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 technology]

[0002] "A defoaming agent containing an aluminum carboxylate (A) and a hydrocarbon oil (B) and not containing an alkaline earth metal carboxylate, wherein (A) is an aluminum dicarboxylate (A2) or a mixture of an aluminum monocarboxylate (A1) and an aluminum dicarboxylate (A2), A defoaming agent, wherein the content of (A) is 0.1 to 60% by weight, 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% by weight or less, based on the total weight of (A1) and (A2). "The defoaming agent according to any one of claims 1 to 3, further comprising a polyoxyalkylene compound (C) represented by general formula (1): [ka] In the general formula (1), R1 represents a hydrogen atom or an organic group having 2 to 22 carbon atoms, R2 represents a hydrogen atom or an acyl group having 8 to 31 carbon atoms, OA represents an oxyalkylene group having 3 to 4 carbon atoms, m represents an integer of 1 to 3, and n represents an integer of 10 to 60" is known (see, for example, claims 1 and 4 of Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2006-87966 Summary of the Invention [Problem to be solved by the invention]

[0004] Conventional defoaming agents have a problem in that when they are added to foaming liquids (paints, inks, etc.) and stored at low temperatures (such as -5 to 0°C), the defoaming performance may decrease. That is, an object of the present invention is to provide a defoaming agent that has excellent defoaming performance even when stored at low temperatures. [Means for solving the problem]

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

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

[0007] 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 of 10 to 60. [Effects of the Invention]

[0008] The defoaming agent of the present invention has excellent defoaming performance even when added to a foaming liquid (paint, ink, etc.) and stored at a low temperature (-5 to 0°C, etc.). DETAILED DESCRIPTION OF THE INVENTION

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

[0010] The carbon number of the carboxylic acid constituting the aluminum monocarboxylate, aluminum dicarboxylate, aluminum tricarboxylate and free fatty acid (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 becomes even better even when stored at low temperatures.

[0011] The carboxylic acid includes aliphatic carboxylic acids and alicyclic carboxylic acids, such as 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) and alicyclic carboxylic acids (cyclopropanecarboxylic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, cyclohexenecarboxylic acid, cycloheptanecarboxylic acid, and cycloheptenecarboxylic acid). Of these, from the viewpoint of defoaming performance and the like, aliphatic carboxylic acids are preferred, and octanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, and docosanoic acid are more preferred, and tetradecanoic acid, hexadecanoic acid, octadecanoic acid, and docosanoic acid are particularly preferred.

[0012] The free fatty acid (FA) may be the same as the carboxylic acid constituting the aluminum carboxylate (A), and the preferred ones are also the same. When a free fatty acid (FA) is contained, it is preferable that the (FA) is the carboxylic acid constituting the aluminum carboxylate (A). The free fatty acid may be a mixture of two or more kinds, and in the case of a mixture, it is preferable that the above-mentioned preferred one is contained as the main component.

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

[0014] The aluminum carboxylate (A) usually contains a free fatty acid (FA), but the free fatty acid (FA) may be added to the aluminum carboxylate (A) so that the content falls within the above-mentioned preferred range.

[0015] Aluminum carboxylates can be produced by known methods (e.g., metathesis method or direct method; Fatty Acid Chemistry, Revised and Enlarged Edition, published by Saiwai Shobo Co., Ltd., August 10, 1970) or are readily available commercially, for example, under trade names such as Aluminum Stearate 300, Aluminum Stearate 600, and Aluminum Stearate 900 (NOF Corporation); Aluminum Stearate (Tannan Chemical Industry Co., Ltd.); Aluminum Stearate (Daikyo Kasei Kogyo Co., Ltd.); and SA-1000, SA-1500, and SA-2000 (Sakai Chemical Industry Co., Ltd.). Aluminum carboxylates are also readily available from reagent manufacturers and the like.

[0016] The defoaming agent of the present invention preferably does not contain an alkaline earth metal carboxylate. The alkaline earth metal carboxylate is composed of a carboxylic acid and an alkaline earth metal. The carboxylic acid is the same as the carboxylic acid constituting the aluminum carboxylate (A). Examples of the alkaline earth metal carboxylate include magnesium dioctadecanoate and calcium monooctadecanoate. If the defoaming agent contains an alkaline earth metal carboxylate, cissing is more likely to occur.

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

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

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

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

[0021] The contents of aromatic carbon (BA), naphthenic carbon (BB), and paraffinic carbon (BC) can be calculated from the density (15°C) and kinematic viscosity (40°C and 100°C) of the measurement sample using the formula described in the ring analysis (ndM) method {ASTM D3238-17a}. Kinematic viscosity is measured in accordance with JIS K2283:2000 "Crude oil and petroleum products - Test method for kinematic viscosity and calculation method for viscosity index," and density can be measured in accordance with JIS K2249-1:2011 "Crude oil and petroleum products - Determination of density - Part 1: Oscillatory method."

[0022] Kinematic viscosity of hydrocarbon oil (B) (mm 2 / s; 40°C) 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 becomes even better even when stored at low temperatures.

[0023] The hydrocarbon oil (B) is readily available on the market, and examples of the product 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 Super Mission, Massimo AT Fluid, and Massimo CVT Fluid (Fuji Kosan Co., Ltd., and "Massimo" is a registered trademark of ENEOS Corporation). These hydrocarbon oils (B) may be a mixture of two or more types.

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

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

[0026] Examples of the acyl group (R2) having 8 to 31 carbon atoms include caproyl, lauroyl, myristyl, stearoyl, behenyloyl, lignocerinyl, serotinyl, and oleiroyl. Among these, from the viewpoint of defoaming performance after low-temperature storage, lauroyl, myristyl, oleiroyl, and stearoyl are preferred, and lauroyl, oleiroyl, and stearoyl are more preferred.

[0027] The oxyalkylene group (AO) having 2 to 4 carbon atoms includes oxyethylene, oxypropylene, oxybutylene, and mixtures thereof. In the case of a mixture of these, i.e., containing multiple types of oxyalkylene groups, the oxyalkylene groups may be block, random, or a mixture of these, but the random type is preferred. Of these, oxypropylene is preferred.

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

[0029] The polyoxyalkylene compound (C) can be prepared by known methods (such as alkylene oxide addition reaction to alcohol and esterification reaction). Alkylene oxide adducts of alcohols are readily available on the market, and examples of such adducts include Newpol LB-385, LB-625, LB-1145, LB-1715, LB-1800X, 50HB-260, 50HB-400, and 50HB-660 (Sanyo Chemical Industries, Ltd., "Newpol" 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). Commercially available alkylene oxide adducts of alcohols are compounds of formula (1) in which R2 is a hydrogen atom, and these compounds can be esterified to produce compounds of formula (1) in which R2 is an acyl group.

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

[0031] <Mixed ester (D) consisting of polyoxyethylene glycol fatty acid diester and polyoxyethylene glycol fatty acid monoester> The mixed ester (D) may be any polyoxyethylene glycol fatty acid diester and polyoxyethylene glycol fatty acid monoester, as long as it has an esterification rate of 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 Calculated by H-NMR method. 30 mg of the mixed ester (D) was weighed into a 5 mm diameter NMR sample tube, and about 0.5 ml of a deuterated solvent (e.g., deuterated chloroform) was added to dissolve it, and then about 0.1 ml of trifluoroacetic anhydride was added to prepare a sample for analysis. 1 Measure H-NMR.

[0033] Here, the unreacted hydroxyl groups contained in the mixed ester (D) react with trifluoroacetic anhydride to form trifluoroacetic esters, and a signal derived from a methylene group bonded to the oxygen atom of the esterified hydroxyl group is observed around 4.5 ppm, while a signal derived from a methylene group bonded to the oxygen atom of the hydroxyl group that has reacted with the fatty acid is observed around 4.2 ppm. Therefore, the esterification rate (mol %) is calculated using the following formula:

[0034] Esterification rate (mol%) = [b / (a+b)] × 100 In the formula, a is the integral of the signal derived from a methylene group bonded to an oxygen atom esterified with trifluoroacetic acid at around 4.5 ppm; and b is the integral of the signal derived from a methylene group bonded to an oxygen atom esterified with a 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 further improved 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, or can be obtained commercially, for example, under the trade name PEG series (Sanyo Chemical Industries, Ltd.).

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

[0039] Unsaturated fatty acids include straight-chain unsaturated fatty acids (such as myristoleic acid, palmitoleic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, and triacontenoic acid) and branched-chain unsaturated fatty acids (such as isomyristoleic acid and isooleic acid).

[0040] Of these, from the viewpoint of defoaming properties after low-temperature storage, straight-chain saturated fatty acids and straight-chain unsaturated fatty acids are preferred, 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 acid 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 acid. The amount of unreacted polyoxyethylene glycol is statistically calculated from the esterification rate, and this amount (wt%) is preferably 0 to 11 based on the weight of the mixed ester (D). The amount of unreacted fatty acid is calculated from the acid value measured in accordance with "3.1 Neutralization Titration" of JIS K0070-1992, and this amount (wt%) 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 (addition reaction of alkylene oxide to ethylene glycol or water, esterification reaction, etc.).

[0044] The content (wt %) of the mixed ester (D) based on the weight of the aluminum carboxylate (A), the hydrocarbon oil (B), the polyoxyalkylene compound (C), and 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. Within this range, the defoaming performance after low-temperature storage is improved and repelling is further reduced.

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

[0046] The content (wt %) of the mixed ester (D) based on the weight of the polyoxyalkylene compound (C) and 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. Within this range, the defoaming performance becomes even better even when stored at low temperatures.

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

[0048] The antifoaming agent of the present invention may contain a silicone oil compound (E). The silicone oil compound (E) is a mixture of silicone oil with hydrophilic powdered silica or hydrophobic powdered silica, etc. Instead of the silicone oil compound (E), a hydrophobic powder such as hydrophobic silica that does not contain silicone oil can also be contained.

[0049] Examples of the silicone oil compound (E) include trade names such as SILFOAM SC370 and SILFOAM SC385 (Wacker Asahi Kasei Silicones 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] When the silicone oil compound (E) is contained, the content (wt %) based on the weight of the aluminum carboxylate (A), the hydrocarbon oil (B), the polyoxyalkylene compound (C), and the mixed ester (D) 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. Within this range, the defoaming properties are further improved even when stored at low temperatures.

[0051] In addition to the aluminum carboxylate (A), the hydrocarbon oil (B), the polyoxyalkylene compound (C), the mixed ester (D), and the silicone oil compound (E), the defoaming agent of the present invention may contain other defoaming components (natural waxes, synthetic waxes, alcohols having 12 to 30 carbon atoms, and fatty acid amides having 8 to 30 carbon atoms) and product stabilizing components (emulsifying agents, thickening components, preservatives, etc.) within the range that does not impair the effects of the present invention.

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

[0053] The heating and mixing device is not limited as long as it can be heated to the above temperature and can perform uniform mixing, and examples thereof include a propeller-type agitator, a dissolver, a homomixer, a ball mill, a sand mill, an ultrasonic disperser, a kneader, and a line mixer. These devices can be used in combination. After heating and mixing, it is preferable to adjust the particle size of the aluminum carboxylate (A). The particle size can be adjusted by stirring at 5 to 40°C, or the device used for heating and mixing can be cooled to 5 to 40°C.

[0054] The viscosity (mPa·s / 25°C) 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 further improved even when stored at low temperatures. The viscosity is measured in accordance with JIS Z8803-2011, Section 9. Viscosity measurement method using a single cylindrical rotational viscometer.

[0055] The amount (wt %) of the antifoaming agent of the present invention to be added may be appropriately determined depending on the foaming state, temperature, viscosity, etc. of the liquid to which it is added, and 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, based on the weight of the liquid to which it is added. The addition temperature is preferably about 0 to 100°C, more preferably 10 to 60°C, and particularly preferably 20 to 50°C. [Example]

[0056] Unless otherwise specified, "parts" below means "parts by weight" and "%" means "% by weight." <Production Example 1> 100 parts of ion-exchanged water, 50 parts of a 50% aqueous sodium hydroxide solution, and 10 parts of a surfactant (Naroacty CL-85 (Sanyo Chemical Industries, Ltd., "Naroacty" is a registered trademark of the company)) were heated to 70°C with stirring, and 90 parts (0.6 mol) of octanoic acid was added with stirring. The mixture was then stirred at 70°C for 1 hour, followed by the addition of 57.1 parts (0.7 mol) of aluminum hydroxide at 70°C over 1 hour and further stirring at 70°C for 1 hour. 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 free octanoic acid (Fa1) content was 5% based on the weight of the aluminum carboxylate (A1).

[0057] The content (wt %) of free fatty acid (FA) {free octanoic acid (fa1)} was obtained as follows (the content of free fatty acid was obtained in the same manner below). Two grams of sample was weighed into a 200 mL Erlenmeyer flask, and 60 mL of a mixed solution consisting of 40 mL of ethanol and 20 mL of xylene was added. After stirring for 10 minutes using a stir bar and magnetic stirrer, the mixture was transferred to a sample bottle. The original Erlenmeyer flask was then washed with the ethanol and xylene mixed solution and transferred to a sample bottle. The mixture was then centrifuged (3,000 rpm x 10 minutes) using a centrifuge, allowed to stand for 10 minutes, and the upper layer was removed 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, and the washings were filtered through No. 2 filter paper (Advantec Toyo Co., Ltd.). The acid value of the filtrate was measured. The acid value was measured according to JIS K0070-1992, section 3.2, potentiometric titration. The free fatty acid content (FA) was calculated using the following formula, based on the molecular weight of potassium hydroxide (56.1): Free fatty acid content (FA) = 100 x molecular weight of carboxylic acid (M) x acid value / 56100

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

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

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

[0061] <Production Example 5> A mixed ester (d4) of oleic acid diester of PEG (Mn1000) and oleic acid monoester of PEG (Mn1000) was obtained in the same manner as in Production Example 2, except that 600 parts (1 part by mole) of polyoxyethylene glycol (Mn600) was replaced with 1000 parts (1 part by 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 a hydrocarbon oil (b1) {Cosmo Pure Spin G, Cosmo Oil Lubricants Co., Ltd., aromatic carbon (BA) content 10% by number, naphthenic carbon (BB) content 17% by number, paraffinic carbon (BC) content 73% by number} and 40 parts of an aluminum carboxylate (a1) {aluminum octanoate} were uniformly mixed and heated to 135°C. Then, 110 parts of a polyoxyalkylene compound (c1) {lauric acid ester of Newpol 50HB-660 (Sanyo Chemical Industries, Ltd., n-butyl alcohol ethylene oxide 20 moles propylene oxide 15 moles block adduct, the chemical structure of which is listed in the product list published by the company in 2019)}, 45 parts of a mixed ester (d1), and 50 parts of a silicone oil compound (e) {SILFOAM SC370, Wacker Asahi Kasei Silicones Co., Ltd.} were added and stirred at 135°C for 1 hour to obtain a mixture. Thereafter, the mixture was cooled to 20°C over 1 hour with stirring to obtain a defoaming agent (S1) of the present invention.

[0063] <Example 2> The following changes were made: "805 parts of hydrocarbon oil (b1)" was changed to "780 parts of hydrocarbon oil (b3) {Cosmo SP5, Cosmo Oil Lubricants Co., Ltd., aromatic carbon (BA) content 17% by number, naphthenic carbon (BB) content 29% by number, paraffinic carbon (BC) content 54% by number}"; "40 parts of aluminum carboxylate (a1)" was changed to "30 parts of aluminum carboxylate (a2) {aluminum stearate, aluminum stearate 600, NOF Corporation, the content of free stearic acid (fa2) was 10% based on the weight of the aluminum stearate (a2)}"; "110 parts of polyoxyalkylene compound (c1)" was changed to "polyoxyalkylene compound (c2) {Newpol LB-625 (Sanyo Chemical Industries, Ltd., n-butanol propylene oxide 31 mol adduct: the same as the company's polyalkylene glycol-based lubricant, Newpol The chemical structure was identified from the content described in the "LB, 50HB" series (polyoxypropylene butyl ether, number average molecular weight 1,870). A defoaming agent (S2) of the present invention was obtained in the same manner as in Example 1, except that the "mixed ester (d1)" was changed to "140 parts of stearic acid ester of (d1)}," "45 parts of mixed ester (d1)" was changed to "50 parts of mixed ester (d2)," and the silicone oil compound (e) was not used.

[0064] Example 3 "805 parts of hydrocarbon oil (b1)" was changed to "hydrocarbon oil consisting of 360 parts of hydrocarbon oil (b2) {Cosmo Pure Spin TK, Cosmo Oil Lubricants Co., Ltd.} and 360 parts of hydrocarbon oil (b4) {Cosmo SP7, Cosmo Oil Lubricants Co., Ltd.} {aromatic carbon (BA) content 14% by number, naphthenic carbon (BB) content 24% by number, paraffinic carbon (BC) content 62% by number}"; and "40 parts of aluminum carboxylate (a1)" 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). A defoaming agent (S3) of the present invention was obtained in the same manner as in Example 1, except that "80 parts of the polyoxyalkylene compound (c1)" was changed to "110 parts of the polyoxyalkylene compound (c1)" and "75 parts of the polyoxyalkylene compound (c1) and 75 parts of the polyoxyalkylene compound (c2)," "45 parts of the mixed ester (d1)" was changed to "50 parts of the mixed ester (d3)," and "50 parts of the silicone oil compound (e)" was changed to "100 parts of the silicone oil compound (e)."

[0065] Example 4 A defoaming agent (S4) of the present invention was obtained in the same manner as in Example 1, except that "805 parts of hydrocarbon oil (b1)" was changed to "650 parts of hydrocarbon oil (b1)," "40 parts of aluminum carboxylate (a1)" was changed 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 the aluminum stearate (a4)}," "110 parts of polyoxyalkylene compound (c1)" was changed to "100 parts of polyoxyalkylene compound (c1) and 100 parts of polyoxyalkylene compound (c2)," "45 parts of mixed ester (d1)" was changed to "70 parts of mixed ester (d4)," and "50 parts of silicone oil compound (e)" was changed to "10 parts of silicone oil compound (e)."

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

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

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

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

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

[0071] <Comparative Example> A comparative antifoaming agent (HS1) was obtained in accordance with Example 1 described in Patent Document 1 (JP-A-2006-87966).

[0072] <Anti-foaming evaluation 1> Emulsion paints were prepared as follows using the defoamers S1 to S9 and HS1 obtained in Examples 1 to 9 and Comparative Example, and were evaluated by the following methods.

[0073] (1) Preparation of emulsion-based paint The raw material composition shown in Table 1 was subjected to grinding and letdown using an Excel Auto Homogenizer (Nippon Seiki Co., Ltd., Model ED) equipped with an impeller blade to obtain an emulsion-based paint.

[0074] [Table 1]

[0075] *1 Thickener, San Nopco Ltd. *2 Dispersant, San Nopco Ltd. *3 Calcium carbonate, Takehara Chemical Industry Co., Ltd., and "Sunlight" are registered trademarks of Kyoei Sangyo Co., Ltd. *4 Titanium oxide and Ishihara Sangyo Kaisha, Ltd., and "Tipake" are registered trademarks of the company. *5 Acrylic binder, resin concentration 50%, BASF Japan Ltd., "ACRONAL" is a registered trademark of BASF Societas Europea. *6 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, KH Neochem Co., Ltd. "Kyowanol" is a registered trademark of the company. *7 Thickener, San Nopco Ltd.

[0076] (2) Preparation of emulsion paint 99.5 parts of emulsion base paint and 0.5 parts of any of antifoaming agents S1 to S9 and HS1 were mixed and stirred for 3 minutes at 2000 rpm in an Excel Auto Homogenizer equipped with an impeller blade to obtain emulsion paints 1 to 10. Emulsion paint 11 (blank) was also obtained in the same manner as above using 100 parts of emulsion base paint (no antifoaming agent).

[0077] (3) Defoaming property A slate board (3.0 mm thick, cut to 15 x 10 cm) was painted with a clear water-based silicone primer sealer (Nippe Home Products Co., Ltd.) and then dried. 30 g of any of emulsion paints 1 to 11 was then placed on the slate board and applied with a roller. The slate board was then dried at 20-25°C and 55-70% RH for one day, and the coating surface was observed. The number of bubbles was counted to evaluate the defoaming properties. The results are shown in Table 3.

[0078] Furthermore, emulsion paints 1 to 11 were each stored in a sealed container at 2°C and 40°C for one month (after aging (2°C) and after aging (40°C)), and then again stirred and mixed at 2000 rpm for three minutes using an Excel Auto Homogenizer 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.

[0079] <Anti-foaming evaluation 2> Emulsion paints were prepared as follows using the defoamers S1 to S9 and HS1 obtained in Examples 1 to 9 and Comparative Example, and were evaluated by the following methods.

[0080] (1) Preparation of emulsion-based paint The raw material composition shown in Table 2 was subjected to grinding and letdown using an Excel Auto Homogenizer (Nippon Seiki Co., Ltd., Model ED) equipped with an impeller blade to obtain an emulsion-based paint.

[0081] [Table 2]

[0082] *8 Dispersant, San Nopco Ltd. *9 Antifoaming agent, San Nopco Ltd. *10 Titanium dioxide, Ishihara Sangyo Kaisha, Ltd., and "Tipake" are registered trademarks of Ishihara Sangyo Kaisha, Ltd. *11 Acrylic binder, resin concentration 46±1%, Hengshui Shinko New Materials Technology Co., Ltd. *12 Tone improver, San Nopco Ltd., "Nopcol" is a registered trademark of the company. *13 Flash rust prevention agent, San Nopco Ltd., and Nopco Checks are registered trademarks of the company. *14 Thickener, San Nopco Ltd.

[0083] (2) Preparation of emulsion paint 99.5 parts of emulsion base paint and 0.5 parts of any of antifoaming agents S1 to S9 and HS1 were mixed and stirred for 3 minutes at 2000 rpm in an Excel Auto Homogenizer equipped with an impeller blade to obtain emulsion paints 12 to 21. Emulsion paint 22 (blank) was also obtained in the same manner as above using 100 parts of emulsion base paint (no antifoaming agent).

[0084] (3) Defoaming property In the same manner as in <Evaluation of defoaming property 2>, the slate board and emulsion paints 12 to 22 were used to apply roller coating, and after drying, the coating surface was observed and the number of bubble marks was counted to evaluate the defoaming property. The results are shown in Table 3.

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

[0086] [Table 3]

[0087] As described above, the defoaming performance of the comparative defoaming agents (Comparative Examples) deteriorated significantly when they were added to a foaming liquid (paint) and stored at low temperatures (-5°C, 0°C, 2°C), whereas the defoaming performance of the defoaming agents of the present invention (Examples 1 to 9) was excellent even when they were added to a 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 production and treatment processes where foaming problems become a problem, such as production and treatment processes that use large amounts of water, 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.

Claims

1. The present invention relates to a composition comprising an aluminum carboxylate (A); an aromatic carbon (BA)-containing hydrocarbon oil (B); a polyoxyalkylene compound (C) represented by formula (1); and a mixed ester (D) consisting of a polyoxyethylene glycol fatty acid diester and a polyoxyethylene glycol fatty acid monoester, A defoaming agent characterized in that, based on the weights of the aluminum carboxylate (A), the hydrocarbon oil (B), the polyoxyalkylene compound (C), and the mixed ester (D), the content of the aluminum carboxylate (A) is 0.1 to 15% by weight, the content of the hydrocarbon oil (B) is 40 to 94.8% by weight, the content of the polyoxyalkylene compound (C) is 5 to 30% by weight, and the content of the mixed ester (D) is 0.1 to 15% by weight, and the content of aromatic carbon (BA) is 1 to 30% by number based on the total number of carbon atoms in the 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 of 10 to 60.

2. 2. The defoaming agent according to claim 1, wherein 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, based on the weights of the polyalkylene compound (C) and the mixed ester (D).

3. 3. The defoaming agent according to claim 1, wherein the content of the 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. 3. The defoaming agent according to claim 1 or 2, wherein the aluminum carboxylate (A) contains a free fatty acid (FA), and the content of the free fatty acid (FA) is 1 to 30% by weight based on the weight of the aluminum carboxylate (A).

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