored at low temperatures (-5 to 0°C, etc.). [Modes for carrying out the invention]

[0009] <Aluminum Carboxylate (A)> Aluminum carboxylate (A) is preferably composed of aluminum dicarboxylate or a mixture of aluminum monocarboxylate and aluminum dicarboxylate, and may also contain aluminum tricarboxylate and / or free fatty acids (FA).

[0010] The carbon number of the carboxylic acids constituting aluminum monocarboxylate, aluminum dicarboxylate, aluminum tricarboxylate, and free fatty acids (FA) is preferably 4 to 30, more preferably 8 to 24, and particularly preferably 14 to 22. When the carbon number is within this range, the defoaming performance is further improved even when stored at low temperatures.

[0011] These carboxylic acids include aliphatic carboxylic acids and alicyclic carboxylic acids, with examples including aliphatic carboxylic acids (butanoic acid, octanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, docosanoic acid, triacontanoic acid, tetradecenoic acid, hexadecenoic acid, octadecenoic acid, eicosenoic acid, docosenoic acid, and linolenic acid, etc.) and alicyclic carboxylic acids (cyclopropaneic acid, cyclobutaneic acid, cyclopentaneic acid, cyclopenteneic acid, cyclohexanecarboxylic acid, cyclohexeneic acid, cycloheptaneic acid, and cyclohepteneic acid). Of these, from the viewpoint of defoaming performance, aliphatic carboxylic acids are preferred, more preferably octanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, and docosanic acid, and particularly preferred are tetradecanoic acid, hexadecanoic acid, octadecanoic acid, and docosanic acid.

[0012] As the free fatty acid (FA), the same carboxylic acid that constitutes aluminum carboxylate (A) can be used, and the preferred ones are also the same. When free fatty acid (FA) is included, (FA) is preferably a carboxylic acid that constitutes aluminum carboxylate (A). The free fatty acid may be a mixture of two or more types, and in the case of a mixture, it is preferable that the above preferred ones are included as the main components.

[0013] When free fatty acids (FA) are present, the free fatty acid (FA) content (by weight) is preferably 1 to 30, more preferably 3 to 22, and particularly preferably 5 to 15, based on the weight of aluminum carboxylate (A). Within this range, the defoaming performance is further improved even when stored at low temperatures.

[0014] Aluminum carboxylate (A) usually contains free fatty acids (FA), but free fatty acids (FA) may be added to aluminum carboxylate (A) to achieve the above-mentioned content within the preferred range.

[0015] Aluminum carboxylate can be manufactured by known methods (for example, the double decomposition method or the direct method; see Fatty Acid Chemistry <Revised and Enlarged Edition>, published August 10, 1970 by Koshobo Co., Ltd.), and is also readily available from the market. Examples of trade names include Aluminum Stearate 300, Aluminum Stearate 600 and Aluminum Stearate 900 (NOF Corporation); Aluminum Stearate (Tannan Chemical Industry Co., Ltd.); Aluminum Stearate (Daikyo Chemical Industry Co., Ltd.); and SA-1000, SA-1500 and SA-2000 (Sakai Chemical Industry Co., Ltd.). In addition to these, it is also readily available from reagent manufacturers and the like.

[0016] The defoaming agent of the present invention preferably does not contain alkaline earth metal carboxylates. Alkaline earth metal carboxylates are composed of a carboxylic acid and an alkaline earth metal. The carboxylic acid is the same as the carboxylic acid that constitutes aluminum carboxylate (A). Examples of alkaline earth metal carboxylates include magnesium dioctadecanoate and calcium monooctadecanoate. Inclusion of alkaline earth metal carboxylates tends to cause repulsion.

[0017] The content (weight %) of aluminum carboxylate (A) is preferably 0.1 to 15, more preferably 0.5 to 13, particularly preferably 1 to 11, and most preferably 3 to 8 based on the weights of aluminum carboxylate (A), hydrocarbon oil (B), polyoxyalkylene compound (C), and mixed ester (D). When within this range, the defoaming performance is even better even when stored at low temperatures.

[0018] <Hydrocarbon oil (B) containing aromatic carbon (BA)> As the hydrocarbon oil (B) containing aromatic carbon (BA), mineral oils obtained by hydrogenating the fraction of crude oil at 250 to 415 °C can be used. The hydrocarbon oil (B) preferably contains aromatic carbon (aromatic carbon) (BA). The content (number %) of aromatic carbon (BA) is preferably 1 to 30, more preferably 4 to 26, particularly preferably 7 to 22, and most preferably 10 to 17 based on the total carbon number of the hydrocarbon oil (B). When within this range, the defoaming performance is even better even when stored at low temperatures.

[0019] When the hydrocarbon oil (B) contains naphthenic carbon (BB), the content (number %) of naphthenic carbon (BB) is preferably 15 to 40, more preferably 15 to 36, particularly preferably 16 to 32, and most preferably 17 to 29 based on the total carbon number of the hydrocarbon oil (B). When within this range, the defoaming performance is even better even when stored at low temperatures.

[0020] When the hydrocarbon oil (B) contains paraffinic carbon (BC), the content (number %) of paraffinic carbon (BC) is preferably 50 to 80, more preferably 51 to 78, particularly preferably 53 to 76, and most preferably 54 to 73 based on the total carbon number of the hydrocarbon oil (B). When within this range, the defoaming performance is even better even when stored at low temperatures.

[0021] The contents of aromatic carbon (BA), naphthenic carbon (BB), and paraffin carbon (BC) can be calculated from the density (15°C) and kinematic viscosity (40°C and 100°C) of the measurement sample using the calculation formulas described in the ring analysis (n-d-M) method {ASTM D3238-17a}. The kinematic viscosity is measured in accordance with JIS K2283:2000 "Crude Oil and Petroleum Products - Test Method for Kinematic Viscosity and Method for Calculating Viscosity Index", and the density can be measured in accordance with JIS K2249-1:2011 "Crude Oil and Petroleum Products - Method for Determining Density - Part 1: Vibration Method".

[0022] The kinematic viscosity (mm 2 / s; 40°C) of the hydrocarbon oil (B) is preferably 3 to 146, more preferably 3 to 30, particularly preferably 3.5 to 28, and most preferably 4 to 25. Within this range, the defoaming performance is even better even when stored at low temperatures.

[0023] The hydrocarbon oil (B) is easily available on the market. Examples of the trade names include Cosmo Pure Spin TK, Cosmo Pure Spin G, Cosmo Pure Spin E, Cosmo SP5, Cosmo SP7, and Cosmo Pure Safety 22 (Cosmo Oil Lubricants Co., Ltd., "Cosmo", "Pure Spin", and "Pure Safety" are registered trademarks of Cosmo Energy Holdings Co., Ltd.); and Massimo Supermission, Massimo AT Fluid, and Massimo CVT Fluid (Fuji Kogyo Co., Ltd., "Massimo" is a registered trademark of ENEOS Co., Ltd.). These hydrocarbon oils (B) may be a mixture of two or more.

[0024] The content (% by weight) of the hydrocarbon oil (B) is preferably 40 to 94.8, more preferably 50 to 92, particularly preferably 55 to 90, and most preferably 65 to 85 based on the weights of the aluminum carboxylate (A), hydrocarbon oil (B), polyoxyalkylene compound (C), and mixed ester (D). Within this range, the defoaming performance is even better even when stored at low temperatures.

[0025] <The polyoxyalkylene compound (C) represented by formula (1)> The alkyl or alkenyl group (R1) having 2 to 22 carbon atoms includes alkyl groups (ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, 2-ethylhexyl, capryl, lauryl, myristyl, stearyl, isostearyl, and behenyl, etc.) and alkenyl groups (vinyl, 1-propenyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 5-hexenyl, 1-hexenyl, octenyl, decanyl, oleyl, octadecenyl, and dococenyl, etc.). Of these, alkyl groups are preferred from the viewpoint of defoaming performance after low-temperature storage, more preferably n-propyl, n-butyl, n-pentyl, and n-hexyl, and particularly preferably n-butyl, n-pentyl, and n-hexyl.

[0026] Examples of acyl groups (R2) having 8 to 31 carbon atoms include caproyl, lauroyl, myristiroyl, stearoyl, beheniroyl, lignocerinyl, cerothinyl, and oleiroyl. Of these, lauroyl, myristiroyl, oleiroyl, and stearoyl are preferred from the viewpoint of defoaming performance after low-temperature storage, and more preferably lauroyl, oleiroyl, and stearoyl.

[0027] The oxyalkylene groups (AO) having 2 to 4 carbon atoms include oxyethylene, oxypropylene, oxybutylene, and mixtures thereof. When these are mixtures, i.e., when multiple types of oxyalkylene groups are included, they may be in block form, random form, or a mixture thereof, but random form is preferred. Of these, oxypropylene is preferred.

[0028] n is preferably an integer between 10 and 60, more preferably an integer between 20 and 50, and particularly preferably an integer between 25 and 45. Within this range, the defoaming performance after low-temperature storage is good, and the occurrence of repellency is further suppressed.

[0029] Polyoxyalkylene compounds (C) can be prepared by known methods (such as alkylene oxide addition and esterification reactions to alcohols). Alkylene oxide adducts of alcohols are readily available from the market, for example, under trade names such as Newport LB-385, LB-625, LB-1145, LB-1715, LB-1800X, 50HB-260, 50HB-400 and 50HB-660 (Sanyo Chemical Industries, Ltd., "Newport" is a registered trademark of the company), and Unilube MB-19, MB-38 and MB-370 (NOF Corporation, "Unilube" is a registered trademark of the company). Alkylene oxide adducts of alcohols readily available from the market are compounds in which R2 is a hydrogen atom in formula (1), and these compounds can be converted to compounds in which R2 is an acyl group in formula (1) by esterification reactions.

[0030] The content (by weight) of the polyoxyalkylene compound (C) is preferably 5 to 30, more preferably 6 to 27, particularly preferably 8 to 24, and most preferably 9 to 20, based on the weights of aluminum carboxylate (A), hydrocarbon oil (B), polyoxyalkylene compound (C), and mixed ester (D). Within this range, the defoaming performance after low-temperature storage is good, and the repulsion is further reduced.

[0031] <Mixed ester (D) consisting of polyoxyethylene glycol fatty acid diester and polyoxyethylene glycol fatty acid monoester> The mixed ester (D) consists of a polyoxyethylene glycol fatty acid diester and a polyoxyethylene glycol fatty acid monoester, and can be used without limitation as long as the esterification rate is 50 to 99 (preferably 65 to 99, more preferably 70 to 97) mol%. Within this range, the defoaming performance is further improved even when stored at low temperatures.

[0032] The esterification rate is as follows: 1 The calculation is performed using 1H-NMR. 30 mg of mixed ester (D) was weighed into a 5 mm diameter NMR sample tube, approximately 0.5 ml of deuterated solvent (such as deuterated chloroform) was added to dissolve it, and then approximately 0.1 ml of anhydrous trifluoroacetic acid was added to prepare the sample for analysis. 1 Perform 1H-NMR measurement.

[0033] Here, the unreacted hydroxyl groups in the mixed ester (D) react with trifluoroacetic anhydride to form trifluoroacetic acid ester. The signal originating from the methylene group bonded to the oxygen atom of the esterified hydroxyl group is observed at around 4.5 ppm, while the signal originating from the methylene group bonded to the oxygen atom of the hydroxyl group that reacted with the fatty acid is observed at around 4.2 ppm. Therefore, the esterification rate (mol%) can be calculated from the following equation.

[0034] Esterification rate (mol%) = [b / (a+b)] × 100 However, in the formula, a is the integral value of the signal originating from the methylene group bonded to the oxygen atom esterified with trifluoroacetic acid at around 4.5 ppm; and b is the integral value of the signal originating from the methylene group bonded to the oxygen atom esterified with fatty acid at around 4.2 ppm.

[0035] The number-average molecular weight of polyoxyethylene glycol is preferably 100 to 2000, more preferably 150 to 1500, and particularly preferably 200 to 1000. Within this range, the defoaming properties are even better, even when stored at low temperatures.

[0036] The number-average molecular weight can be determined from the hydroxyl value measured in accordance with JIS K1557-1:2007 (Method B).

[0037] Polyoxyethylene glycol can be obtained by known organic chemical synthesis methods, as well as from the market. For example, it is sold under the trade name PEG series (Sanyo Chemical Industries, Ltd.).

[0038] Fatty acids include saturated and unsaturated fatty acids with 12 to 30 carbon atoms. Examples of saturated fatty acids include straight-chain saturated fatty acids (lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, cerotic acid, and melissic acid, etc.) and branched-chain saturated fatty acids (isostearic acid, etc.).

[0039] Examples of unsaturated fatty acids include straight-chain unsaturated fatty acids (such as myristoleic acid, palmitoleic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, and triaconthenic acid) and branched-chain unsaturated fatty acids (such as isomylistoleic acid and isoleic acid).

[0040] Of these, linear saturated fatty acids and linear unsaturated fatty acids are preferred from the viewpoint of defoaming properties after low-temperature storage, more preferably lauric acid, myristic acid, palmitic acid, stearic acid, myristoleic acid, palmitoleic acid, oleic acid, erucic acid, linoleic acid and linolenic acid, particularly preferably lauric acid, myristic acid, palmitic acid, stearic acid, myristoleic acid, palmitoleic acid, oleic acid, erucic acid, linoleic acid and linolenic acid, and most preferably lauric acid and oleic acid.

[0041] The polyoxyethylene glycol and fatty acids contained in the mixed ester (D) may be a single component or may contain multiple types of fatty acids.

[0042] The mixed ester (D) may contain unreacted polyoxyethylene glycol and / or unreacted fatty acids. The amount of unreacted polyoxyethylene glycol is statistically calculated from the esterification rate, and this amount (weight %) is preferably 0 to 11 based on the weight of the mixed ester (D). The amount of unreacted fatty acids is calculated from the acid value measured in accordance with "3.1 Neutralization Titration" of JIS K0070-1992, and this amount (weight %) is preferably 0 to 10 based on the weight of the mixed ester (D).

[0043] The mixed ester (D) can be prepared by known methods (such as the addition reaction and esterification reaction of alkylene oxide to ethylene glycol or water).

[0044] The content (by weight) of the mixed ester (D) is preferably 0.1 to 15, more preferably 0.5 to 13, particularly preferably 1 to 10, and most preferably 3 to 7, based on the weight of aluminum carboxylate (A), hydrocarbon oil (B), polyoxyalkylene compound (C), and mixed ester (D). Within this range, the defoaming performance after low-temperature storage is good, and the repulsion is further reduced.

[0045] The content (by weight) of the polyoxyalkylene compound (C) is preferably 50 to 85, more preferably 53 to 83, particularly preferably 57 to 80, and most preferably 60 to 77, based on the weight of the polyoxyalkylene compound (C) and the mixed ester (D). Within this range, the defoaming performance is further improved even when stored at low temperatures.

[0046] The content (by weight) of the mixed ester (D) is preferably 15 to 50, more preferably 17 to 47, particularly preferably 20 to 43, and most preferably 23 to 40, based on the weight of the polyoxyalkylene compound (C) and the mixed ester (D). Within this range, the defoaming performance is further improved even when stored at low temperatures.

[0047] The content (by weight) of aluminum carboxylate (A) is preferably 0.4 to 70, more preferably 1 to 60, particularly preferably 10 to 50, and most preferably 15 to 40, based on the total weight of the polyoxyalkylene compound (C) and the mixed ester (D). Within this range, the defoaming performance is further improved even when stored at low temperatures.

[0048] The defoaming agent of the present invention may contain a silicone oil compound (E). The silicone oil compound (E) is a mixture of silicone oil and hydrophilic silica powder, hydrophobic silica powder, etc. Alternatively, the silicone oil compound (E) can be replaced with a hydrophobic powder such as hydrophobic silica that does not contain silicone oil.

[0049] Examples of silicone oil compounds (E) include, under the trade names, SILFOAM SC370 and SILFOAM SC385 (Asahi Kasei Wacker Silicone Co., Ltd., "SILFOAM" is a registered trademark of Wacker Chemie Aktiengesellschaft); KS-66, KS-69, and KS-7716 (Shin-Etsu Chemical Co., Ltd.); and mixtures thereof.

[0050] If a silicone oil compound (E) is included, its content (by weight) is preferably 0.01 to 30, more preferably 0.05 to 25, particularly preferably 0.1 to 20, and most preferably 0.2 to 10, based on the weights of aluminum carboxylate (A), hydrocarbon oil (B), polyoxyalkylene compound (C), and mixed ester (D). Within this range, the defoaming properties are further improved even when stored at low temperatures.

[0051] In addition to aluminum carboxylate (A), hydrocarbon oil (B), polyoxyalkylene compound (C), mixed ester (D), and silicone oil compound (E), other defoaming components (natural wax, synthetic wax, C12-C30 alcohol and C8-C30 fatty acid amide) and product stabilizing components (emulsifiers, thickeners, and preservatives, etc.) may be added to the defoaming agent of the present invention, to the extent that they do not impair the effects of the present invention.

[0052] The defoaming agent of the present invention can be obtained by a method of uniformly mixing aluminum carboxylate (A), hydrocarbon oil (B), a polyoxyalkylene compound represented by formula (1) (C), a mixed ester (D), and optionally a silicone oil compound (E), other defoaming components and / or product stabilizing components. Heating is preferable during uniform mixing. The heating and mixing temperature (°C) is preferably the temperature at which the aluminum carboxylate melts or dissolves, for example, preferably 80 to 190, more preferably 100 to 180, particularly preferably 130 to 170, and most preferably 140 to 160.

[0053] The heating and mixing apparatus is not limited to any apparatus that can heat to the above temperature and mix uniformly, and examples include propeller-type stirrers, dissolvers, homomixers, ball mills, sand mills, ultrasonic dispersers, kneaders, and line mixers. These apparatuses can be used in combination. After heating and mixing, it is preferable to adjust the particle size of aluminum carboxylate (A). Methods for adjusting the particle size include stirring at 5 to 40°C, and the mixture may be cooled to 5 to 40°C in the apparatus where it was heated and mixed.

[0054] The viscosity (mPa·s / 25℃) of the defoaming agent of the present invention is preferably 30 to 2000, more preferably 50 to 1000, and particularly preferably 70 to 500. Within this range, the defoaming performance is even better, even when stored at low temperatures. The viscosity is measured in accordance with JIS Z8803-2011, section 9, Method for measuring viscosity using a single cylindrical rotational viscometer.

[0055] The amount (by weight) of the defoaming agent of the present invention to be added can be appropriately set according to the foaming state, temperature, viscosity, etc. of the liquid to be added, but based on the weight of the liquid to be added, it is preferably 0.0001 to 10, more preferably 0.0005 to 8, particularly preferably 0.001 to 5, and most preferably 0.005 to 3. The addition temperature is preferably around 0 to 100°C, more preferably 10 to 60°C, and particularly preferably 20 to 50°C. [Examples]

[0056] Unless otherwise specified, "parts" refers to parts by weight, and "%" refers to percentage by weight. <Manufacturing Example 1> 100 parts of deionized water, 50 parts of a 50% sodium hydroxide aqueous solution, and 10 parts of the surfactant {Naroacty CL-85 (Sanyo Chemical Industries, Ltd., "Naroacty" is a registered trademark of the company)} were heated to 70°C with stirring. 90 parts (0.6 mol) of octanoic acid were added while stirring, and the mixture was stirred at 70°C for 1 hour. Then, 57.1 parts (0.7 mol) of aluminum hydroxide were added over 1 hour at 70°C, and the mixture was stirred for another 1 hour at 70°C. The resulting mixture was then cooled to 30°C over 1 hour, filtered, washed with water, and dried at 90°C for 6 hours to obtain aluminum carboxylate (a1) {aluminum octanoate}. The content of free octanoic acid (fa1) was 5% based on the weight of aluminum carboxylate (a1).

[0057] The content (by weight) of free fatty acids (FA) {free octanoic acid (fa1)} was obtained as follows (the content of free fatty acids was obtained similarly below). After accurately weighing 2 g of the sample into a 200 mL Erlenmeyer flask, 60 mL of a mixed solution consisting of 40 mL of ethanol and 20 mL of xylene was added. The mixture was stirred for 10 minutes using a stirring bar and a magnetic stirrer, then transferred to a sample bottle. The original Erlenmeyer flask was washed with the ethanol and xylene mixed solution and transferred to the sample bottle. Next, centrifugation was performed using a centrifuge (3,000 rpm x 10 minutes), followed by standing for 10 minutes. The upper layer was drawn out using a dropper and filtered through No. 2 filter paper (Advantec Toyo Co., Ltd.). The original sample bottle was washed with the ethanol and xylene mixed solution, the washing solution was filtered through No. 2 filter paper (Advantec Toyo Co., Ltd.), and the acid value of the filtrate was measured. The acid value was determined in accordance with JIS K0070-1992 3.2 potentiometric titration method. The free fatty acid content (FA) was calculated from the molecular weight of potassium hydroxide, 56.1, using the following formula. Free fatty acid content (FA) = 100 × molecular weight of carboxylic acid (M) × acid value / 56100

[0058] <Manufacturing Example 2> A mixed ester (d1) consisting of PEG(Mn600) oleic acid diester and PEG(Mn600) oleic acid monoester was prepared by dehydrating 600 parts (1 mole) of polyoxyethylene glycol (PEG, number average molecular weight Mn600, PEG-600, Sanyo Chemical Industries, Ltd.) and 564 parts (2 moles) of oleic acid (molecular weight 282) at 130°C for 5 hours in the presence of 0.01 moles of p-toluenesulfonic acid. 1 The esterification rate of the mixed ester (d1) was determined using 1H-NMR spectral analysis (the same method is used hereafter), and it was found to be 95 mol%.

[0059] <Manufacturing Example 3> A mixed ester (d2) consisting of PEG(Mn600) oleic acid diester and PEG(Mn600) oleic acid monoester was obtained in the same manner as in Production Example 2, except that "564 parts (2 moles) of oleic acid" was changed to "415 parts (1.47 moles) of oleic acid". The esterification rate was 70 mol%.

[0060] <Manufacturing Example 4> A mixed ester (d3) of PEG(Mn200) lauric acid diester and PEG(Mn200) lauric acid monoester was obtained in the same manner as in Production Example 2, except that "564 parts (2 moles) of oleic acid" was changed to "401 parts (2 moles) of lauric acid" and "600 parts (1 mole) of polyoxyethylene glycol (Mn600)" was changed to "200 parts (1 mole) of polyoxyethylene glycol (PEG, number average molecular weight Mn200, PEG-200, Sanyo Chemical Industries, Ltd.)". The esterification rate was 97 mol%.

[0061] <Manufacturing Example 5> A mixed ester (d4) of PEG(Mn1000) oleic acid diester and PEG(Mn1000) oleic acid monoester was obtained in the same manner as in Production Example 2, except that "600 parts (1 mole) of polyoxyethylene glycol (Mn600)" was changed to "1000 parts (1 mole) of polyoxyethylene glycol (PEG, number average molecular weight Mn1000, PEG-1000, Sanyo Chemical Industries, Ltd.)". The esterification reaction rate was 94%.

[0062] <Example 1> 805 parts of hydrocarbon oil (b1) {Cosmo Pure Spin G, Cosmo Oil Lubricants Co., Ltd., aromatic carbon (BA) content 10%; naphthenic carbon (BB) content 17%; paraffinic carbon (BC) content 73%} and 40 parts of aluminum carboxylate (a1) {aluminum octanoate} were homogeneously mixed and heated to 135°C. Then, 110 parts of polyoxyalkylene compound (c1) {lauric acid ester of Newport 50HB-660 (Sanyo Chemical Industries, Ltd., n-butyl alcohol ethylene oxide 20 molars, propylene oxide 15 molars, block adduct, chemical structure as described in the company's product catalog issued in 2019)}, 45 parts of mixed ester (d1), and 50 parts of silicone oil compound (e) {SILFOAM SC370, Asahi Kasei Wacker Silicone Co., Ltd.} were added and stirred at 135°C for 1 hour to obtain a mixture. The mixture was then cooled to 20°C over 1 hour while stirring to obtain the defoaming agent (S1) of the present invention.

[0063] <Example 2> The following changes were made: "Hydrogen oil (b1) 805 parts" was changed to "Hydrogen oil (b3) {Cosmo SP5, Cosmo Oil Lubricants Co., Ltd., aromatic carbon (BA) content 17% of units, naphthenic carbon (BB) content 29% of units, paraffinic carbon (BC) content 54% of units} 780 parts"; "Aluminum carboxylate (a1) 40 parts" was changed to "Aluminum carboxylate (a2) {Aluminum stearate, aluminum stearate 600, NOF Corporation, free stearic acid (fa2) content was 10% based on the weight of aluminum stearate (a2)} 30 parts"; "Polyoxyalkylene compound (c1) 110 parts" was changed to "Polyoxyalkylene compound (c2) {Newpol LB-625 (Sanyo Chemical Industries, Ltd., n-butanol propylene oxide 31 molar adduct: the company's "Polyalkylene glycol-based lubricant "Newpol The chemical structure was identified from the information described in the "LB, 50HB" series (polyoxypropylene butyl ether, number average molecular weight 1870). The defoaming agent (S2) of the present invention was obtained in the same manner as in Example 1, except that the amount was changed to "140 parts of stearic acid ester of )", "45 parts of mixed ester (d1)" was changed to "50 parts of mixed ester (d2)", and silicone oil compound (e) was not used.

[0064] <Example 3> The following changes were made: "Hydrogen oil (b1) 805 parts" was changed to "Hydrogen oil (b2) {Cosmo Pure Spin TK, Cosmo Oil Lubricants Co., Ltd.} 360 parts and hydrocarbon oil (b4) {Cosmo SP7, Cosmo Oil Lubricants Co., Ltd.} consisting of hydrocarbon oil {Aromatic carbon (BA) content 14%; naphthenic carbon (BB) content 24%; paraffinic carbon (BC) content 62%}", and "Aluminum carboxylate (a1) 40 parts" was changed to "Aluminum carboxylate (a3) ​​{Aluminum stearate, SA-1500, Sakai Chemical Industry Co., Ltd., free stearic acid". The content of (fa3) was 15% based on the weight of aluminum stearate (a3). Except for changing "80 parts" to "80 parts" to "110 parts of polyoxyalkylene compound (c1)" to "75 parts of polyoxyalkylene compound (c1) and 75 parts of polyoxyalkylene compound (c2)", changing "45 parts of mixed ester (d1)" to "50 parts of mixed ester (d3)", and changing "50 parts of silicone oil compound (e)" to "100 parts of silicone oil compound (e)", the defoaming agent (S3) of the present invention was obtained in the same manner as in Example 1.

[0065] <Example 4> Except for changing "805 parts of hydrocarbon oil (b1)" to "650 parts of hydrocarbon oil (b1)", changing "40 parts of aluminum carboxylate (a1)" to "80 parts of aluminum carboxylate (a4) {aluminum stearate, SA-1000, Sakai Chemical Industry Co., Ltd., the content of free stearic acid (fa4) was 5% based on the weight of aluminum stearate (a4)}", changing "110 parts of polyoxyalkylene compound (c1)" to "100 parts of polyoxyalkylene compound (c1) and 100 parts of polyoxyalkylene compound (c2)", changing "45 parts of mixed ester (d1)" to "70 parts of mixed ester (d4)", and changing "50 parts of silicone oil compound (e)" to "10 parts of silicone oil compound (e)", the defoaming agent (S4) of the present invention was obtained in the same manner as in Example 1.

[0066] <Example 5> Except for changing "805 parts of hydrocarbon oil (b1)" to "500 parts of hydrocarbon oil (b2) and 350 parts of hydrocarbon oil (b4) {aromatic carbon (BA) content 13%; naphthenic carbon (BB) content 23%; paraffinic carbon (BC) content 63%}", changing "40 parts of aluminum carboxylate (a1)" to "10 parts of aluminum carboxylate (a2) and 20 parts of aluminum carboxylate (a4)", changing "110 parts of polyoxyalkylene compound (c1)" to "90 parts of polyoxyalkylene compound (c1)", changing "45 parts of mixed ester (d1)" to "30 parts of mixed ester (d1)", and not using silicone oil compound (e), the defoaming agent (S5) of the present invention was obtained in the same manner as in Example 1.

[0067] <Example 6> Except for changing "805 parts of hydrocarbon oil (b1)" to "hydrocarbon oil consisting of 200 parts of hydrocarbon oil (b2) and 590 parts of hydrocarbon oil (b4) {aromatic carbon (BA) content 14%; naphthenic carbon (BB) content 24%; paraffinic carbon (BC) content 63%}", changing "40 parts of aluminum carboxylate (a1)" to "60 parts of aluminum carboxylate (a1)", changing "110 parts of polyoxyalkylene compound (c1)" to "45 parts of polyoxyalkylene compound (c1) and 45 parts of polyoxyalkylene compound (c2)", changing "45 parts of mixed ester (d1)" to "60 parts of mixed ester (d3)", and not using silicone oil compound (e), the defoaming agent (S6) of the present invention was obtained in the same manner as in Example 1.

[0068] <Example 7> Except for changing "805 parts of hydrocarbon oil (b1)" to "700 parts of hydrocarbon oil (b1)", changing "40 parts of aluminum carboxylate (a1)" to "40 parts of aluminum carboxylate (a3)", changing "110 parts of polyoxyalkylene compound (c1)" to "150 parts of polyoxyalkylene compound (c1) and 50 parts of polyoxyalkylene compound (c2)", changing "45 parts of mixed ester (d1)" to "60 parts of mixed ester (d2)", and changing "50 parts of silicone oil compound (e)" to "2 parts of silicone oil compound (e)", the defoaming agent (S7) of the present invention was obtained in the same manner as in Example 1.

[0069] <Example 8> Except for changing "805 parts of hydrocarbon oil (b1)" to "820 parts of hydrocarbon oil (b1)", changing "40 parts of aluminum carboxylate (a1)" to "50 parts of aluminum carboxylate (a4)", changing "110 parts of polyoxyalkylene compound (c1)" to "100 parts of polyoxyalkylene compound (c2)", changing "45 parts of mixed ester (d1)" to "30 parts of mixed ester (d4)", and not using silicone oil compound (e), the defoaming agent (S8) of the present invention was obtained in the same manner as in Example 1.

[0070] <Example 9> Except for changing "805 parts of hydrocarbon oil (b1)" to "750 parts of hydrocarbon oil (b3)", changing "40 parts of aluminum carboxylate (a1)" to "20 parts of aluminum carboxylate (a1) and 40 parts of aluminum carboxylate (a2)", changing "110 parts of polyoxyalkylene compound (c1)" to "120 parts of polyoxyalkylene compound (c1)", changing "45 parts of mixed ester (d1)" to "35 parts of mixed ester (d1) and 35 parts of mixed ester (d4)", and changing "50 parts of silicone oil compound (e)" to "30 parts of silicone oil compound (e)", the defoaming agent (S9) of the present invention was obtained in the same manner as in Example 1.

[0071] <Comparative Example> A comparative defoaming agent (HS1) was obtained in accordance with Example 1 described in Patent Document 1 (Japanese Unexamined Patent Publication No. 2006-87966).

[0072] <Defoaming performance evaluation 1> Emulsion coatings were prepared using the defoamers S1-S9 and HS1 obtained in Examples 1-9 and Comparative Examples, and evaluated by the following method.

[0073] (1) Preparation of emulsion-based paints Using the raw material composition shown in Table 1, an emulsion-based paint was obtained by grinding and letting down the mixture using an Excel autohomogenizer (Nippon Seiki Co., Ltd., Model ED) equipped with an impeller-type blade.

[0074] [Table 1]

[0075] *1 Thickening agent, Sunopco Co., Ltd. *2 Dispersant, Sunopco Corporation *3 Calcium carbonate, Takehara Chemical Industry Co., Ltd., and "Sunlight" are registered trademarks of Kyoei Sangyo Co., Ltd. *4 Titanium dioxide, Ishihara Sangyo Co., Ltd., and "Typeque" are registered trademarks of the company. *5 Acrylic binder, resin concentration 50%, BASF Japan Ltd., "ACRONAL" is a registered trademark of BASF Societas Europa. *6 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, KH Neochem Co., Ltd., and "Kyowanol" are registered trademarks of the company. *7 Thickening agent, Sunopco Co., Ltd.

[0076] (2) Preparation of emulsion coatings Emulsion paints 1 to 10 were obtained by mixing 99.5 parts of emulsion base paint with 0.5 parts of any of the defoaming agents S1 to S9 and HS1, and stirring the mixture at 2000 rpm for 3 minutes in an Excel autohomogenizer equipped with an impeller-type blade. Emulsion paint 11 (blank) was also obtained using 100 parts of emulsion base paint (without defoaming agent) in the same manner as above.

[0077] (3) Defoaming property After applying a water-based silicone primer sealer (Nippe Home Products Co., Ltd.) to a slate board (3.0 mm thick, cut to 15 x 10 cm) and allowing it to dry, 30 g of one of the emulsion paints 1 to 11 was placed on the slate board and applied with a roller. The board was then dried for one day at 20-25°C and 55-70% RH. The defoaming properties were evaluated by observing the surface of the paint film and counting the number of bubble marks, as shown in Table 3.

[0078] Furthermore, emulsion paints 1 to 11 were stored in sealed containers at 2°C and 40°C for one month, respectively. After that, they were stirred and mixed again at 2000 rpm for 3 minutes using an Excel autohomogenizer equipped with an impeller-type blade, and the defoaming properties were evaluated in the same manner as above, as shown in Table 3.

[0079] <Defoaming performance evaluation 2> Emulsion coatings were prepared using the defoamers S1-S9 and HS1 obtained in Examples 1-9 and Comparative Examples, and evaluated by the following method.

[0080] (1) Preparation of emulsion-based paints Using the raw material composition shown in Table 2, an emulsion-based paint was obtained by grinding and let-down using an Excel autohomogenizer (Nippon Seiki Co., Ltd., Model ED) equipped with an impeller-type blade.

[0081] [Table 2]

[0082] *8 Dispersant, Sunopco Co., Ltd. *9 Antifoaming agent, Sunopco Co., Ltd. *10 Titanium dioxide, Ishihara Sangyo Co., Ltd., and "Typeque" are registered trademarks of Ishihara Sangyo Co., Ltd. *11 Acrylic binder, resin concentration 46±1%, Hengshui Xingguang New Materials Technology Co., Ltd. *12 Color-correcting agent, Sunnopco Corporation, and "Nopcol" are registered trademarks of the company. *13 Flash rust inhibitor, Sunnopco Co., Ltd., "Nopco Checks" is a registered trademark of the company. *14 Thickening agent, Sunopco Co., Ltd.

[0083] (2) Preparation of emulsion coatings Emulsion base paint 99.5 parts and 0.5 parts of any of the defoaming agents S1-S9 and HS1 were mixed and stirred for 3 minutes at 2000 rpm in an Excel autohomogenizer equipped with an impeller-type blade to obtain emulsion paints 12-21. Emulsion paint 22 (blank) was also obtained in the same manner as above using 100 parts of emulsion base paint (without defoaming agent).

[0084] (3) Defoaming property In the same manner as in <Defoaming Performance Evaluation 2>, roller coating was applied to slate boards and emulsion paints 12-22. After drying, the surface of the coating film was observed, and the number of bubble marks was counted to evaluate the defoaming performance, which is shown in Table 3.

[0085] Emulsion paints 12-22 were stored in sealed containers at -5°C and 0°C for one month, respectively. After aging (-5°C) and aging (0°C), they were again stirred and mixed at 2000 rpm for 3 minutes using an Excel autohomogenizer equipped with an impeller-type blade. The defoaming properties were then evaluated in the same manner as above, and the results are shown in Table 3.

[0086] [Table 3]

[0087] As described above, when the comparative defoaming agents (comparative examples) were added to the foaming liquid (paint) and stored at low temperatures (-5°C, 0°C, 2°C), their defoaming performance deteriorated significantly. In contrast, the defoaming agents of the present invention (Examples 1-9) exhibited excellent defoaming performance even when added to the foaming liquid (paint) and stored at low temperatures (-5°C, 0°C, 2°C). [Industrial applicability]

[0088] The defoaming agent of the present invention can be used in all manufacturing and processing processes where foaming problems are a concern, such as the paper and pulp industry, food industry, textile industry, synthetic resin industry, synthetic rubber industry, resin emulsion industry, concrete industry, paint industry, sewage treatment, and wastewater treatment, which use large amounts of water.

Claims

1. It contains aluminum carboxylate (A); aromatic carbon (BA)-containing hydrocarbon oil (B); a polyoxyalkylene compound represented by formula (1) (C); and a mixed ester (D) consisting of polyoxyethylene glycol fatty acid diester and polyoxyethylene glycol fatty acid monoester. An antifoaming agent characterized by having a content of 0.1 to 15% by weight of aluminum carboxylate (A), hydrocarbon oil (B), polyoxyalkylene compound (C), and mixed ester (D), where the content of aluminum carboxylate (A) is 0.1 to 15% by weight, the content of hydrocarbon oil (B) is 40 to 94.8% by weight, the content of polyoxyalkylene compound (C) is 5 to 30% by weight, and the content of mixed ester (D) is 0.1 to 15% by weight, and the content of aromatic carbon (BA) is 1 to 30 percent based on the total number of carbon atoms of hydrocarbon oil (B). R1-(AO)n-OR2 (1) R1 represents an alkyl or alkenyl group having 2 to 22 carbon atoms, R2 represents an acyl group having 8 to 31 carbon atoms, AO represents an oxyalkylene group having 2 to 4 carbon atoms, and n represents an integer from 10 to 60.

2. The defoaming agent according to claim 1, wherein, based on the weight of the polyoxyalkylene compound (C) and the mixed ester (D), the content of the polyoxyalkylene compound (C) is 50 to 85% by weight and the content of the mixed ester (D) is 15 to 50% by weight.

3. The defoaming agent according to claim 1 or 2, wherein the content of aluminum carboxylate (A) is 0.4 to 70% by weight based on the total weight of the polyoxyalkylene compound (C) and the mixed ester (D).

4. The defoaming agent according to claim 1 or 2, wherein free fatty acids (FA) are contained in aluminum carboxylate (A), and the content of free fatty acids (FA) is 1 to 30% by weight based on the weight of aluminum carboxylate (A).

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