JP6627040B2 - Defoamer - Google Patents

Description

  The present invention relates to an antifoaming agent.

  Conventionally, "as essential components, 100 parts by weight of a polyether polyol having a molecular weight of 2,000 to 8,000, 5 to 100 parts by weight of a mineral oil, 5 to 60 parts by weight of an amine having an aliphatic group having 8 to 22 carbon atoms and 5 carbon atoms A synthetic rubber containing 1 to 30 parts by weight of a higher fatty acid of 8 to 22; an antifoaming agent for latex industry "(Patent Document 1); and a" silicone oil composition comprising silicone and a surfactant (the surfactant is A nonionic surfactant comprising an alkyl chain and a polyoxyalkylene chain, wherein the alkyl chain has 12 to 20 carbon atoms, and the polyoxyalkylene chain has 1 to 100 oxyethylene units and 3 to 10 carbon atoms. And the number of oxyethylene units is at least the number of oxyalkylene units having 3 to 10 carbon atoms.) Patent Document 2) are known.

JP-A-53-23888 JP 2005-298689 A

  However, the defoaming agent described in Patent Document 1 has a problem that the defoaming property is poor. In addition, the antifoaming agent described in Patent Document 2 has a problem that repelling is generated due to a silicone component and the appearance of a coating film is significantly impaired. That is, an object of the present invention is to provide an antifoaming agent which is excellent in suppressing cissing and defoaming.

The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention. That is, the feature of the antifoaming agent for a water-based coating material of the present invention is that it contains the compound (A) represented by the general formula (1) and the hydrocarbon oil (B).

R (OA) _n- OH (1)

In the general formula (1), R represents an alkyl group, alkenyl group or aryl group having 12 to 30 carbon atoms, OA represents an oxyalkylene group having 3 to 4 carbon atoms, OH represents a hydroxy group, and n represents an integer of 12 to 30. .

  The feature of the water-based coating composition of the present invention is that it comprises a water-based coating material and the above-described antifoaming agent.

  The antifoaming agent of the present invention suppresses cissing and exhibits excellent antifoaming properties.

  Since the water-based coating composition of the present invention contains the above-described antifoaming agent, cissing is suppressed and excellent antifoaming properties are exhibited. Therefore, a coating film obtained by applying the water-based coating composition of the present invention does not impair the appearance due to residual foam marks or the like.

It is the perspective view which showed typically the defoaming test device for evaluating defoaming property in an Example.

  In the general formula (1), among the alkyl group, alkenyl group and aryl group (R) having 12 to 30 carbon atoms, examples of the alkyl group include dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, hexacosyl, octakosyl and Triacontyl and the like. Examples of the alkenyl group include dodecenyl, tetradecenyl and octadecenyl. Examples of the aryl group include 4-heptylphenyl, 4-octylphenyl, 4-nonylphenyl, and 9-phenylnonyl. These alkyl group and alkenyl group (including the alkyl group included in the aryl group) may be linear or branched. Among these, from the viewpoint of defoaming properties, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, hexacosyl, octakosyl, triacontyl, tetradecenyl, octadecenyl and 4-nonylphenyl are preferred, and hexadecyl, octadecyl, eicosyl and docosyl are more preferred. , Tetracosyl, hexacosyl, tetradecenyl, octadecenyl, particularly preferably hexadecyl, octadecyl, eicosyl, docosyl and tetracosyl.

  The oxyalkylene group (OA) having 3 to 4 carbon atoms includes oxypropylene and oxybutylene. Among these, oxypropylene and a mixture of oxypropylene and oxybutylene are preferred from the viewpoint of defoaming properties and suppression of repellency.

  When a plurality of types of oxyalkylene groups are contained in the oxyalkylene group (OA), the order of binding (block-like, random-like and combinations thereof) and the content of these oxyalkylene groups are not limited, but may be block-like or block-like. A combination of a shape and a random shape is preferred, and a block shape is more preferred.

  When a plurality of types of oxyalkylene groups are contained in the oxyalkylene group (OA), the content ratio (mol%) of oxypropylene is preferably from 50 to 99, based on the total number of moles of the oxyalkylene group (OA). Preferably it is 70-90. In this case, the content ratio (mol%) of oxybutylene is preferably 1 to 50, and more preferably 10 to 30, based on the total number of moles of the oxyalkylene group (OA).

  n is preferably an integer of 10 to 100, more preferably an integer of 12 to 30. Within this range, the defoaming property and the suppression of cissing are further improved.

  The compound (A) represented by the general formula (1) can be easily obtained by a known method (such as an alkylene oxide addition reaction). That is, the compound (A) can be easily obtained by a chemical reaction between an alcohol and an alkylene oxide having 3 to 4 carbon atoms.

  Examples of the alcohol include natural alcohols having 12 to 30 carbon atoms and synthetic alcohols.

  Natural alcohols include saturated alcohols (such as lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, eicosanol, docosanol, tetracosanol, hexacosanol, octacosanol, and myricyl alcohol) and unsaturated alcohols (such as oleyl alcohol). Can be Examples of the synthetic alcohol include a linear, non-branched saturated alcohol synthesized by the Ziegler method, a linear primary or branched primary alcohol synthesized by the oxo method, and an alcohol mixture having a different number of carbon atoms, and Linear secondary alcohols formed by air oxidation of paraffin are exemplified. Among these, from the viewpoint of defoaming properties, natural alcohols and synthetic alcohols having 14 to 30 carbon atoms are preferable, more preferably natural alcohols and / or synthetic alcohols having 16 to 28 carbon atoms, and most preferably carbon alcohols having 16 to 28 carbon atoms. 16 to 24 synthetic alcohols.

  The alkylene oxide having 3 to 4 carbon atoms includes propylene oxide and butylene oxide. Among these, propylene oxide and a mixture of propylene oxide and butylene oxide are preferred from the viewpoints of defoaming properties and suppression of repellency.

In the chemical reaction between the alcohol and the oxyalkylene, a reaction catalyst may be used.
Examples of the reaction catalyst include hydroxides of alkali metals or alkaline earth metals (such as potassium hydroxide, rubidium hydroxide and cesium hydroxide), alcoholates of alkali metals (such as potassium methylate and cesium ethylate), alkali metals and alkalis. Earth metal carbonates (such as potassium carbonate, cesium carbonate and barium carbonate), tertiary amines having 3 to 24 carbon atoms (such as trimethylamine, trioctylamine, triethylenediamine and tetramethylethylenediamine) and Lewis acids (secondary chloride) Tin and boron trifluoride). Of these, alkali metal hydroxides and tertiary amines are preferred, and potassium hydroxide, cesium hydroxide and trimethylamine are more preferred.

  When a reaction catalyst is used, the amount (% by weight) based on the weight of the alcohol and the oxyalkylene is preferably from 0.01 to 2, more preferably from 0.05 to 1, and particularly preferably from 0.1 to 1. 0.6.

  As the reaction vessel, it is preferable to use a pressure-resistant reaction vessel capable of stirring, heating, cooling, dropping, replacing with nitrogen, pressurizing with nitrogen, and depressurizing with a vacuum pump. The reaction atmosphere is preferably an atmosphere of a vacuum or dried inert gas (argon, nitrogen, carbon dioxide, or the like) in the reactor.

  When a reaction catalyst is used, it is preferable to remove the reaction catalyst from the reaction product, and the removal method may be an alkali adsorbent {synthetic aluminosilicate or the like; KYOWARD (registered trademark) 600, 700, Kyowa Chemical Industry Co., Ltd.} (JP-A-53-123499, etc.), a method of dissolving in a solvent such as xylene or toluene and washing with water (JP-B-49-14359, etc.), and a method of using an ion-exchange resin (JP-A-51-143). No. 23211) and a method of filtering carbonate generated by neutralizing an alkaline catalyst with carbon dioxide (Japanese Patent Publication No. 52-33000).

The hydrocarbon oil (B) includes mineral oil, animal and vegetable oil, and synthetic lubricating oil.
Mineral oils include spindle oil, machine oil, and refrigeration oil. Animal and vegetable oils include fish oil, rapeseed oil, soybean oil, sunflower seed oil, cottonseed oil, peanut oil, rice bran oil, corn oil, safflower oil, olive oil, sesame oil, evening primrose oil, palm oil, shea butter, monkey fat, cocoa butter, Palm oil and palm kernel oil; Examples of the synthetic lubricating oil include polyolefin oil (α-olefin oil), polyglycol oil, polybutene oil, alkylbenzene oil (alkylate oil), and isoparaffin oil.

The hydrocarbon oil (B) preferably contains a mineral oil and / or a synthetic lubricating oil, and more preferably has a kinematic viscosity (mm ² / s; 40 ° C.) of 0.5 to 30 (preferably 0.8 to 27). , And more preferably 1 to 25) mineral oil and / or synthetic lubricating oil.

Mineral oils, animal and vegetable oils and synthetic lubricating oils are easily available from the market. As mineral oils and synthetic lubricating oils, Cosmo SC22 (21 mm ² / s), Cosmo SP10 (10 mm ² / s), Cosmo RC spindle oil ( 10 mm ² / s), Cosmo RB spindle oil (15 mm ² / s), Cosmo Neutral 150 (32 mm ² / s), Cosmo Pure Spin G (21 mm ² / s) and Cosmo Pure Spin E (5 mm ² / s) (Cosmo Petroleum Lubricant Co., Ltd., “Cosmo” is a registered trademark of Cosmo Oil Co., Ltd.); Nisseki Super Oil C (93 mm ² / s), Nisseki Super Oil D (141 mm ² / s) and Nisseki Super Oil B (54 mm ² / s) (Nippon Oil Corporation); Stanol 43N (27 mm ² / s), Stanol 52 (56 mm ² / s), stanol 69 (145 mm ² / s), stanol 35 (9 mm ² / s) and stanol LP35 (11 mm ² / s) (Esso Oil Co., Ltd.); and Fuchor SH spin (9 mm ² / s); Fukkor NT100 (21 mm ² / s), Fukkor NT150 (28 mm ² / s), Fukkor NT200 (39 mm ² / s), Fukkor NT60 (10 mm ² / s), and Fukkor ST machine (9 mm ² / s) (Fujikosan Co., Ltd.) , "Fucall" is a registered trademark of Nippon Oil Co., Ltd.) (The numbers in parentheses indicate "kinematic viscosity (40 ° C)"). Oil LR-1, Fine Oil ISB-12 (Miyoshi Oil & Fat Co., Ltd.) and the like.

  The content (% by weight) of the compound (A) represented by the general formula (1) is 5 to 5 based on the weight of the compound (A) represented by the general formula (1) and the hydrocarbon oil (B). It is preferably 80, more preferably 10 to 75, particularly preferably 20 to 60. The content (% by weight) of the hydrocarbon oil (B) is preferably 20 to 95 based on the weight of the compound (A) represented by the general formula (1) and the hydrocarbon oil (B). It is preferably from 25 to 90, particularly preferably from 40 to 80. Within this range, the defoaming property and the suppression of cissing are further improved.

  The production method of the antifoaming agent of the present invention is not limited as long as it contains the compound (A) represented by the general formula (1) and the hydrocarbon oil (B). it can.

The antifoaming agent of the present invention may further contain a hydrophobic compound (C) selected from hydrophobic silica, amide, wax or metal soap.
The hydrophobic silica (C1) includes hydrophobic silica obtained by subjecting amorphous synthetic silica to a hydrophobic treatment with a hydrophobizing agent.

  Examples of the amorphous synthetic silica include wet method (precipitation method, gel method) silica and gas phase method (pyrolysis method, fusion method) silica. In addition, since amorphous synthetic silica has a silanol group on the particle surface, it shows hydrophilicity.

Amorphous synthetic silica can be easily obtained from the market, and examples thereof include the following products.
<Precipitation silica>
Nipsil Series @ Tosoh Silica Corporation, "Nipsil" is a registered trademark of Tosoh Silica Corporation. ｝, Sipernat Series ｛Evonik Degussa Japan Co., Ltd., “Sipernat” is a registered trademark of Evonik Degussa Gamembeher. ｝, Carplex series ｛DSL. Japan Inc., "Carplex" is DSL. It is a registered trademark of Japan Corporation. Ｆ, FINESIL series ｛Tokuyama Corporation, “FINESIL” is a registered trademark of Tokuyama Corporation. ｝, TOKUSIL ｛Tokuyama Corporation, “TOKUSIL” is a registered trademark of Tokuyama Corporation. ｝, Zeosil ｛Rhodia, “Zeosil” is a registered trademark of Rhodia Simi. ｝, MIZUKASIL Series ｛Mizusawa Chemical Industry Co., Ltd., “MIZUKASIL” is a registered trademark of Mizusawa Chemical Industry Co., Ltd. }etc.

<Gel method silica>
Carplex series, SYLYSIA series @ Fuji Silysia Ltd., "SYLYSIA" is a registered trademark of YK F. ｝, Nipgel series ｛Tosoh Silica Corporation, “Nipgel” is a registered trademark of Tosoh Silica Corporation. ｝, MIZUKASIL Series ｛Mizusawa Chemical Industry Co., Ltd., “MIZUKASIL” is a registered trademark of Mizusawa Chemical Industry Co., Ltd. }etc.

<Fused silica>
Admafine Series @ Admatex Co., Ltd., "Admafine" is a registered trademark of Admatex Co., Ltd. ｝, Fuselex series 龍 Tatsumori ｛, Denka fused silica series ｛Denki Kagaku Kogyo KK, etc.

<Pyrogenic silica>
Aerosil series @ Nippon Aerosil Co., Ltd. and Evonik Degussa, Inc., "Aerosil" is a registered trademark of Evonik Degussa GmbH. ｝, Reolosil Series ｛Tokuyama Corporation, “Reorosil” is a registered trademark of Tokuyama Corporation. ｝, Cab-O-Sil Series ｛Cabot Corporation, “Cab-O-Sil” is a registered trademark of Cabot Corporation. }etc.

  Examples of the hydrophobizing agent include halosilanes, alkoxysilanes, fatty acids having 4 to 28 carbon atoms, aliphatic alcohols having 4 to 36 carbon atoms, aliphatic amines having 12 to 22 carbon atoms, and silicone compounds.

  Examples of the halosilane include an alkylhalosilane and an arylhalosilane having an alkyl group or an aryl group having 1 to 12 carbon atoms, such as methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, trimethylbromosilane, ethyltrichlorosilane, and dodecyltrichlorosilane. Phenyltrichlorosilane, diphenyldichlorosilane and t-butyldimethylchlorosilane.

  Examples of the alkoxysilane include an alkoxysilane having an alkyl group or an aryl group having 1 to 12 carbon atoms and an alkoxy group having 1 to 2 carbon atoms, such as methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, and diphenyldimethoxysilane. Silane, o-methylphenyltrimethoxysilane, p-methylphenyltrimethoxysilane, n-butyltrimethoxysilane, i-butyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxy Silane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, i-butyltriethoxysilane, decyltriethoxysilane, Cycloalkenyl triethoxysilane and γ- methacryloxypropyl trimethoxy silane, and the like.

  Examples of the fatty acid having 4 to 28 carbon atoms include butanoic acid, hexanoic acid, lauric acid, stearic acid, oleic acid, behenic acid and montanic acid.

  Examples of the aliphatic alcohol having 4 to 36 carbon atoms include n-butyl alcohol, n-amyl alcohol, n-octanol, lauryl alcohol, stearyl alcohol, and behenyl alcohol.

  Examples of the aliphatic amine having 12 to 22 carbon atoms include dodecylamine, stearylamine, and oleylamine.

  Examples of the silicone compound include dimethyl polysiloxane, aryl-modified polysiloxane (aryl group having 6 to 10 carbon atoms), alkyl-modified polysiloxane (alkyl group having 2 to 6 carbon atoms), hydroxyl-modified polysiloxane, amino-modified polysiloxane, Tricyclic to pentameric cyclic silicone, methyl hydrogen polysiloxane, silicone resin and the like can be mentioned.

As the dimethylpolysiloxane, those having a kinematic viscosity (25 ° C.) of 1 to 500,000 mm ² / s can be used.

As the aryl-modified polysiloxane and the alkyl-modified polysiloxane, those having a kinematic viscosity (25 ° C.) of 1 to 10,000 mm ² / s can be used.

  Hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and the like can be used as the tri- to pentamer cyclic silicone.

Examples of the hydroxyl group-modified polysiloxane, amino group-modified polysiloxane and methyl hydrogen polysiloxane include those having a kinematic viscosity (25 ° C.) of 1 to 10,000 mm ² / s and a functional group equivalent of 300 to 8,000 g / mol. Can be used.

As the silicone resin, an MQ resin composed of an arbitrary combination of a triorganosiloxy unit (M unit) and a siloxy unit (Q unit) can be used.
Further, it is preferable to use the silicone resin in the form of a solution in which the silicone resin is dissolved in a cyclic silicone or a low-viscosity chain silicone.

  As the hydrophobizing agent used in the hydrophobizing treatment, other than the above, known coupling agents (such as silane coupling agents, titanate coupling agents, and zircoaluminate coupling agents other than those described above) and the like can also be used.

  Of these hydrophobizing agents, halosilanes, alkoxysilanes, and silicone compounds are preferred, and silicone compounds are more preferred, and dimethylpolysiloxane, methylhydrogenpolysiloxane, and silicone resins are more preferred.

  As the hydrophobizing treatment of the amorphous synthetic silica with the hydrophobizing agent, a known method can be applied. For example, while the mixture of the hydrophobizing agent and the amorphous synthetic silica is stirred, the hydrophobizing agent is synthesized by the amorphous synthesizing. A dry method in which the surface of silica is adsorbed or reacted to make the surface hydrophobic is applicable.

  When the hydrophobizing treatment is performed using a hydrophobizing agent, the amount (% by weight) of the hydrophobizing agent is preferably 1 to 50, more preferably 3 to 40, and particularly preferably, based on the weight of the amorphous synthetic silica. Is 5 to 30. Within this range, the defoaming property is further improved.

  The methanol wettability (M value) of the hydrophobic silica (C1) is preferably 50 to 85, more preferably 55 to 80, and particularly preferably 60 to 75. Within this range, the defoaming property is further improved.

  The M value is a concept representing the degree of hydrophobicity, and the higher the M value, the lower the hydrophilicity. When the hydrophobic fine particles are uniformly dispersed in a water / methanol mixed solution, the volume ratio of the necessary minimum amount of methanol is measured. It can be obtained by the following method.

<M value calculation method>
0.2 g of the measurement sample (silica particles) is added to 50 mL of water in a 250 mL beaker, and then methanol is added dropwise from the burette until the entire amount of the silica particles is suspended. At this time, the solution in the beaker is constantly stirred with a magnetic stirrer, and the time when the entire amount of the measurement sample (silica particles) is uniformly suspended in the solution is defined as the end point, and the volume percentage of methanol of the liquid mixture in the beaker at the end point is determined by the M value. It becomes. That is, (the volume of dropped methanol) × 100 ° (the volume of dropped methanol) + 50 ° is calculated as the M value.

  The volume average particle size (μm) of the hydrophobic silica particles (C1) is preferably 1 to 20, more preferably 1.5 to 15, and particularly preferably 2 to 11. Within this range, the defoaming property is further improved.

  The volume average particle diameter can be determined by dispersing a measurement sample in an appropriate dispersion medium (for example, water, methanol, or a mixture thereof), and measuring the particle size according to JIS Z8825: 2013 “Particle size analysis-Laser diffraction / scattering method”. (For example, SALD-1100 manufactured by Shimadzu Corporation, LA-950 manufactured by Horiba, and Micro manufactured by Nikkiso Co., Ltd.) having the measurement principle described in (corresponding ISO: ISO13320: 2009). "Microtrack" is a registered trademark of Leeds, And, Northlap, Company, etc., such as a truck particle size distribution measuring device UPA-ST150).

  The hydrophobic silica particles (C1) can be easily obtained from the market, and examples thereof include the following products.

<Silica particles obtained by hydrophobizing precipitated silica>
Nipsil SS series (SS-10, SS-40, SS-50, SS-115, etc.) @ Tosoh Silica Corporation, "Nipsil" is a registered trademark of Tosoh Silica Corporation. )｝, Sipernat D and C series (D10, D17, C600 and C630 etc.) ｛Degussa Japan Co., Ltd. and SYLOPHOBIC series (100, 702, 505 and 603 etc.) ｛Fuji Silysia Chemical Co., Ltd., “SYLOPHOBIC” is Fuji It is a registered trademark of Silysia Chemical Ltd. }etc.

<Silica particles obtained by hydrophobizing pyrogenic silica>
Aerosil series (R972, RX200, RY200, R202, R805 and R812, etc.) {Nippon Aerosil Co., Ltd. and Evonik Degussa Co., Ltd.}, Reolosil MT and DM series (MT-10, DM-10, DM-20, etc.) >> Tokuyama Corporation {(TS-530TS-610TS-720 etc.)} {Cabot Carbon Co.}

  Examples of the amide (C2) include a reaction product of a C1 to C6 alkylenediamine or an alkenylenediamine with a C10 to C22 fatty acid (fatty acid diamide) and / or a C1 to C22 alkylamine, alkenylamine or ammonia. And a fatty acid having 10 to 22 carbon atoms (fatty acid monoamide).

  Fatty acid diamides include ethylene bisstearyl amide, ethylene bis palmitylamide, ethylene bis myristyl amide, ethylene bis lauryl amide, ethylene bis oleyl amide, propylene bis stearyl amide, propylene bis palmityl amide, propylene bis myristyl amide, propylene bis lauryl Amide, propylene bisoleylamide, butylene bisstearylamide, butylene bispalmitylamide, butylene bismyristylamide, butylene bis lauryl amide, butylene bis oleyl amide, methylene bis lauryl amide, methylene bis stearyl amide, hexamethylene bis stearyl amide and the like No.

  Examples of the fatty acid monoamide include N-stearylstearylamide, oleic amide, erucamide, and stearylamide.

  Among these, from the viewpoint of defoaming properties and the like, fatty acid diamides are preferred, and ethylene bisstearyl amide, ethylene bis palmitylamide, ethylene bis lauryl amide, methylene bis stearyl amide and hexamethylene bis stearyl amide are particularly preferred. Ethylenebisstearylamide, ethylenebispalmitylamide and ethylenebismyristylamide. These amides may be a mixture of two or more kinds, and in the case of a mixture, it is preferable that the above-mentioned preferable one is contained as a main component.

  The main component means a component containing at least 40% by weight based on the weight of the fatty acid amide, preferably 50% by weight or more, more preferably 60% by weight or more, particularly preferably 70% by weight or more. Most preferably, the content is 80% by weight or more.

  As the subcomponents (components other than the main components) in the fatty acid amide, unreacted amines, unreacted carboxylic acids, and the like are included in addition to the amides outside the preferred ranges described above. The content (% by weight) of the minor component is preferably less than 60, more preferably less than 50, particularly preferably less than 40, then more preferably less than 30, most preferably less than 20, based on the weight of the fatty acid amide. .

  The wax (C3) preferably contains at least one selected from the group consisting of oxidized polyethylene wax, microcrystalline wax, hydroxyl group-containing wax, paraffin wax and natural wax, and includes oxidized polyethylene wax, microcrystalline wax, paraffin wax, Examples include alcohol-modified wax, maleic acid-modified wax, ethylene-vinyl acetate copolymer wax, ethylene-acrylic acid copolymer wax, Fischer-Tropsch wax, wood wax, beeswax, palm wax, carnauba wax, montan wax and the like.

  Examples of the metal soap (C4) include salts of fatty acids having 12 to 22 carbon atoms and metals (alkaline earth metals, aluminum, manganese, cobalt, copper, iron, zinc, nickel, etc.), aluminum stearate, stearic acid Manganese, cobalt stearate, copper stearate, iron stearate, nickel stearate, calcium stearate, zinc laurate, magnesium behenate and the like are included.

  Regarding the metal soap, the quantity relationship between the metal and the fatty acid may be any of 1 to 3 moles of the fatty acid (mono-form, di-form, tri-form) with respect to 1 mole of the metal. It may be a mixture. From the viewpoint of defoaming properties and the like, when the metal is aluminum and iron, the di- and tri-forms are preferable, and when the metal is alkaline earth metal (such as calcium), zinc, cobalt, manganese, nickel and copper, the di-form is preferable.

  The hydrophobic compound (C) may be one kind or a mixture of two or more kinds.

  When the hydrophobic compound (C) is contained, the content (% by weight) of the hydrophobic compound (C) is based on the weight of the compound (A) represented by the general formula (1) and the hydrocarbon oil (B). The number is preferably 2 to 30, more preferably 4 to 25, and particularly preferably 5 to 20. Within this range, the defoaming property and the suppression of cissing are further improved.

The antifoaming agent of the present invention can further contain a polyoxyalkylene compound (D) other than the compound (A) represented by the general formula (1).
The polyoxyalkylene compound (D) is not limited as long as it is a polyoxyalkylene compound other than the compound (A) represented by the general formula (1), but is represented by the same general formula as the general formula (1). Compound: wherein R is an alkyl or alkenyl group having 1 to 10 carbon atoms, OA is an oxyalkylene group having 2 to 4 carbon atoms, OH is a hydroxy group, and n is an integer of 10 to 100. ｝, Polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxypropylene glycol, fatty acid ester of polyoxyalkylene alkyl ether, fatty acid ester of polyoxyethylene glycol, alkylene oxide of glycerin Examples include adducts, sorbitan fatty acid esters, polyoxyethylene polyoxypropylene block polymers, fatty acid esters of polyoxyethylene polyoxypropylene block polymers, ethylene oxide adducts of vegetable oils, glycerin fatty acid esters, and silicones modified with polyoxyalkylene chains.

  Among these, from the viewpoint of defoaming properties, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxypropylene glycol, fatty acid ester of polyoxyalkylene alkyl ether, fatty acid ester of polyoxyethylene glycol, glycerin Alkylene oxide adducts, sorbitan fatty acid esters, polyoxyethylene polyoxypropylene block polymers, fatty acid esters of polyoxyethylene polyoxypropylene block polymers, ethylene oxide adducts of vegetable oils, and polyoxyalkylene chain-modified silicones are preferred.

  When the polyoxyalkylene compound (D) is contained, the content (% by weight) of the polyoxyalkylene compound (D) is based on the weight of the compound (A) represented by the general formula (1) and the hydrocarbon oil (B). Is preferably from 2 to 400, more preferably from 5 to 300, and particularly preferably from 65 to 200. Within this range, the defoaming property and the suppression of cissing are further improved.

  The antifoaming agent of the present invention may further contain water, a thickener, a dispersant, a preservative, a film-forming regulator, an antifreezing agent and / or a solvent.

  Examples of the thickener include xanthan gum, locust bean gum, guar gum, carrageenan, alginic acid and salts thereof, tragacanth gum, magnesium aluminum silicate, bentonite, synthetic hydrated silicic acid, and a synthetic polymer type thickener containing a carboxyl group (trade name; For example, SN thickener 636, SN thickener 641; San Nopco Co., Ltd.), an association thickener containing a polyoxyethylene chain (for example, SN thickener 625N, SN thickener 665T; San Nopco Co., Ltd.) and the like can be mentioned.

  Examples of the dispersant include polyacrylic acid (salt), partially saponified polyvinyl alcohol, and sulfated polyvinyl alcohol.

  As the preservative, known preservatives (Bactericidal and Fungicide Dictionary, published by the Japan Society of Antimicrobial and Fungicide, 1st Edition, 1986, pp. 1-32) can be used, and formalin and 5-chloro-2 can be used. -Methyl-4-isothiazolin-3-one and the like.

  Examples of the film-forming modifier include Texanol (trade name, manufactured by Eastman Chemical Co., Ltd .; “Texanol” is a registered trademark of Yoshimura Oil Chemical Co., Ltd.).

  Examples of the antifreeze include ethylene glycol, propylene glycol, glycerin and the like.

  As the solvent, known solvents (Solvent Handbook, published by Kodansha 1979, pp. 143-881) and the like can be used, and examples thereof include butyl cellosolve, propylene glycol monopropyl ether, and 1-butanol.

  The production method of the antifoaming agent of the present invention is not limited as long as it is uniformly mixed, and a known mixing method can be applied.

  The antifoaming agent of the present invention may be used as it is, may be used after being diluted with a solvent, water, an aqueous solution, or the like, or may be used after being supported on a powder such as silica or calcium carbonate.

  The antifoaming agent of the present invention includes an antifoaming agent for paints, an antifoaming agent for cement building materials (concrete, mortar, plaster, etc.) and various manufacturing processes (papermaking process, fermentation process, wastewater treatment process, monomer stripping process, polymer Polymerization step, etc.) It can be applied as an antifoaming agent. Among them, it is suitable as an antifoaming agent for paints and an antifoaming agent for building materials, and is also suitable as an antifoaming agent for water-based coating materials.

  Suitable water-based coating materials include coating materials containing an acrylic binder, a vinyl acetate binder, a styrene binder, a halogenated olefin binder, a urethane binder, an acryl-silicone binder or a fluorine binder.

  When the antifoaming agent of the present invention is applied to a paint, the antifoaming agent of the present invention may be added (1) at the time of dispersing the pigment and / or (2) after the preparation of the paint. When applied to various manufacturing processes, the antifoaming agent of the present invention is added to (1) the supply of raw materials, (2) before heating and / or depressurizing treatment, and / or (3) the final finishing process and the like. Any method may be used.

  The amount of the antifoaming agent of the present invention can be appropriately determined depending on the application object, application, and the like.For example, when the antifoaming agent of the present invention is used as an antifoaming agent for a water-based coating material, The content (% by weight) is preferably from 0.05 to 5, more preferably from 0.1 to 4.5, particularly preferably from 0.2 to 4, most preferably from 0.2 to 4, based on the weight of the aqueous coating material. 3 to 3. Within this range, the defoaming property and the suppression of cissing are further improved.

  The water-based coating material to which the antifoaming agent of the present invention has been added can be applied to an object to be coated by a usual method, such as brush coating, roller coating, air spray coating, airless coating, roll coater coating, and flow coater coating. Although a coating method and the like can be applied, the effect is particularly remarkable in brush coating and roller coating.

  Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. Unless otherwise specified, parts mean parts by weight and% means% by weight.

<Production Example 1>
In a pressure-resistant reaction vessel capable of stirring, heating, cooling, dropping, replacing with nitrogen, pressurizing with nitrogen, and depressurizing with a vacuum pump, calcol 8098 {Kao Corporation, stearyl alcohol (98% or more)} 270 parts (1 mol part) And 5 parts of potassium hydroxide, and then dehydrated at 120 ° C. under a reduced pressure of 0.6 to 1.3 kPa for 2 hours. Next, 1160 parts (20 mol parts) of propylene oxide (PO) were added dropwise at 120 ° C. over 12 hours while maintaining the reduced pressure, and stirring was further continued at 120 ° C. for 2 hours to react the remaining (PO). Next, the reaction catalyst is removed by a method using an alkali adsorbent {synthetic aluminosilicate; KYOWARD (registered trademark) 600, Kyowa Chemical Industry Co., Ltd.} (JP-A-53-123499, etc.). Processing ". The compound (A1) was obtained.

<Production Example 2>
"Calcol 8098 270 parts (1 mol part)" to "Calcol 220-80 Kao Corporation, mixed alcohol of behenyl alcohol (80% or more) and stearyl alcohol (7% or less) @ 321 parts (1 mol part)" Except having changed, it carried out similarly to manufacture example 1, and obtained compound (A2).

<Production Example 3>
"CALCOL 8098 270 parts (1 mol part)" was converted to "NAFOL 1822B @ SASOL Co., Ltd., a mixed alcohol having 16 to 24 carbon atoms (1% or less of alcohol having 24 carbon atoms, 69% of alcohol having 22 carbon atoms, and 20% of alcohol having 20 carbon atoms). 15% alcohol, 15% alcohol with 18 carbon atoms, 1% or less alcohol with 16 carbon atoms), the same "NAFOL" is manufactured except that it has been changed to its registered trademark "316 parts (1 mol part)" Compound (A3) was obtained in the same manner as in Example 1.

<Production Example 4>
"Calcol 8098 270 parts (1 mol part)" was changed to "NAFOL 1822B 316 parts (1 mol part)", and "propylene oxide (PO) 1160 parts (20 mol parts)" was changed to "propylene oxide (PO) Compound (A4) was obtained in the same manner as in Production Example 1 except that 870 parts (15 mol parts) was used.

<Production Example 5>
"Calcol 8098 270 parts (1 mol part)" was changed to "NAFOL 1822B 316 parts (1 mol part)", and "propylene oxide (PO) 1160 parts (20 mol parts)" was changed to "propylene oxide (PO) Compound (A5) was obtained in the same manner as in Production Example 1 except that "1740 parts (30 mol parts)" was changed.

<Production Example 6>
"Calcol 8098 270 parts (1 mol part)" was changed to "NAFOL 1822B 316 parts (1 mol part)", and "propylene oxide (PO) 1160 parts (20 mol parts)" was changed to "propylene oxide (PO) Compound (A6) was obtained in the same manner as in Production Example 1, except that 1160 parts (20 mol parts) and butylene oxide (BO) 360 parts (5 mol parts) were used.

<Production Example 7>
"Calcol 8098 270 parts (1 mol part)" was changed to "Calcol 6098 @ Kao Corporation, cetyl alcohol (98% or more) @ 242 parts (1 mol part)", and "Propylene oxide (PO) 1160 parts Compound (A7) was obtained in the same manner as in Production Example 1 except that “(20 mol parts)” was changed to “696 parts (12 mol parts) of propylene oxide (PO)”.

<Production Example 8>
In a vessel that can be heated, stirred, and cooled, hydrocarbon oil (B1) ｛Cosmo SC22, Cosmo Oil Lubricant Co., Ltd. 949 parts, hydrophobic silica (C11) ｛SIPERNAT D10, Degussa Japan Co., Ltd., volume average particle size The temperature was raised to 120 ° C. while heating and stirring 10.8 μm, M value 65｝ 51 parts, and further heating and stirring was continued at this temperature for 3 hours, and then cooled to about 25 ° C. to obtain hydrophobic silica (C11). (BC11) was obtained.

<Production Example 9>
In a vessel capable of heating, stirring and cooling, hydrocarbon oil (B1) ｛Cosmo SC22, Cosmo Oil Lubricant Co., Ltd. 800 parts, hydrophobic silica (C11) ｛SIPERNAT D10, Degussa Japan KK, volume average particle size The temperature was raised to 120 ° C. while heating and stirring 10.8 μm, M value of 65 to 200 parts, and the mixture was further heated and stirred at this temperature for 3 hours, and then cooled to about 25 ° C. to obtain hydrophobic silica (C12). (BC12) was obtained.

<Production Example 10>
In a vessel that can be heated, stirred and cooled, the hydrocarbon oil (B1) Cosmo SC22, Cosmo Oil Lubricant Co., Ltd. 800 parts, hydrophobic silica (C12) Nipseal SS-15, Tosoh Silica Co., Ltd., volume The temperature was raised to 120 ° C. while heating and stirring an average particle diameter of 10.1 μm and an M value of 60 to 200 parts. The mixture was further heated and stirred at this temperature for 3 hours, and then cooled to about 25 ° C. to obtain a hydrophobic silica. A dispersion (BC13) containing (C12) was obtained.

<Production Example 11>
In a container capable of heating, stirring and cooling, amorphous synthetic silica (Nipsil G300, Tosoh Silica Co., Ltd., 770 parts, hydrophobizing agent, BY 11-908, Toray Dow Corning Co., Ltd., silicone resin, 230) The portion was heated to 220 ° C. while heating and stirring, and further heated and stirred at this temperature for 5 hours to obtain hydrophobic silica (C13). The volume average particle diameter of the hydrophobic silica (C13) was 10.0 μm, and the M value was 75.

  Then, in a container capable of heating, stirring and cooling, 800 parts of hydrocarbon oil (B1) (Cosmo SC22, Cosmo Oil Lubricant Co., Ltd.) and 200 parts of hydrophobic silica (C13) are heated and stirred to 120 ° C. After heating and stirring at this temperature for another 3 hours, the mixture was cooled to about 25 ° C. to obtain a dispersion (BC14) containing hydrophobic silica (C13).

<Production Example 12>
In a vessel that can be heated, stirred and cooled, amorphous synthetic silica (Nipsil G300, Tosoh Silica Co., Ltd., 770 parts, hydrophobizing agent, SH200-50CS, Toray Dow Corning Co., Ltd., dimethyl silicone oil, 230) The portion was heated to 220 ° C. while heating and stirring, and further heated and stirred at this temperature for 5 hours to obtain hydrophobic silica (C14). The volume average particle diameter of the hydrophobic silica (C14) was 10.0 μm, and the M value was 65.

  Then, in a container capable of heating, stirring and cooling, the hydrocarbon oil (B1) (Cosmo SC22, Cosmo Oil Lubricant Co., Ltd.) (800 parts) and hydrophobic silica (C14) (200 parts) were heated to 120 ° C. while heating and stirring. After heating and stirring at this temperature for another 3 hours, the mixture was cooled to about 25 ° C. to obtain a dispersion (BC15) containing hydrophobic silica (C14).

<Production Example 13>
Using a bead mill, the dispersion (BC15) obtained in <Production Example 12> was stirred at 25 to 40 ° C for 1 hour to obtain a dispersion (BC16) containing hydrophobic silica (C15). The volume average particle diameter of the hydrophobic silica (C15) was 2 μm, and the M value was 65.

<Production Example 14>
Amide (C21) (Alflo H-50S, NOF Corporation, ethylene bisstearyl amide (20 parts and polyoxyalkylene compound (D1)) Newpole PP-2000, Sanyo Kasei in a vessel capable of heating, stirring and cooling. Industry Co., Ltd., heated to 145 ° C. while heating and mixing polyoxypropylene glycol, number average molecular weight 2,000 to 480 parts, and further heated and stirred at this temperature for another 15 minutes to obtain a hydrophobic compound solution (CD21). Obtained.

  Subsequently, while cooling and stirring 500 parts of the polyoxyalkylene compound (D1) adjusted to 25 ° C., a hydrophobic compound solution (CD21) at 145 ° C. was added thereto little by little, and the mixture (CD21) was stirred for 15 minutes. Got. The temperature of the mixture (CD21) during and after the introduction of the hydrophobic compound solution was 25 to 70 ° C.

  The mixture (CD21) was homogenized at 3500 psi (24.1 MPa) using a Gaulin homogenizer (manton-Gaulin) to obtain a hydrophobic compound mixture (CD21).

<Example 1>
20 parts of the compound (A3) obtained in Production Example 3 and 80 parts of the hydrocarbon oil (B2) {Cosmo Pure Spin E, Cosmo Oil Lubricant Co., Ltd.} at 25 ° C, an Excel auto homogenizer equipped with an impeller-type blade { The mixture was stirred for 15 minutes using Nippon Seiki Co., Ltd., Model ED} to obtain an antifoaming agent (DF1) of the present invention.

<Example 2>
60 parts of the compound (A7) obtained in Production Example 7 and 40 parts of the hydrocarbon oil (B2) {Cosmo Pure Spin E, Cosmo Oil Lubricant Co., Ltd.} at 25 ° C, an Excel auto-homogenizer equipped with an impeller-type blade { The mixture was stirred for 15 minutes using Nippon Seiki Co., Ltd., Model ED} to obtain an antifoaming agent (DF2) of the present invention.

<Example 3>
It contains 5 parts of the compound (A2) obtained in Production Example 2 and 100.1 parts of the dispersion (BC11) obtained in Production Example 8/95 parts of the hydrocarbon oil (B1). ｝ Was stirred at 25 ° C. for 15 minutes using an Excel auto-homogenizer {Nippon Seiki Co., Ltd., Model ED} equipped with impeller type blades to obtain an antifoaming agent (DF3) of the present invention.

<Example 4>
It contains 20 parts of the compound (A3) obtained in Production Example 3 and 100 parts of the dispersion (BC12) obtained in Production Example 9/80 parts of the hydrocarbon oil (B1). ｝ Was stirred at 25 ° C. for 15 minutes using an Excel auto-homogenizer {Nippon Seiki Co., Ltd., Model ED} equipped with impeller type blades to obtain an antifoaming agent (DF4) of the present invention.

<Example 5>
18.4 parts of the compound (A6) obtained in Production Example 6, hydrocarbon oil (B2) {Cosmo Pure Spin E, Cosmo Oil Lubricant Co., Ltd.} 81.6 parts and polyoxyalkylene compound (D2) {Ionnet DO-600 , Sanyo Kasei Kogyo Co., Ltd., a diester of polyoxyethylene glycol having a number average molecular weight of 600 and oleic acid｝ 2 parts at 25 ° C., an Excel auto homogenizer equipped with impeller type blades {Nippon Seiki Co., Ltd., Model ED And stirred for 15 minutes to obtain the antifoaming agent (DF5) of the present invention.

<Example 6>
75 parts of compound (A5) obtained in Production Example 5, hydrocarbon oil (B2) {Cosmo Pure Spin E, Cosmo Oil Lubricant Co., Ltd.} 25 parts and polyoxyalkylene compound (D3) Newpole PE-61, Sanyo Chemical Industrial Co., Ltd., polyoxyethylene (5 mol) polyoxypropylene (30 mol) block polymer (5 parts) at 25 ° C. Excel auto homogenizer equipped with impeller type blades (Nippon Seiki Co., Ltd., Model ED) And stirred for 15 minutes to obtain an antifoaming agent (DF6) of the present invention.

<Example 7>
60 parts of compound (A4) obtained in Production Example 4, hydrocarbon oil (B2) {Cosmo Pure Spin E, Cosmo Oil Lubricant Co., Ltd.} 40 parts and polyoxyalkylene compound (D1) Newpole PP-2000, Sanyo Chemical Industrial Co., Ltd., polyoxypropylene glycol, 2000-400 parts of number average molecular weight was stirred at 25 ° C. for 15 minutes using an Excel autohomogenizer {Nippon Seiki Co., Ltd., Model ED} equipped with impeller type blades. Thus, an antifoaming agent (DF7) of the present invention was obtained.

<Example 8>
43.7 parts of compound (A1) obtained in Production Example 1, hydrocarbon oil (B1) {Cosmo SC22, Cosmo Oil Lubricant Co., Ltd.} 48.1 parts, dispersion (BC12) 10.2 obtained in Production Example 9 Part ｛Includes 8.2 parts of hydrocarbon oil (B1). {And polyoxyalkylene compound (D1)} Newpole PP-2000, Sanyo Kasei Kogyo Co., Ltd., polyoxypropylene glycol, number average molecular weight 2,000 (189.5 parts) at 25 ° C, Excel equipped with an impeller type blade The mixture was stirred for 15 minutes using an auto-homogenizer {Nippon Seiki Co., Ltd., Model ED} to obtain an antifoaming agent (DF8) of the present invention.

<Example 9>
45.6 parts of compound (A3) obtained in Production Example 3, hydrocarbon oil (B1) {Cosmo SC22, Cosmo Oil Lubricant Co., Ltd.} 23.4 parts, dispersion liquid (BC13) obtained in Production Example 10 38.8 Parts ｛Including 31 parts of hydrocarbon oil (B1). {155.3 parts of hydrophobic compound mixture (CD21) obtained in Production Example 14} 152.2 parts of polyoxyalkylene compound (D1). {And polyoxyalkylene compound (D4)} Newpole GP-3000, Sanyo Kasei Kogyo Co., Ltd., propylene oxide 50 mol adduct of glycerin} 47.5 parts at 25 ° C., Excel Auto equipped with impeller type blade The mixture was stirred for 15 minutes using a homogenizer (Nippon Seiki Co., Ltd., Model ED) to obtain an antifoaming agent (DF9) of the present invention.

<Example 10>
45.6 parts of compound (A4) obtained in Production Example 4, hydrocarbon oil (B1) {Cosmo SC22, Cosmo Oil Lubricant Co., Ltd.} 23.4 parts, dispersion liquid (BC14) obtained in Production Example 11 38.8. Parts ｛Including 31 parts of hydrocarbon oil (B1). {155.3 parts of hydrophobic compound mixture (CD21) obtained in Production Example 14} 152.2 parts of polyoxyalkylene compound (D1). ｝ And polyoxyalkylene compound (D4) ｛Newpole GP-3000, Sanyo Chemical Industries, Ltd.｝ 47.5 parts, Excel autohomogenizer equipped with impeller-type blades at 25 ° C. {Model of Nippon Seiki Co., Ltd. The mixture was stirred for 15 minutes using ED} to obtain an antifoaming agent (DF10) of the present invention.

<Example 11>
10.1 parts of the compound (A5) obtained in Production Example 5, hydrocarbon oil (B1) (Cosmo SC22, 44.9 parts of Cosmo Oil Lubricant Co., Ltd.), and 56.2 dispersion liquid (BC15) obtained in Production Example 12. Parts ｛Including 45 parts of hydrocarbon oil (B1). {56.2 parts of hydrophobic compound mixture (CD21) obtained in Production Example 14} 55 parts of polyoxyalkylene compound (D1). {And polyoxyalkylene compound (D5)} Newpole LB-3000, Sanyo Kasei Kogyo Co., Ltd., adduct of 45 mol of propylene oxide with butanol {57.3 parts at 25 ° C., Excel Auto equipped with impeller-type blades The mixture was stirred for 15 minutes using a homogenizer {Nippon Seiki Co., Ltd., Model ED} to obtain an antifoaming agent (DF11) of the present invention.

<Example 12>
22.3 parts of compound (A3) obtained in Production Example 3, hydrocarbon oil (B1) {Cosmo SC22, Cosmo Oil Lubricant Co., Ltd.} 33.3 parts, dispersion (BC16) 55.6 obtained in Production Example 13 Parts ｛Including 44.5 parts of hydrocarbon oil (B1). {55.6 parts of the hydrophobic compound mixture (CD21) obtained in Production Example 14} contains 54.5 parts of the polyoxyalkylene compound (D1). ｝, Polyoxyalkylene compound (D2) ネ ッ ト Ionnet DO-600, Sanyo Chemical Industry Co., Ltd., diester of polyoxyethylene glycol having a number average molecular weight of 600 with oleic acid｝ 11.1 parts and film forming regulator ｛texanol, yeast 44.4 parts of Man Chemical Co., Ltd. were stirred at 25 ° C. for 15 minutes using an Excel Auto Homogenizer {Nippon Seiki Co., Ltd., Model ED} equipped with impeller type blades, and the antifoaming agent of the present invention ( DF12) was obtained.

<Example 13>
It contains 42.9 parts of the compound (A5) obtained in Production Example 5, 71.4 parts of the dispersion (BC16) obtained in Production Example 13 and 57.1 parts of the hydrocarbon oil (B1). {And 171.4 parts of the hydrophobic compound mixture (CD21) obtained in Production Example 14} {containing 168 parts of the polyoxyalkylene compound (D1)} were added at 25 ° C to an Excel auto homogenizer equipped with impeller-type blades { The mixture was stirred for 15 minutes using Nippon Seiki Co., Ltd., Model ED} to obtain an antifoaming agent (DF13) of the present invention.

<Comparative Example 1>
An antifoaming agent (H1) for comparison was obtained in the same manner as in Example 1, except that "the compound (A3) obtained in Production Example 3" was changed to "polyoxyalkylene compound (D1)".

<Comparative Example 2>
Based on the description in Example 1 of Patent Document 1, polyoxypropylene glyceryl ether {Newpol GP-3000, Sanyo Chemical Industries, Ltd., propylene oxide 50 mol adduct of glycerin} 70 parts, spindle oil Cosmo Pure Spin E (Cosmo Oil Lubricant Co., Ltd.) 10 parts and oleic acid (6 parts) were mixed and heated to a temperature of 65 ° C., and then 14 parts of distearylamine was added and stirred for 15 minutes to give a defoaming agent for comparison. (H2) was obtained.

<Comparative Example 3>
The hydrocarbon oil (B1) was used as it was as a defoamer (H3) for comparison.

<Comparative Example 4>
An antifoaming agent (H4) for comparison was obtained in the same manner as in Example 4, except that the "compound (A3) obtained in Production Example 3" was changed to "polyoxyalkylene compound (D2)".

<Comparative Example 5>
An antifoaming agent for comparison (H5) was obtained in the same manner as in Example 11, except that “the compound (A3) obtained in Production Example 3” was changed to “polyoxyalkylene compound (D2)”.

<Comparative Example 6>
In accordance with the description of Example 1 of Patent Document 2, silicone AK350, Asahi Kasei Wacker Silicone Co., Ltd., polydimethylsiloxane having a kinematic viscosity of 350 mm ² / s 35 parts of surfactant NIKKOL PBC-33, Nikko Chemicals Co., Ltd., polyoxypropylene (4 mol) polyoxyethylene (10 mol) glycol monohexadecyl ether (4 parts) and ion exchange water (61 parts) are added and uniformly mixed and emulsified to prepare a silicone emulsion mold for comparison. A foaming agent (H6) was obtained.

<Defoaming test 1>
After putting 500 ml of a defoaming test solution (factory drainage from a paper mill) into a glass transparent container (10, height 25 cm, diameter 8 cm) of the defoaming test device (FIG. 1), While the test liquid is discharged from the bottom (12) of the transparent glass container at a rate of 1300 ml / min by the pump (20), the height of the upper part of the transparent glass container ｛the outlet of the test liquid (40) is set to the opening of the transparent glass container ( 11) The test solution was foamed by dropping from 2 cm｝, and when the foam height reached 10 cm, 5 μl (10 ppm) of antifoaming agents (DF1) to (DF13) and (H1) to (H6) ( Examples 1 to 13 and Comparative Examples 1 to 6) were added, and the height of the foam surface (mm) (initial foam breaking property) at which the height of the foam surface was reduced most and the height of the foam surface after 3 minutes ( mm) was read from the scale (30) (defoaming persistence). The smaller the height of the foam surface, the better the defoaming property.
The height of the foam surface was read in the same manner as above, except that the defoaming agent was changed to water (blank).

<Defoaming test 2>
1. Preparation of Emulsion Base Paint Using the raw material composition shown in Table 2, grinding and let down were performed using an Excel auto homogenizer equipped with impeller blades to prepare an emulsion base paint.

Note 1: Dispersant manufactured by San Nopco Co., Ltd. Note 2: Thickener manufactured by San Nopco Co., Ltd. Note 3: Calcium carbonate manufactured by Takehara Chemical Co., Ltd. Note 4: Titanium dioxide manufactured by Ishihara Sangyo Co., Ltd. Note 5: Acrylic emulsion manufactured by BASF, " ACRONAL "is a registered trademark of BSF Actiengezelshaft.
Note 6: Texanol, a membrane conditioner manufactured by Eastman Chemical Company, is a registered trademark of Yoshimura Oil Chemical Co., Ltd.
Note 7: Thickener manufactured by San Nopco Co., Ltd.

2. Preparation of emulsion paint 0.3 g each of defoamers (DF1) to (DF13) or defoamers (H1) to (H6) for comparison were added to 100 g of the emulsion base paint, and an Excel equipped with a Coreless blade was added. The mixture was stirred and mixed at 25 ° C. and 2500 rpm for 5 minutes with an auto homogenizer to obtain an emulsion paint for evaluation. Also, an emulsion paint for blank was obtained in the same manner as described above except that no defoaming agent was added.

3. Evaluation of defoaming properties Using a medium wool roller (Otsuka Brush Co., Ltd.), each of the emulsion paint for evaluation and the emulsion paint for blank were roller-coated on a tin plate with a 15 cm square, and the initial defoaming property and defoaming speed were measured. The results were evaluated and the results are shown in Table 3.
The initial defoaming property was visually determined by counting the number of bubbles immediately after application. A smaller number of bubbles means that the initial defoaming property of the defoamer is excellent. The defoaming speed was measured from the time immediately after the application to the time when no more bubbles could be observed. The shorter this time is, the faster the defoaming speed is, which means that it is excellent.

4. Evaluation of repellency After degreased a glass plate (thickness: 5 mm, cut to 20 × 30 cm) with acetone / cloth, the emulsion paint for evaluation was adjusted to a wet film thickness of 100 μm under conditions of 25 ° C. and 60% relative humidity. Was coated with an applicator, the surface of the coating film was observed, and the number of cissing marks was counted visually. It should be noted that the smaller the number is, the more excellent the suppression of repelling is.

  When the antifoaming agents (DF1) to (DF13) of the present invention are used, the minimum foam height and the foam height after 3 minutes are higher than when the antifoaming agents (H1) to (H6) for comparison are used. Was remarkably low and showed very excellent defoaming property. In addition, the antifoaming agents (DF1) to (DF13) of the present invention are superior to the defoaming agents (H1) to (H6) for comparison in suppressing the occurrence of cissing and defoaming, and are obtained by applying a paint. The resulting coating did not impair the appearance.

  Since the antifoaming agent of the present invention is excellent in repelling and defoaming properties, it can be used for all purposes. It is particularly effective to include it in an antifoaming agent for an aqueous foaming liquid. For example, paper pulp manufacturing industry (pulping process, paper making process, coating process, etc.), construction industry (paper making process, etc.), dye industry, dyeing The present invention can be applied to an antifoaming agent used for bubbles generated in various processes such as industry, fermentation industry, synthetic resin manufacturing industry, synthetic rubber manufacturing industry, ink, paint industry, and textile processing industry. Among these, they are suitable as antifoaming agents for paints, and are also suitable as antifoaming agents for aqueous paints.

Reference Signs List 10 transparent glass container 11 opening of transparent glass container 12 bottom of transparent glass container 20 pump 30 scale 40 test liquid outlet

Claims (7)

An antifoaming agent for a water-based coating material, comprising the compound (A) represented by the general formula (1) and a hydrocarbon oil (B).

R (OA) _n- OH (1)

In the general formula (1), R represents an alkyl group, alkenyl group or aryl group having 12 to 30 carbon atoms, OA represents an oxyalkylene group having 3 to 4 carbon atoms, OH represents a hydroxy group, and n represents an integer of 12 to 30. . The antifoaming agent according to claim 1, further comprising a hydrophobic compound (C) selected from hydrophobic silica, amide, wax and metal soap. The antifoaming agent according to claim 1 or 2, further comprising a polyoxyalkylene compound (D) other than the compound (A) represented by the general formula (1). Based on the weight of the compound (A) represented by the general formula (1) and the hydrocarbon oil (B), the content of the compound (A) represented by the general formula (1) is 5 to 80% by weight; The defoaming agent according to any one of claims 1 to 3, wherein the content of the hydrogen oil (B) is 20 to 95% by weight. The content of the hydrophobic compound (C) is 2 to 30% by weight based on the weight of the compound (A) represented by the general formula (1) and the hydrocarbon oil (B). An antifoaming agent according to any one of the above. The content of the polyoxyalkylene compound (D) other than the compound (A) represented by the general formula (1) is based on the weight of the compound (A) represented by the general formula (1) and the hydrocarbon oil (B). The defoaming agent according to any one of claims 3 to 5, based on 2 to 400% by weight based on the weight of the antifoaming agent. An aqueous coating composition comprising an aqueous coating material and the antifoaming agent according to any one of claims 1 to 6.

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