JP2011083715A - Defoaming agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a defoaming agent demonstrating the defoaming property equal to or more than that of conventional ones, and causing little cissing even if adapted for paint to be applied as a thin coating film. <P>SOLUTION: The defoaming agent is used containing an aliphatic metal salt (A), a polyoxyalkylene compound (B) and a polyhydric alcohol aliphatic acid ester (C). The aliphatic metal salt (A) preferably contains a compound expressed by formula (1): (R<SP>1</SP>-COO)pM (1), R<SP>1</SP>is a 1-30C alkyl group or a 2-30C alkenyl group, M is mono- to tri-valent metal atom, and p is an integer of 1-3. The polyoxyalkylene compound (B) is preferably a compound expressed by formula (2): R<SP>2</SP>-(OA)n-OR<SP>3</SP>(2), R<SP>2</SP>is a 2-30C acyl group, a 1-30C alkyl group or alkenyl group or a hydrogen atom, R<SP>3</SP>is a hydrogen atom or 2-30C acyl group, OA is 2-4C oxyalkylene group, and n is an integer of 2-100. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an antifoaming agent. More specifically, the present invention relates to an antifoaming agent suitable in the fields of chemical industry, food industry, petroleum industry, civil engineering and construction industry, textile industry, paper pulp industry, paint industry, pharmaceutical industry or wastewater treatment process.

  Conventionally, an antifoaming agent (Patent Document 1) containing an aluminum carboxylate, an aromatic carbon-containing hydrocarbon oil, and a polyoxyalkylene compound is known.

Japanese Patent No. 40385565

  Although the conventional antifoaming agent exhibits sufficient defoaming properties (foam breaking and foam suppressing effect), when applied to a paint for coating a thin coating film (for example, the thickness of the coating film is 200 μm or less), There is a problem that repelling occurs. That is, the object of the present invention is to provide an antifoaming agent that exhibits an antifoaming property equal to or higher than that of a conventional antifoaming agent and that generates little repellency even when applied to a paint for coating a thin coating film. is there.

  The inventor of the present invention has reached the present invention as a result of intensive studies to solve the above problems. That is, the feature of the antifoaming agent of the present invention is that it contains a fatty acid metal salt (A), a polyoxyalkylene compound (B) and a polyhydric alcohol fatty acid ester (C).

A feature of the production method of the present invention is a method for producing the antifoaming agent described above,
(1) A heating and dissolving step (1) in which a fatty acid metal salt (A), a polyoxyalkylene compound (B) and a polyhydric alcohol fatty acid ester (C) are heated with stirring to obtain a uniform solution,
(2) Cooling step (2) to cool the homogeneous solution while stirring to precipitate the fatty acid metal salt (A) to obtain a dispersion, and (3) Cool the uniform dispersion to obtain an antifoaming agent. A method (10) comprising a final step (3);

(1) A heating and dissolving step (1) in which a part of the fatty acid metal salt (A) and the polyhydric alcohol fatty acid ester (C) is heated with stirring to obtain a uniform solution,
(2) Cooling step (2) in which the homogeneous solution is cooled with stirring to precipitate the fatty acid metal salt (A) to obtain a dispersion, and (3) The remaining polyhydric alcohol fatty acid ester ( A method (20) comprising the final step (3) of adding C), cooling and stirring to obtain an antifoaming agent; or

(1) A heating and dissolving step (1) in which a part of the fatty acid metal salt (A) and the polyhydric alcohol fatty acid ester (C) is heated with stirring to obtain a uniform solution,
(2) Cooling step (2) in which a uniform solution is added to the remaining polyhydric alcohol ester (C) adjusted at 0 to 40 ° C. with stirring to obtain a dispersion, and (3) a uniform dispersion. The gist of the method is the method (30) including the final step (3) for cooling and stirring to obtain an antifoaming agent.

  The antifoaming agent of the present invention exhibits excellent defoaming performance with less occurrence of repellency even with a thin coating film having a thickness of 200 μm or less as compared with a conventional antifoaming agent.

  The fatty acid metal salt (A) is composed of a salt of a residue obtained by removing a hydrogen atom from a fatty acid and a metal atom. In addition, the meaning of both a salt and a complex is contained in a fatty acid metal salt. Moreover, fatty acid metal salt (A) may be comprised only by 1 type, and 2 or more types of mixtures may be sufficient as it.

Fatty acids include saturated fatty acids and unsaturated fatty acids.
Metal atoms include alkali metals (such as lithium, sodium and potassium), alkaline earth metals (such as barium, calcium and magnesium), transition metals (zinc, nickel, iron, copper, manganese, cobalt, silver, gold, platinum, Palladium, titanium, zirconium, cadmium, etc.), periodic table group 13 metals (aluminum, etc.), group 14 metals (tin, lead, etc.) or lanthanoid metals (lanthanum, cerium, etc.) are included.

As such a fatty acid metal salt (A), the compound represented by General formula (1) is preferable.

(R ¹ -COO) pM (1)

R ¹ represents an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 2 to 30 carbon atoms, M represents a 1 to 3 valent metal atom, and p represents an integer of 1 to 3.

In the general formula (1), among the alkyl group having 1 to 30 carbon atoms or the alkenyl group having 2 to 30 carbon atoms (R ¹ ), the alkyl group having 1 to 30 carbon atoms includes a linear alkyl group and a branched alkyl group. Groups etc. can be used.

  Linear alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, docosyl , Tricosyl, tetracosyl, heptacosyl, hexaxyl, heptacosyl, octacosyl, nonacosyl and triaconsil.

  Examples of the branched alkyl group include isopropyl, isobutyl, t-butyl, isopentyl, neopentyl, isohexyl, 2-ethylhexyl, isotridecyl, isotetradecyl, isooctadecyl, isotriaconyl, 2-ethylhexyl, 2-propylheptyl, 2-propyl Examples include butyloctyl, 2-hexyldecyl, 2-octyldodecyl, 2-decyltetradecyl, 2-dodecylhexyl, 2-dodecylhexadecyl, 3,5,5-trimethylhexyl, and 3,7,11-trimethyldodecyl. It is done.

Moreover, a linear alkenyl group, a branched alkenyl group, etc. can be used as a C2-C30 alkenyl group among (R < ¹ >).

  Linear alkenyl groups include vinyl, allyl, propenyl, butenyl, pentenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, icocenyl, hexocenyl, , Tetracosenyl, heptacosenyl, hexaxenyl, heptacosenyl, octacocenyl, nonacosenyl, triaconenyl and the like.

  Examples of the branched alkenyl group include isobutenyl, isopentenyl, neopentenyl, isohexenyl, isotridecenyl, isooctadecenyl, and isotriacontenyl.

  Among these, from the viewpoint of defoaming properties and repellency, a straight chain alkyl group and a straight chain alkenyl group are preferable, more preferably a straight chain alkyl group, particularly preferably a straight chain alkyl group having 8 to 24 carbon atoms, and most preferably. Are dodecyl and octadecyl.

  Examples of the 1-3 valent metal atom (M) include the above metal atoms. Among these, a divalent metal atom and a trivalent metal atom are preferable from the viewpoint of defoaming property, etc., more preferably a zinc atom, a magnesium atom and an aluminum atom, and particularly preferably an aluminum atom.

  p represents an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably an integer of 3.

  The fatty acid metal salt (A) may be a single compound having one kind of p or a plurality of mixtures having different p. Moreover, the mixture from which the kind of alkyl group or alkenyl group differs may be sufficient.

Preferred examples of the fatty acid metal salt (A) include zinc laurate, zinc behenate, calcium stearate, zinc stearate, aluminum stearate and barium stearate.
Such a preferable fatty acid metal salt (A) can be easily obtained from the market, and examples thereof include the following products.

  Calcium stearate, Oblate CA-65, Powder base L, Zinc behenate, Aluminum stearate 300, Aluminum stearate 600, Aluminum stearate 900 and barium stearate {NOF Corporation}

  As the polyoxyalkylene compound (B), any compound containing a polyoxyalkylene chain can be used without limitation. Examples of the oxyalkylene constituting the polyoxyalkylene chain include oxyalkylene groups having 2 to 4 carbon atoms (oxyethylene, oxypropylene and oxybutylene).

  The polyoxyalkylene chain may be composed of one kind of oxyalkylene group or may be composed of two or more kinds of oxyalkylene groups. When composed of two or more oxyalkylene groups, the bonding mode may be block, random, or a mixture thereof.

As a polyoxyalkylene compound (B), the compound represented by General formula (2) is preferable.

^{R 2 - (OA) n-} OR 3 (2)

R ² is an acyl group having 2 to 30 carbon atoms, an alkyl group or alkenyl group having 1 to 30 carbon atoms, or a hydrogen atom, R ³ is a hydrogen atom or an acyl group having 2 to 30 carbon atoms, and OA is an alkyl group having 2 to 4 carbon atoms. An oxyalkylene group, n represents an integer of 2 to 100.

Examples of the acyl group having 2 to 30 carbon atoms include a saturated carboxylic acyl group and an unsaturated carboxylic acyl group.
Saturated carboxylic acid acyl groups include acetyl (ethanoyl), propanoyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, heptadecanoyl, Examples include decanoyl, nonadecanoyl, icosanoyl, eicosanoyl, heicosanoyl, henecosanoyl, docosanoyl, tricasanoyl, tetracosanoyl, pentacosanoyl, hexacosanoyl, heptacosanoyl, octacosanoyl, nonacosanoyl and triacontanoyl.

  Unsaturated carboxylic acid acyl groups include acryloyl, methacryloyl, crotonoyl, isocrotonoyl, butenoyl, butadienoyl, pentenoyl, hexenoyl, heptenoyl, octenoyl, nonenoyl, decenoyl, undecenoyl, dodecenoyl, tetradecenoyl, oleroyl, oleoyl , Cycloheptanoyl, methylcyclopentanoyl, methylcyclohexanoyl, methylcycloheptanoyl, cyclopentenoyl, 2,4-cyclopentadienoyl, cyclohexenoyl, 2,4-cyclohexadenoyl, cycloheptenoyl Methylcyclopentenoyl, methylcyclohexenoyl, methylcycloheptenoyl and the like.

The alkyl group and alkenyl group having 1 to 30 carbon atoms are the same as R ^{1 in} the general formula (1).

  OA represents an oxyalkylene group having 2 to 4 carbon atoms, and includes oxyethylene, oxypropylene, and oxybutylene. Of these, oxyethylene and oxypropylene are preferred.

  OA may contain two or more oxyalkylene groups. When two or more kinds of oxyalkylene groups are contained, any of block, random and a mixture thereof may be used, but a block of oxyethylene and oxypropylene is preferable.

  n represents an integer of 2 to 100, preferably an integer of 2 to 99, more preferably an integer of 3 to 50, and particularly preferably an integer of 4 to 30. Within this range, antifoaming properties and repellency are further improved.

  As a compound represented by General formula (2), it is preferable that the compound represented by General formula (2-1) and the compound represented by General formula (2-2) are included.

R ² '-(OA) n-OR ³ ' (2-1)

^{R 2 "- (OA) n} -OR 3" (2-2)

R ² ′ is an acyl group having 2 to 30 carbon atoms or a hydrogen atom, R ³ ′ is an acyl group having 2 to 30 carbon atoms, R ² ″ is an alkyl group or alkenyl group having 1 to 30 carbon atoms, and R ³ ″ is hydrogen. An atom or an acyl group having 2 to 30 carbon atoms, OA represents an oxyalkylene group having 2 to 4 carbon atoms, and n represents an integer of 2 to 100.

  The acyl group having 2 to 30 carbon atoms, the alkyl or alkenyl group having 1 to 30 carbon atoms, the oxyalkylene group (OA) having 2 to 4 carbon atoms and n are the same as those in the general formula (2). is there.

Among R ² ′, a hydrogen atom and an acyl group having 2 to 22 carbon atoms are preferable from the viewpoint of defoaming properties and repelling, more preferably a hydrogen atom, dodecanoyl, octadecanoyl and oleoyl, particularly preferably a hydrogen atom and oleoyl. It is.

Among R ³ ′, an acyl group having 2 to 22 carbon atoms is preferable from the viewpoint of defoaming properties and repellency, more preferably dodecanoyl, octadecanoyl and oleoyl, particularly preferably oleoyl.

Of R ² ″, a hydrogen atom and an alkyl group are preferable from the viewpoint of defoaming properties and repellency, more preferably a hydrogen atom and a linear alkyl group, particularly preferably a hydrogen atom and a linear alkyl group having 3 to 8 carbon atoms. Most preferably, they are a hydrogen atom and butyl.

Among R ³ ″, from the viewpoint of defoaming properties and repellency, a hydrogen atom and an acyl group having 2 to 22 carbon atoms are preferable, more preferably a hydrogen atom, dodecanoyl, octadecanoyl and oleoyl, and particularly preferably oleoyl.

Examples of the polyoxyalkylene compound (B) include polyoxyethylene glycol (mono, di) laurate, polyoxyethylene glycol (mono, di) oleate, polyoxyethylene glycol (mono, di) stearate, poly Preferred examples include oxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxypropylene butyl ether, polyoxypropylene decyl ether and polyoxypropylene isodecyl ether.
Such a preferable polyoxyalkylene compound (B) can be easily obtained from the market, and examples thereof include the following products.

<Polyoxyethylene glycol (mono, di) laurate, polyoxyethylene glycol (mono, di) oleate, polyoxyethylene glycol (mono, di) stearate>
Ionette (registered trademark) series (MS-400, MS-1000, MO-200, DL-200, DO-600, DS-400, DS-4000, etc.) {Sanyo Chemical Industries, Ltd.}

<Polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxypropylene butyl ether>
Emarumin (registered trademark) series (L-380, NL-110, CC-200, CO-200, etc.) {Sanyo Chemical Industries, Ltd.}

<Polyoxypropylene decyl ether, polyoxypropylene isodecyl ether>
Braunon series (NDB-800, NDB-1400, IDEP-608, IDEP-802, etc.) {Aoki Yushi Kogyo Co., Ltd.}

  The polyhydric alcohol fatty acid ester (C) includes a partial ester or a complete ester of a fatty acid and a polyhydric alcohol.

Fatty acids include saturated fatty acids and unsaturated fatty acids.
As a saturated fatty acid, a C1-C30 saturated fatty acid is contained and a linear saturated fatty acid and a branched saturated fatty acid can be used.

  Examples of the linear saturated fatty acid include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, serotic acid, and melicic acid.

  Examples of the branched saturated fatty acid include isobutyric acid, isovaleric acid, pivalic acid, and isostearic acid.

  As unsaturated fatty acid, a C3-C30 linear unsaturated fatty acid is contained, and a linear unsaturated fatty acid and a branched unsaturated fatty acid can be used.

  Examples of the linear unsaturated fatty acid include acrylic acid, crotonic acid, heptenoic acid, myristoleic acid, palmitoleic acid, oleic acid and triacontenoic acid.

  Examples of branched unsaturated fatty acids include methacrylic acid, isomiristoleic acid and isooleic acid.

  Of these, from the viewpoint of antifoaming properties and repelling, linear saturated fatty acids and linear unsaturated fatty acids are preferable, and lauric acid, myristic acid, palmitic acid, stearic acid, crotonic acid, heptenoic acid, myristoleic acid are more preferable. Palmitic acid and oleic acid, particularly preferably myristic acid, palmitic acid, stearic acid, myristoleic acid, palmitoleic acid and oleic acid, most preferably palmitic acid, stearic acid, palmitoleic acid and oleic acid.

Examples of polyhydric alcohols include diols, triols, and tetravalent or higher polyols.
Examples of the diol include diols having 2 to 6 carbon atoms such as ethylene glycol, propylene glycol, butylene glycol, isobutylene glycol, and cyclohexanediol.

  Triols include triols having 3 to 6 carbon atoms, and examples include trimethylolethane, trimethylolpropane, glycerin, hexanetriol, and cyclohexanetriol.

  Examples of the tetravalent or higher polyol include polyglycerin {diglycerin, triglycerin, tetraglycerin, pentaglycerin and the like}, pentaerythritol, dipentaerythritol, sorbitan, sorbitol, sugars {glucose, sucrose, xylitol, sucrose, etc.} and Cellulosic compounds {methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose, etc.} and the like.

  Of these, triols and tetravalent or higher polyols are preferable, triols are more preferable, trimethylolethane, trimethylolpropane, and glycerin are most preferable, and glycerin is most preferable.

Preferred examples of the polyhydric alcohol fatty acid ester (C) include glycerin fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, trimethylolpropane fatty acid ester and sucrose fatty acid ester.
Such preferable polyhydric alcohol fatty acid ester (C) can be easily obtained from the market, and examples thereof include the following products.

<Glycerin fatty acid ester>
RHEODOL (registered trademark) series (MS-50, MS-60, MS-165V, etc.) {Kao Co., Ltd. product}
NIKKOL (registered trademark) series (MGU, MGM, AMV, ASEV, BV, MGIS, MGOL-70, DGS-80, etc.) {Nippon Chemicals Co., Ltd.}
Soybean oil, palm oil, palm oil, linseed oil, cottonseed oil, rapeseed oil, etc. {Nisshin Oilio Co., Ltd.}

<Polyglycerin fatty acid ester>
NIKKOL (registered trademark) series (DGMS, Tetlaglyn 1-SV, Tetlaglyn 5-S, Hexaglyn 1-L, Hexaglyn 5-SV, Decaglyn 1-M, Decaglyn 2-ISV, and Decaglyn 5 )}
SY Glister Series (THL-3, THL-15, THL-17, THL-50, CLT-707, etc.) {Sakamoto Pharmaceutical Co., Ltd. product}

<Sorbitan fatty acid ester>
Ionette (registered trademark) series (S-80, S-60C, S-80, S-85, etc.) {Sanyo Chemical Industries, Ltd.}

<Trimethylolpropane fatty acid ester>
Trimethylolpropane tricaprylate, trimethylolpropane trilaurate, trimethylolpropane trioleate, etc. {Sanko Chemical Co., Ltd. product}

<Sucrose fatty acid ester>
Ryoto (registered trademark) series (S-070, S-170, S-1670, P-170, P-1670, O-170, O-1570, L-195, L-1695, B-370, ER-190 And POS-135) etc. {Mitsubishi Chemical Foods Corporation}

   The content (% by weight) of the fatty acid metal salt (A) is 0.1 to 0.1% based on the total weight of the fatty acid metal salt (A), the polyoxyalkylene compound (B) and the polyhydric alcohol fatty acid ester (C). 10 is preferable, more preferably 0.2 to 8, and particularly preferably 0.5 to 5. Within this range, the defoaming property is further improved and repellency is reduced.

  The content (% by weight) of the polyoxyalkylene compound (B) is 5 to 50 based on the total weight of the fatty acid metal salt (A), the polyoxyalkylene compound (B) and the polyhydric alcohol fatty acid ester (C). Is more preferable, 7 to 42 is more preferable, and 9 to 30 is particularly preferable. Within this range, the defoaming property is further improved and repellency is reduced.

  The content (% by weight) of the polyhydric alcohol fatty acid ester (C) is 40 based on the total weight of the fatty acid metal salt (A), the polyoxyalkylene compound (B) and the polyhydric alcohol fatty acid ester (C). -94 are preferable, More preferably, it is 50-90, Most preferably, it is 65-86. Within this range, the defoaming property is further improved and repellency is reduced.

In addition to the fatty acid metal salt (A), the polyoxyalkylene compound (B) and the polyhydric alcohol fatty acid ester (C), the antifoaming agent of the present invention may contain other components (such as a surfactant). Good.
As the surfactant, nonionic, cationic, anionic or amphoteric surfactants can be used.

  Examples of the nonionic surfactant include alkylene oxide adducts of higher alkylamines, alkylene oxide adducts of higher fatty acid amides, alkylene oxide adducts of acetylene glycol, and polyoxyalkylene-modified silicones (polyether-modified silicones). However, the nonionic surfactant does not include the polyoxyalkylene compound (B).

  Examples of cationic surfactants include higher alkylamine salts, higher alkylamine alkylene oxide adducts, solomin A type cationic surfactants, sapamin A type cationic surfactants, Arcobel A type cationic surfactants, and imidazoline type cationic surfactants. Agents, higher alkyltrimethylammonium salts, higher alkyldimethylbenzylammonium salts, sapamine-type quaternary ammonium salts and pyridinium salts.

  Anionic surfactants include fatty acid alkali metal salts, fatty acid ammonium salts, fatty acid amine salts, α-olefin sulfonates, alkylbenzene sulfonic acids and salts thereof, alkyl sulfate esters, alkyl ether sulfates, N-acyl alkyls. Examples include taurine salts and alkylsulfosuccinates. However, the fatty acid metal salt (A) is not included in the anionic surfactant.

  Examples of amphoteric surfactants include higher alkylaminopropionates and higher alkyldimethylbetaines.

  When the surfactant is contained, the content (% by weight) is 0.1 to 0.1, based on the weight of the fatty acid metal salt (A), the polyoxyalkylene compound (B) and the polyhydric alcohol fatty acid ester (C). 20, more preferably 0.5 to 10, particularly preferably 1 to 5. If it is within this range, the fluidity may be further improved.

The antifoaming agent of this invention can be manufactured by a well-known method, for example, the following method etc. are applicable.
<Manufacturing method 1>
(1) First, the fatty acid metal salt (A), the polyoxyalkylene compound (B) and the polyhydric alcohol fatty acid ester (C) are heated with stirring to obtain a uniform solution (1),
(2) Cooling step (2) in which the homogeneous solution is cooled with stirring to precipitate the fatty acid metal salt (A) to obtain a dispersion; and (3) The uniform dispersion is cooled to remove the defoaming of the present invention. A method (10) comprising a final step (3) for obtaining an agent.

<Manufacturing method 2>
(1) A heating and dissolving step (1) in which a part of the fatty acid metal salt (A) and the polyhydric alcohol fatty acid ester (C) is heated with stirring to obtain a uniform solution,
(2) Cooling step (2) in which the homogeneous solution is cooled with stirring to precipitate the fatty acid metal salt (A) to obtain a dispersion, and (3) The remaining polyhydric alcohol fatty acid ester ( A method (20) comprising the final step (3) of adding C), cooling and stirring to obtain the antifoaming agent of the present invention.

<Manufacturing method 3>
(1) A heating and dissolving step (1) in which a part of the fatty acid metal salt (A) and the polyhydric alcohol fatty acid ester (C) is heated with stirring to obtain a uniform solution,
(2) Cooling step (2) in which a uniform solution is added to the remaining polyhydric alcohol ester (C) adjusted at 0 to 40 ° C. with stirring to obtain a dispersion, and (3) a uniform dispersion. A method comprising a final step (3) of cooling and stirring to obtain the antifoaming agent of the present invention.

  In the heating and dissolving step (1), a part of the polyoxyalkylene compound (B) and the polyhydric alcohol fatty acid ester (C) is used, and the remaining polyoxyalkylene compound (B) and the polyhydric alcohol fatty acid ester (C) are used. It may be added in a later process.

  After the cooling step (2), the material may be refined by a ball mill, a disper mill, a homogenizer, a gourn homogenizer, or the like.

  The heating temperature (° C.) in the heating and dissolving step (1) is appropriately determined depending on the type of the fatty acid metal salt (A) to be used, but is preferably 80 to 250, more preferably 90 to 200, and particularly preferably 100 to 100. 150, most preferably 110-140.

  The cooling temperature (° C.) in the cooling step (2) is preferably 90 or less.

  40 or less is preferable and, as for the cooling temperature (degreeC) in the last process (3), More preferably, it is 5-40.

The antifoaming agent of the present invention is effective for aqueous foaming liquid, and in particular, it is used for chemical industry, food industry, petroleum industry, civil engineering and construction industry, textile industry, paper pulp industry, pharmaceutical industry or wastewater treatment process. Suitable as a foaming agent.
Further, the antifoaming agent of the present invention is excellent in biodegradability as compared with a conventional antifoaming agent (Patent Document 1) containing an aluminum carboxylate, an aromatic carbon-containing hydrocarbon oil and a polyoxyalkylene compound. Therefore, from the viewpoint of environmental protection, it can also be applied to fields where there have been problems and limitations of use.

  The amount of the antifoaming agent of the present invention can be appropriately increased or decreased depending on the type, temperature, concentration, amount of treatment, etc. of foaming liquid (degree of foaming, etc.). 10 weight% is preferable, More preferably, it is 0.1-5 weight%, Most preferably, it is 0.2-2 weight%.

  EXAMPLES Next, although an Example demonstrates this invention further, this invention is not limited to this. Hereinafter, unless otherwise specified, “part” means “part by weight” and “%” means “% by weight”.

<Example 1>
Fatty acid metal salt (a1) {magnesium distearate, Orlabrite (registered trademark) MA-76, NOF Corporation} 0.1 part, polyoxyalkylene compound (b11) {polyoxyethylene (degree of polymerization: 20) Glycol dioleic acid ester, Ionette DO-1000, Sanyo Chemical Industries, Ltd.} 50 parts, polyhydric alcohol fatty acid ester (c1) {glycerin monostearic acid ester, Rheidol MS-50, Kao Corporation} 49.9 Was put into a stainless steel container, and then the temperature was raised to 150 ° C. while stirring at 4000 rpm with a homogenizer (High Flex Disperser HG-92G, manufactured by Taitec Co., Ltd.), and this temperature was further increased for 3 hours. Stir with heating. Then, stirring the obtained mixture, it cooled by air cooling to 30 degreeC, and obtained the antifoamer (1) of this invention.
About the obtained antifoaming agent, it was confirmed by the dispersity test [JIS K5600-2-5: 1999 (corresponding to ISO 1524: 1983)] that there are no particles of 5 microns or more.

<Example 2>
"Fatty acid metal salt (a1) 0.1 part", "Polyoxyalkylene compound (b11) 50 part" and "Polyhydric alcohol fatty acid ester (c1) 49.9 part" are combined with "Fatty acid metal salt (a2) {tri Aluminum stearate, aluminum stearate 900, NOF Corporation 1 part "," polyoxyalkylene compound (b12) {polyoxyethylene (degree of polymerization: 9) glycol monostearate, Ionette MS-400, Sanyo Chemical Industrial Co., Ltd.} 5 parts ”and“ Polyhydric alcohol fatty acid ester (c2) {Rapeseed oil, Nissin Oilio Group Co., Ltd.} 94 parts ” An antifoaming agent (2) was obtained.
About the obtained antifoaming agent, it was confirmed by the dispersity test [JIS K5600-2-5: 1999 (corresponding to ISO 1524: 1983)] that there are no particles of 5 microns or more.

<Example 3>
“Fatty acid metal salt (a1) 0.1 part”, “Polyoxyalkylene compound (b11) 50 part” and “Polyhydric alcohol fatty acid ester (c1) 49.9 part” are replaced with “Fatty acid metal salt (a3) {mono Aluminum stearate, aluminum stearate 300, NOF Corporation 10 parts "," polyoxyalkylene compound (b13) {polyoxyethylene (degree of polymerization: 4) glycol dilaurate, Ionette DL-200, Sanyo Chemical Industrial Co., Ltd.} 50 parts ”and“ polyhydric alcohol fatty acid ester (c3) {monolaurin decaglycerin ester, NIKKOL Decaglyn 1-L, Nikko Chemicals Co., Ltd.} 40 parts ” Thus, an antifoaming agent (3) of the present invention was obtained.
About the obtained antifoaming agent, it was confirmed by the dispersity test [JIS K5600-2-5: 1999 (corresponding to ISO 1524: 1983)] that there are no particles of 5 microns or more.

<Example 4>
"Fatty acid metal salt (a1) 0.1 part", "Polyoxyalkylene compound (b11) 50 part" and "Polyhydric alcohol fatty acid ester (c1) 49.9 part" are replaced with "Fatty acid metal salt (a4) {Dilaurin Zinc acid, Zinclaurate GP, NOF Corporation 10 parts "," Polyoxyalkylene compound (b21) {Polyoxypropylene (degree of polymerization: 40) butyl ether, Newpol (registered trademark) LB-1715, Sanyo Chemical Except for the change to "Industry Co., Ltd.} 5 parts" and "Polyhydric alcohol fatty acid ester (c4) {Sorbitan trioleate, Ionette S-85, Sanyo Chemical Industries Co., Ltd.} 85 parts" Similarly, the antifoamer (4) of this invention was obtained.
About the obtained antifoaming agent, it was confirmed by the dispersity test [JIS K5600-2-5: 1999 (corresponding to ISO 1524: 1983)] that there are no particles of 5 microns or more.

<Example 5>
"Fatty acid metal salt (a1) 0.1 part", "Polyoxyalkylene compound (b11) 50 part" and "Polyhydric alcohol fatty acid ester (c1) 49.9 part" were converted into "Fatty acid metal salt (a5) {distearin. Aluminum acid, aluminum stearate 600, NOF Corporation} 0.5 part ”,“ Polyoxyalkylene compound (b22) {Polyoxypropylene (degree of polymerization: 40) ester of butanol ether and oleic acid} 30 parts ” And “polyhydric alcohol fatty acid ester (c5) {trimethylolpropane caprylic acid ester, Sanko Chemical Co., Ltd.} in the same manner as in Example 1 except that the amount was changed to 69.5 parts. )
About the obtained antifoaming agent, it was confirmed by the dispersity test [JIS K5600-2-5: 1999 (corresponding to ISO 1524: 1983)] that there are no particles of 5 microns or more.

The polyoxyalkylene compound (b22) was obtained as follows.
In a four-neck flask reaction vessel equipped with a thermometer, a stirrer, and a cooling device for dehydration, 282 parts (1.00 mol part) of oleic acid [reagent grade 1, Wako Pure Chemical Industries, Ltd.], polyoxypropylene (polymerization) Degree: 40) butyl ether [Newpol LB-1715, Sanyo Chemical Industries, Ltd.] 2256 parts (1.01 mol parts) and paratoluenesulfonic acid [reagent special grade, Wako Pure Chemical Industries, Ltd.] 8.6 parts ( 0.05 mol part) was charged, and the inside of the reaction vessel was purged with nitrogen, and then the temperature of the reaction mixture was raised to 130 ° C., and the reaction was carried out for 20 hours while removing generated water.
Then, 172 parts of magnesium oxide [KYOWARD 100, Kyowa Chemical Co., Ltd.] was added to the reaction product, and the mixture was stirred at 100 ° C. for 1 hour, and then the magnesium oxide was removed by vacuum filtration to remove polyoxyalkylene. Compound (b22) was obtained.

<Example 6>
"Fatty acid metal salt (a1) 0.1 part", "Polyoxyalkylene compound (b11) 50 part" and "Polyhydric alcohol fatty acid ester (c1) 49.9 part" are combined with "Fatty acid metal salt (a6) {Stear "Calcium phosphate, calcium stearate GP, NOF Corporation} 5 parts", "polyoxyalkylene compound (b11) 40 parts" and "polyhydric alcohol fatty acid ester (c6) {sucrose stearate (monoester content) : 50%), Ryoto S-970, Mitsubishi Chemical Foods Co., Ltd.} 55 parts ”, the antifoaming agent (6) of the present invention was obtained in the same manner as in Example 1.
About the obtained antifoaming agent, it was confirmed by the dispersity test [JIS K5600-2-5: 1999 (corresponding to ISO 1524: 1983)] that there are no particles of 5 microns or more.

<Example 7>
1 part of fatty acid metal salt (a1), 1 part of fatty acid metal salt (a7) {barium stearate, barium stearate GF, NOF Corporation}, 5 parts of polyoxyalkylene compound (b12), and polyoxyalkylene compound (B22) 5 parts, 40 parts of a polyhydric alcohol fatty acid ester (c1) and 48 parts of a polyhydric alcohol fatty acid ester (c2) were put into a stainless steel container, and then homogenizer (High Flex Disperser HG-92G, Tytech Corp. The temperature was raised to 150 ° C. while stirring at 4000 rpm, and the mixture was further heated and stirred at this temperature for 3 hours. Then, stirring the obtained mixture, it cooled by air cooling to 30 degreeC, and obtained the antifoamer (7) of this invention.
About the obtained antifoaming agent, it was confirmed by the dispersity test [JIS K5600-2-5: 1999 (corresponding to ISO 1524: 1983)] that there are no particles of 5 microns or more.

<Example 8>
2 parts of fatty acid metal salt (a2), 1 part of fatty acid metal salt (a5), 1 part of fatty acid metal salt (a8) {zinc behenate, zinc behenate, NOF Corporation}, and polyoxyalkylene compound (b11) 10 parts, 10 parts of a polyoxyalkylene compound (b21) and 76 parts of a polyhydric alcohol fatty acid ester (c3) were put into a stainless steel container, and then placed in a homogenizer (High Flex Disperser HG-92G, manufactured by Tytech Co., Ltd.). The temperature was raised to 150 ° C. while stirring at 4000 rpm, and the mixture was further heated and stirred at this temperature for 3 hours. Then, stirring the obtained mixture, it cooled by air cooling to 30 degreeC, and obtained the antifoamer (8) of this invention.
About the obtained antifoaming agent, it was confirmed by the dispersity test [JIS K5600-2-5: 1999 (corresponding to ISO 1524: 1983)] that there are no particles of 5 microns or more.

<Comparative Example 1>
0.19 parts of fatty acid metal salt (a1), 50 parts of polyoxyalkylene compound (b11) and hydrocarbon oil (t1) [Pure Spin (registered trademark) G, Cosmo Oil Lubricants Co., Ltd.] 49.9 Then, the mixture was heated to 150 ° C. with stirring at 4000 rpm with a homogenizer (High Flex Disperser HG-92G, manufactured by Taitec Corporation), and further heated and stirred at this temperature for 3 hours. Then, stirring the obtained mixture, it cooled by air cooling to 30 degreeC, and obtained the antifoamer (H1) for a comparison.
About the obtained antifoaming agent, it was confirmed by the dispersity test [JIS K5600-2-5: 1999 (corresponding to ISO 1524: 1983)] that there are no particles of 5 microns or more.

<Comparative Example 2>
“Fatty acid metal salt (a1) 0.1 part”, “Polyoxyalkylene compound (b11) 50 part” and “Hydrocarbon oil (t1)” are combined with “Fatty acid metal salt (a2) 1 part”, “Polyoxyalkylene” An antifoaming agent (H2) for comparison was obtained in the same manner as in Comparative Example 1, except that the compound was changed to “5 parts of compound (b12)” and “94 parts of hydrocarbon oil (t1)”.
About the obtained antifoaming agent, it was confirmed by the dispersity test [JIS K5600-2-5: 1999 (corresponding to ISO 1524: 1983)] that there are no particles of 5 microns or more.

<Comparative Example 3>
After 3 parts of fatty acid metal salt (a3) and 97 parts of polyhydric alcohol fatty acid ester (c1) were put into a stainless steel container, they were stirred at 4000 rpm with a homogenizer (High Flex Disperser HG-92G, manufactured by Taitec Corporation). While raising the temperature to 150 ° C., the mixture was further heated and stirred at this temperature for 3 hours. Thereafter, the obtained mixture was cooled with air cooling to 30 ° C. with stirring to obtain a comparative antifoaming agent (H3).
About the obtained antifoaming agent, it was confirmed by the dispersity test [JIS K5600-2-5: 1999 (corresponding to ISO 1524: 1983)] that there are no particles of 5 microns or more.

  Table 1 summarizes the content of each component of the antifoaming agents obtained in Examples 1 to 8 and Comparative Examples 1 to 3.

<Evaluation Example 1>
Using the antifoaming agents obtained in Examples 1 to 8 and Comparative Examples 1 to 3, emulsion paints were prepared as follows, and these emulsion paints were evaluated for antifoaming properties and repellency by the following methods. . These results are shown in Table 3.

(1) Preparation of Emulsion Base Paint Using the raw material composition shown in Table 2, using an Excel Auto Homogenizer (model ED, manufactured by Nippon Seiki Co., Ltd.) equipped with impeller blades, the paint was ground and let down. It was decided. The obtained paint was confirmed to have no particles of 5 microns or more by a dispersity test in the same manner as described above.
Next, this paint was diluted with water so as to be 77 KU (25 ° C.) with a stoma viscometer (JIS K5400-1990) to obtain an emulsion base paint.

(2) Preparation of emulsion paint Addition of antifoaming agent to emulsion base paint so as to be 1% by weight (vs. emulsion base paint), and 15 to 25 ° C, 2000 rpm, with an Excel auto homogenizer equipped with impeller blades The mixture was stirred and mixed for 3 minutes to obtain an emulsion paint.
Moreover, the coating material which does not add an antifoamer was created and it was set as the emulsion coating material (no antifoamer addition).

(3) Evaluation of defoaming property and repellency After degreasing a tin plate {cut to a thickness of 0.5 mm and 20 x 30 cm} with acetone / cloth, and then applying an emulsion paint with a roller to a wet film thickness of 200 μm The film was dried for 1 day in a control room adjusted to 25 ° C. and 60% relative humidity, and the surface of the coating film was observed to evaluate defoaming properties and repellency according to the following criteria.
In addition, after the emulsion paint was stored at 40 ° C. for 1 month (after aging), it was agitated and mixed for 15 minutes at 15 to 25 ° C. and 2000 rpm with an Excel auto homogenizer equipped with impeller blades. The emulsion paint was obtained, and the antifoaming property and repellency were similarly evaluated.

<Defoaming property>
The number of bubble marks was confirmed visually.
(A smaller value means higher defoaming properties and is preferable)

<Repel>
The number of repels or cratering marks was confirmed visually.
(A smaller number means less repelling and is preferable)

<Evaluation Example 2>
Using the antifoaming agents obtained in Examples 1 to 8 and Comparative Examples 1 to 4, coating colors for paper coating were prepared as follows. These coating colors were evaluated for antifoaming properties and repellency by the following methods. The results are shown in Table 5.

(1) Preparation of coating color base A coating color base was prepared using an Excel auto homogenizer (model ED, manufactured by Nippon Seiki Co., Ltd.) having the impeller type blades with the raw material composition shown in Table 4.

(2) Evaluation of antifoaming properties and repelling Add a defoaming agent to the coating color base to 1%, and stir and mix in an Excel auto homogenizer equipped with impeller type blades at 15-25 ° C, 2000 rpm for 10 minutes. Coating color was obtained. Further, a blank coating color (no antifoaming agent added) was obtained in the same manner as the above method except that no antifoaming agent was added. And about these coating colors, specific gravity of the coating color immediately after stirring for 10 minutes was measured according to JISK5600-2-4: 1999 (metal specific gravity bottle: specific gravity cup). The larger the specific gravity, the less the foam is bite and the better the defoaming property.

Also, after degreasing a glass plate {thickness 5 mm, cut to 20 × 30 cm} with acetone / cloth, and coating the coating color with an applicator so that the wet film thickness becomes 100 μm, the surface of the coating film was observed and The repelling was evaluated according to the criteria.
The coating color was stored at 40 ° C. for 1 month (after aging), and was then stirred and mixed at 15-25 ° C., 2000 rpm for 10 minutes using an Excel auto homogenizer equipped with impeller blades. The coating color was obtained, and the antifoaming property and repellency were similarly evaluated.

<Repel>
The number of cissing marks was visually confirmed.
(A smaller number means less repelling and is preferable)

  When the antifoaming agent of the present invention is used, high antifoaming properties can be exhibited and repelling occurs even when a thin coating film (100 to 200 μm) is used as compared with a coating using a comparative antifoaming agent. There were few.

  The antifoaming agent of the present invention can be used for any application, but is effective for aqueous foaming liquids, for example, chemical industry, food industry, petroleum industry, civil engineering and construction industry, textile industry, paper pulp industry, It is suitable in the fields of paint industry, pharmaceutical industry or wastewater treatment process.

Claims (7)

An antifoaming agent comprising a fatty acid metal salt (A), a polyoxyalkylene compound (B) and a polyhydric alcohol fatty acid ester (C). The antifoaming agent according to claim 1, wherein the fatty acid metal salt (A) comprises a compound represented by the general formula (1).

(R ¹ -COO) pM (1)

R ¹ represents an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 2 to 30 carbon atoms, M represents a 1 to 3 valent metal atom, and p represents an integer of 1 to 3. The antifoaming agent according to claim 1 or 2, wherein the polyoxyalkylene compound (B) is a compound represented by the general formula (2).

^{R 2 - (OA) n-} OR 3 (2)

R ² is an acyl group having 2 to 30 carbon atoms, an alkyl group or alkenyl group having 1 to 30 carbon atoms, or a hydrogen atom, R ³ is a hydrogen atom or an acyl group having 2 to 30 carbon atoms, and OA is an alkyl group having 2 to 4 carbon atoms. An oxyalkylene group, n represents an integer of 2 to 100. The polyoxyalkylene compound (B) comprises a compound represented by the general formula (2-1) and a compound represented by the general formula (2-2). Antifoam agent.

R ² '-(OA) n-OR ³ ' (2-1)

^{R 2 "- (OA) n} -OR 3" (2-2)

R ² ′ is an acyl group having 2 to 30 carbon atoms or a hydrogen atom, R ³ ′ is an acyl group having 2 to 30 carbon atoms, R ² ″ is an alkyl group or alkenyl group having 1 to 30 carbon atoms, and R ³ ″ is hydrogen. An atom or an acyl group having 2 to 30 carbon atoms, OA represents an oxyalkylene group having 2 to 4 carbon atoms, and n represents an integer of 2 to 100. The polyhydric alcohol fatty acid ester (C) is at least one selected from the group consisting of glycerin fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, trimethylolpropane fatty acid ester and sucrose fatty acid ester. The antifoamer in any one. Based on the total weight of the fatty acid metal salt (A), the polyoxyalkylene compound (B) and the polyhydric alcohol fatty acid ester (C), the content of (A) is 0.1 to 10% by weight, The antifoaming agent according to any one of claims 1 to 5, wherein the content is 5 to 50% by weight and the content of (C) is 40 to 94. A method for producing the antifoaming agent according to any one of claims 1 to 6,
(1) A heating and dissolving step (1) in which a fatty acid metal salt (A), a polyoxyalkylene compound (B) and a polyhydric alcohol fatty acid ester (C) are heated with stirring to obtain a uniform solution,
(2) Cooling step (2) to cool the homogeneous solution while stirring to precipitate the fatty acid metal salt (A) to obtain a dispersion, and (3) Cool the uniform dispersion to obtain an antifoaming agent. A method (10) comprising a final step (3);

(1) A heating and dissolving step (1) in which a part of the fatty acid metal salt (A) and the polyhydric alcohol fatty acid ester (C) is heated with stirring to obtain a uniform solution,
(2) Cooling step (2) in which the homogeneous solution is cooled with stirring to precipitate the fatty acid metal salt (A) to obtain a dispersion, and (3) The remaining polyhydric alcohol fatty acid ester ( A method (20) comprising the final step (3) of adding C), cooling and stirring to obtain an antifoaming agent; or

(1) A heating and dissolving step (1) in which a part of the fatty acid metal salt (A) and the polyhydric alcohol fatty acid ester (C) is heated with stirring to obtain a uniform solution,
(2) Cooling step (2) in which a uniform solution is added to the remaining polyhydric alcohol ester (C) adjusted at 0 to 40 ° C. with stirring to obtain a dispersion, and (3) a uniform dispersion. A production method comprising a method (30) comprising a final step (3) for cooling and stirring to obtain an antifoaming agent.