JP5608845B2 - Antifoam - Google Patents

Description

  The present invention relates to an antifoaming agent.

Contains C12-22 alkanol and / or C12-22 fatty acid ester of divalent or trivalent alcohol and 50% or less paraffin oil and / or C12-22 fatty acid based on the weight of the non-water portion An emulsion antifoaming agent having a particle diameter of 4 to 9 μm is known (Patent Document 1).
However, this has a drawback that the defoaming performance is low at a temperature of 50 ° C. or higher.
Therefore, in order to exhibit good defoaming property even at a temperature of 50 ° C. or higher, an alcohol comprising 10 to 90% by weight of a higher alcohol and 10 to 90% by weight of a compound having an alkylene oxide adduct structure of glycols or glycols. A foaming agent composition has been proposed (Patent Document 2).

JP-A 48-62683 JP-A-55-129116

In a water-dispersed antifoaming agent containing a higher alcohol as an essential component (higher alcohol-based antifoaming agent, the same shall apply hereinafter), it is desired to exhibit good antifoaming properties even at a high temperature of 50 ° C. However, the conventional higher alcohol antifoaming agent has a problem that sufficient high-temperature suitability cannot be obtained. An object of the present invention is to provide a higher alcohol-based antifoaming agent that exhibits excellent antifoaming properties even at high temperatures (50 ° C. or higher).

As a result of intensive studies to solve the above problems, the present inventors have formulated a polyether compound containing a specific nucleating agent in an underwater dispersion type antifoaming agent containing a higher alcohol as an essential component. The present inventors have found that stable and good defoaming properties can be obtained in a wide temperature range of 10 to 60 ° C., and have reached the present invention.
That is, the defoamer of the present invention is characterized by at least one selected from the group consisting of an alcohol (A) having 12 to 30 carbon atoms, mineral oil, animal / vegetable oil, fatty acid ester, polyorganosiloxane, and polyether compound. A dispersion (Z) in which particles (X) composed of a hydrophobic component (B) having a melting point or pour point lower than the melting point of the alcohol (A) as an essential component are dispersed in water,
A nucleating agent comprising, as essential components, at least one nucleating agent (C) selected from the group consisting of fatty acid metal salts, fatty acid amides, waxes, hydrophobic metal oxides, and synthetic resins, and a polyether compound (D). only contains a poly ether (Y) enters,
Based on the weight of the dispersion (Z) and the polyether (Y) containing the nucleating agent, the weight of the dispersion (Z) is 65 to 95% by weight, and the weight of the polyether (Y) containing the nucleating agent is 5 to 35% by weight. It is a summary.

  The antifoaming agent of the present invention exhibits a stable and good antifoaming property in a wide temperature range of 10 to 60 ° C. Therefore, it exhibits excellent antifoaming properties even at high temperatures (50 ° C. or higher).

  As alcohol (A), a C12-C30 natural alcohol and / or synthetic alcohol are contained.

  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). It is done.

  Synthetic alcohols include linear, unbranched saturated alcohols synthesized by the Ziegler method, linear primary alcohols or branched primary alcohols synthesized by the oxo method, and mixtures of these alcohols having different carbon numbers, and Examples include linear secondary alcohols produced by air oxidation of paraffin.

  The content (% by weight) of the alcohol (A) is preferably 10 to 90, more preferably 11 to 89, particularly preferably 12 to 88, based on the weight of the alcohol (A) and the hydrophobic component (B). Most preferably, it is 13-87. Within this range, the antifoaming property is further improved.

  The hydrophobic component (B) is at least one selected from the group consisting of mineral oils, animal and vegetable oils, fatty acid esters, polyorganosiloxanes and polyether compounds, and has a melting point lower than the melting point of the alcohol (A) or Any material having a pour point can be used without limitation.

  Mineral oil includes mineral oil that is liquid at 25 ° C, and is refined by appropriately combining vacuum distillation, oil removal, solvent extraction, hydrocracking, solvent dewaxing, sulfuric acid washing, clay refining, and hydrorefining. As product names, Cosmo Pure Spin G, Cosmo Pure Spin E, Cosmo SP-10, Cosmo SP-32 and Cosmo SC22 (above, Cosmo Oil Co., Ltd., “Cosmo” and “Pure Spin” Registered trademark of the company), MC Oil P-22, S-10S (above, Idemitsu Kosan Co., Ltd.), and Stanol 40 (ExxonMobil Corporation).

  Among animal and vegetable oils, animal oil includes beef tallow, hardened beef tallow, pork tallow, horse tallow, sheep tallow and fish oil, and trade names include beef tallow 45 ° hardened oil HO (hardened beef tallow, manufactured by NOF Corporation) and ITR (refined beef tallow, made by Miyoshi oil and fat) and the like.

  Among the animal and vegetable oils, the vegetable oil includes palm oil, rapeseed oil, palm oil, corn oil, sesame oil, castor oil, sunflower oil, safflower oil, olive oil, flaxseed oil, cottonseed oil, soybean oil and peanut oil.

  Fatty acid esters include fatty acid esters derived from 1 to 8 carbon alcohols having 1 to 30 carbon atoms and carboxylic acids having 12 to 30 carbon atoms.

  Examples of the carboxylic acid having 12 to 30 carbon atoms include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, ricinoleic acid, arachidic acid, and behenic acid.

  Among the 1 to 8 valent alcohols having 1 to 30 carbon atoms, examples of the monovalent alcohol include methanol, ethanol, propanol, butanol, hexanol, octanol and decanol.

  Similarly, examples of the dihydric alcohol include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, cyclohexanediol, butanediol, pentanediol, hexanediol, trimethylene glycol, catechol, resorcin, and hydroquinone.

  Similarly, examples of the trihydric alcohol include glycerin, trimethylolpropane, trimethylolethane, butanetriol and pentanetriol.

  Similarly, examples of the tetrahydric alcohol include pentaerythritol, diglycerin, sorbitan, and mannitan.

  Similarly, the pentahydric alcohol includes arabit, the hexavalent alcohol includes tetraglycerin, sorbit, mannitol, and the like, and the octavalent alcohol includes sucrose.

  Examples of these 1-8 octahydric alcohols include partial esters obtained by partially esterifying polyglycerol and the like.

  Polyorganosiloxane includes polydimethylsiloxane and modified polyorganosiloxane.

Examples of the polydimethylsiloxane include polydimethylsiloxane having a kinematic viscosity of 5 to 10,000 (mm ² / s, 25 ° C.), and also includes cyclooctamethyltetrasiloxane.

  As the modified polyorganosiloxane, part of the methyl group of the above polyorganosiloxane is an alkyl group having 2 to 6 carbon atoms, an alkoxyl group having 2 to 4 carbon atoms, a phenyl group, a hydrogen atom, halogen (such as chlorine and bromine). An atom, an alkoxy polyoxyalkyleneoxypropyl group (alkoxy having 1 to 6 carbon atoms, an alkylene having 2 to 3 carbon atoms), an alkoxy polyoxyalkylene group (alkoxy having 1 to 6 carbon atoms, an alkylene having 2 to 3 carbon atoms) and And / or those substituted with an aminoalkyl group having 2 to 6 carbon atoms.

  The polyether compound includes a polymer having HLB 0 to 3.4 and having an oxyalkylene group having 2 to 4 carbon atoms as a unit. The polyether compound represented by the general formula (1) is represented by the general formula (2). Selected from the group consisting of a polyether compound represented by formula (3), a polyether compound represented by formula (4), and a polyether compound represented by formula (5) Preferably, at least one selected from the above can be exemplified.

  In addition, HLB is calculated | required by the method described in 128-131 pages of "Introduction to a new surface active agent" (Takehiko Fujimoto, Sanyo Chemical Industries Co., Ltd. issue), 0-2.9 are preferable, More preferably Is 0 to 2.4, particularly preferably 0 to 1.9.

R ¹ is a reaction residue of an active hydrogen compound having 1 to 25 carbon atoms, R ² and R ³ are monovalent organic groups having 1 to 24 carbon atoms, R ⁴ is a divalent organic group having 1 to 24 carbon atoms, R ⁵ is a hydroxyl group or a monovalent organic group having 1 to 24 carbon atoms, AO and OA are oxyalkylene groups having 2 to 18 carbon atoms, or glycidol, a reaction residue of an alkyl glycidyl ether or alkenyl glycidyl ether having 4 to 18 carbon atoms. In the case where (OA) _n or (AO) n represents a group, the proportion of the oxyethylene group is 0 to 20% by weight, and n is an integer of 1 to 100, and a plurality of n is present in one molecule. S is an integer of 1 to 10, p is an integer of 0 to 10, q is an integer of 0 to 9, r is an integer of 0 to 9, m is an integer of 0 to 9, p + r is an integer of 1 to 10, p + q + r is an integer of 1 to 10, p q + r + m is 2 to 10.

The reaction residue (R ¹ ) of an active hydrogen compound having 1 to 25 carbon atoms means a reaction residue obtained by removing active hydrogen from an active hydrogen compound having 1 to 25 carbon atoms.
Examples of the active hydrogen-containing compound having 1 to 25 carbon atoms include compounds containing at least one hydroxyl group (—OH), imino group (—NH—), amino group (—NH ₂ ) and / or carboxyl group (—COOH). And includes alcohols, amides, amines, carboxylic acids, hydroxycarboxylic acids and aminocarboxylic acids.

  Examples of alcohol include monool (methanol, butanol, stearyl alcohol, oleyl alcohol and isostearyl alcohol) and polyol (ethylene glycol, propylene glycol, glycerin, diglycerin, tetraglycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, Dihydroxyacetone, fructose, glucose, mannose, galactose, sucrose, lactose, trehalose, etc.).

  Examples of the amide include monoamide (formic acid amide, propionic acid amide, stearyl amide, etc.), polyamide (malonic acid diamide, ethylene bisoctylamide, etc.) and the like.

  Examples of amines include monoamines (such as dimethylamine, ethylamine, aniline and stearylamine) and polyamines (such as ethylenediamine, diethylenetriamine and triethylenetetramine).

  Examples of the carboxylic acid include monocarboxylic acids (such as acetic acid, stearic acid, oleic acid, and benzoic acid) and polycarboxylic acids (such as maleic acid and hexanedioic acid).

  Examples of the hydroxycarboxylic acid include hydroxyacetic acid, tartaric acid, malic acid and 12-hydroxystearic acid.

  Examples of aminocarboxylic acids include glycine, 4-aminobutyric acid, 6-aminohexanoic acid and 12-aminolauric acid.

Examples of the monovalent organic group (R ² , R ³ ) having 1 to 24 carbon atoms include an alkyl group (R), an alkenyl group (R ′), an acyl group (—COR), an aroyl group (—COR ′), N -Alkylcarbamoyl group (-CONHR), N-alkenylcarbamoyl group (-CONHR '), alkylcarbonylamino group (-NHCOR), alkenylcarbonylamino group (-NHCOR'), alkylcarboxyamino group (alkylcarbamate group, -NHCOOR) ) And an alkenylcarboxyamino group (alkenyl carbamate group, —NHCOOR ′).

  Examples of the alkyl group (R) include methyl, ethyl, isopropyl, t-butyl, octyl, 2-ethylhexyl, dodecyl and octadecyl.

  Examples of the alkenyl group (R ′) include vinyl, propenyl, hexenyl, isooctenyl, dodecenyl and octadecenyl.

Among the hydroxyl groups or monovalent organic groups having 1 to 24 carbon atoms (R ⁵ ), the monovalent organic groups having 1 to 24 carbon atoms include the same organic groups as described above.

Examples of the divalent organic group (R ⁴ ) having 1 to 24 carbon atoms include an alkylene group (T), an alkenylene group (T ′), a 1-oxaalkylene group (—OT—), and a 1-oxaalkenylene group (—OT). '-), 1-oxoalkylene group (-COT-), 1-oxoalkenylene group (-COT'-), 1-aza-2-oxoalkylene group (-NHCOT-), 1-aza-2-oxoalkenylene Group (-NHCOT'-), 1-oxo-2-azaalkylene group (-CONHT-), 1-oxo-2-azaalkenylene group (-CONHT'-), 1-aza-2-oxo-3-oxa An alkylene group (—NHCOOT—) and a 1-aza-2-oxo-3-oxaalkenylene group (—NHCOOT′—) are included.

  Examples of the alkylene group (T) include methylene, ethylene, isobutylene, 1,10-decylene, 1,2-decylene, 1,12-dodecylene, 1,2-dodecylene and 1,2-octadecylene.

  Examples of the alkenylene group (T ′) include ethynylene, isobutynylene, 1,10-decynylene, 1-octylethynylene, 1-octenylethylene, 1,12-dodecynylene, and 1-octadecenylethylene.

  Of the oxyalkylene group having 2 to 18 carbon atoms or the reaction residue (AO, OA) of glycidol, alkyl glycidyl ether having 4 to 18 carbon atoms or alkenyl glycidyl ether, the oxyalkylene group having 2 to 18 carbon atoms is the above. Oxyalkylene groups having 2 to 18 carbon atoms (oxyethylene, oxypropylene, oxybutylene, oxyisobutylene, oxy-1,2-decylene, oxy-1,12-dodecylene, oxy-1,2-dodecylene And oxy-1,2-octadecylene).

  Further, among (AO, OA), examples of the alkyl glycidyl ether having 4 to 18 carbon atoms include methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, and octadecyl glycidyl ether. It is done.

  Moreover, among (AO, OA), as alkenyl glycidyl ether having 5 to 18 carbon atoms, vinyl glycidyl ether, butenyl glycidyl ether, 2-ethylhexenyl glycidyl ether, dodecenyl glycidyl ether and octadecenyl glycidyl ether are used. Examples include ether.

  n is an integer of 1 to 100, preferably an integer of 2 to 75, and more preferably an integer of 3 to 50.

  The polyether compound represented by the general formula (1) includes polyoxypropylene monobutyl ether, propylene oxide ethylene oxide block adduct of tetradecyl alcohol, propylene oxide ethylene oxide block adduct of trimethylolpropane, polyoxypropylene glycol, polyoxy Ethylene polyoxypropylene glycol (block addition), propylene oxide oxide adduct of glycerin, ethylene oxide propylene oxide block adduct of glycerin, propylene oxide adduct of monododecylamine, polyoxypropylene monooleate, propylene oxide 2-ethylhexyl glycidyl of glycerin Block adducts, propylene oxide butylene oxide block adducts of sucrose and pentaerythritol Ethylene oxide propylene oxide oxide block adduct of Lithol like.

  The polyether compound represented by the general formula (2) includes polyoxypropylene monobutyl ether monooleate, distearate of polyoxyethylene polyoxypropylene glycol (block addition), monostearate of propylene oxide adduct of glycerin, maleic acid And mono-N-hexylcarbamic acid ester of propylene oxide adduct of sucrose and the like.

  Examples of the polyether compound represented by the general formula (3) include propylene oxide adducts of ethylenebisstearylamide, propylene oxide adducts of glycerin monostearyl ester and propylene oxide adducts of sucrose mono (2-ethylhexylglycidyl) ether. And mono N-decylcarbamic acid ester.

  Examples of the polyether compound represented by the general formula (4) include a monooleate of a propylene oxide adduct of castor oil and a propylene oxide adduct of glycerin bis (12-hydroxystearate).

  Examples of the polyether compound represented by the general formula (5) include a reaction product of polyoxypropylene monolauryl ether, polyoxypropylene glycol and hexamethylene diisocyanate, and polyoxypropylene monostearyl ether and polyoxyethylene polyoxypropylene glycol ( And a reaction product of xylene diisocyanate with a block addition).

  The content (% by weight) of the hydrophobic component (B) is preferably from 10 to 90, more preferably from 11 to 89, and particularly preferably from 12 to 90, based on the weight of the alcohol (A) and the hydrophobic component (B). 88, most preferably 13-87. Within this range, the antifoaming property is further improved.

  The hydrophobic component (B) has a melting point or pour point lower than the melting point of the alcohol (A), preferably a melting point or pour point lower by 3 to 120 ° C. than the melting point of the alcohol (A), more preferably 5 to 105. A melting point or pour point having a low melting point or pour point, particularly preferably a melting point or pour point having a low temperature of 10 to 90 ° C. The melting point or pour point (° C.) of the hydrophobic component (B) is preferably −75 to 55, more preferably −70 to 50, and particularly preferably −65 to 45. Within this range, the antifoaming property is further improved.

  The particles (X) are composed of the alcohol (A) and the hydrophobic component (B), but may include a hydrophobic metal oxide, a fatty acid amide, a wax and the like as other components in addition to these.

The hydrophobic metal oxide includes a hydrophobic metal oxide obtained by hydrophobizing a metal oxide powder with a hydrophobizing agent, and examples include hydrophobic silica, hydrophobic alumina, hydrophobic titania, and hydrophobic zinc oxide. .
Examples of hydrophobic metal oxides available on the market include Nipsil SS-10, SS-40, SS-50 and SS-100 (hydrophobic silica, Tosoh Silica Corporation, “Nipsil” is Tosoh Silica). ), AEROSIL R972, RX200 and RY200 (hydrophobic silica, Nippon Aerosil Co., Ltd., “AEROSIL” is a registered trademark of Evonik Degussa GmbH)), SIPERNAT D10, D13 and D17 (hydrophobic) Silica, Degussa Japan Co., Ltd., “SIPRNAT” is a registered trademark of Evonik Degussa GmbH, TS-530, TS-610, TS-720 (hydrophobic silica, Cabot Corporation), AEROSIL R202, R805 And R812 (hydrophobic silica, Degussa Japan Co., Ltd.), REOLOSIL MT-10, DM-10 and DM-20S (hydrophobic silica, Tokuyama Co., Ltd., “REOLOSIL” is a registered trademark of the same company), SYLOPHOBIC 100, 702 , 505 and 603 (hydrophobic silica, Fuji Silysia Chemical Co., Ltd., “SYLOPHOBIC” is a registered trademark of the company), MT-100Z (hydrophobic titania, Teica Co., Ltd.), MTY-700BS (hydrophobic titania, Teica Co., Ltd.) Co., Ltd.), MZY-303S (hydrophobic zinc oxide, Teika Co., Ltd.) and SpectrAl TA-78 (hydrophobic alumina, Cabot Corporation, “SpectrAl” is a registered trademark of the same company).

  As fatty acid amide, a reaction product (fatty acid diamide) of a C1-C6 alkylenediamine or alkenylenediamine and a C10-C22 fatty acid and / or a C1-C22 alkylamine, alkenylamine or ammonia and carbon A reaction product (fatty acid monoamide) with a fatty acid of several tens to 22 is included.

  Examples of fatty acid diamides include ethylene bisstearylamide, ethylene bispalmitylamide, ethylene bismyristylamide, ethylene bislaurylamide, ethylene bisoleylamide, propylene bisstearylamide, propylene bispalmitylamide, propylene bismyristylamide, propylene bislauryl Amide, propylene bis oleyl amide, butylene bis stearyl amide, butylene bis palmityl amide, butylene bis myristyl amide, butylene bis lauryl amide, butylene bis oleyl amide, methylene bis lauryl amide, methylene bis stearyl amide, hexamethylene bis stearyl amide, etc. Can be mentioned.

  Examples of the fatty acid monoamide include N-stearyl stearyl amide, oleic acid amide, erucic acid amide, and stearyl amide.

  Of these, fatty acid diamide is preferable from the viewpoint of antifoaming property, etc., more preferably ethylene bisstearylamide, ethylene bispalmitylamide, ethylene bislaurylamide, methylene bisstearylamide, and hexamethylene bisstearylamide, particularly preferably Ethylene bisstearyl amide, ethylene bis palmityl amide and ethylene bis myristyl amide. These amides may be a mixture of two or more, and in the case of a mixture, it is preferable that the above-mentioned preferable ones are 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, it is contained by 80% by weight or more.

  As a subcomponent (component contained in addition to the main component) in the fatty acid amide, an unreacted amine, an unreacted carboxylic acid, and the like are included in addition to the amide other than the preferred range. The content (% by weight) of the accessory component is preferably less than 60, more preferably less than 50, particularly preferably less than 40, then preferably less than 30 and most preferably less than 20 based on the weight of the fatty acid amide. .

  The wax preferably includes at least one selected from the group consisting of oxidized polyethylene wax, microcrystalline wax, hydroxyl group-containing wax, paraffin wax, and natural wax. Oxidized polyethylene wax, microcrystalline wax, paraffin wax, 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 and montan wax.

  The volume average particle diameter (μm) of the particles (X) is preferably 1 to 50 μm, more preferably 1.3 to 40, particularly preferably 1.5 to 35, and most preferably 2 to 30. Within this range, the defoaming property is even better.

  The volume average particle diameter (μm) of the particles (X) is determined by a laser diffraction / scattering particle size distribution measuring apparatus {for example, Partica LA-950V2 (flow cell type, refractive index of dispersoid = 1.45, refractive index of dispersion medium). = 1.33, number of iterations 15), HORIBA, Ltd.} is measured as follows.

<Measurement method>
Blank measurement is performed while ion-exchanged water is circulated in the flow cell (circulation strength 5). About 10 mL of ion-exchanged water is put into a 100 mL glass beaker, and a few drops of a measurement sample (dispersion (Z)) are added and mixed until uniform to prepare a dispersion. The dispersion is added little by little to the flow cell, and the measurement is performed by adjusting to an appropriate transmitted light intensity (transmitted light intensity of blue LED is 80 to 90% or transmitted light intensity of red LED is 70 to 90%).
The measured value is calculated by subtracting the blank measurement value.

  The volume average particle diameter of the particles (X) can be adjusted by the step of obtaining a dispersion (Z) described later (dispersing step), the content of a surfactant (Fz) that can be used as necessary, and the like. When dispersion is performed by applying stronger shear in the dispersion step, the volume average particle diameter of the emulsion particles tends to be small. Moreover, there exists a tendency for the volume average particle diameter of emulsion particle | grains to become small, so that there is much content of surfactant (Fz).

  The content (% by weight) of the particles (X) is preferably 10 to 60, more preferably 11 to 58, particularly preferably 12 to 56, and most preferably 13 to 54, based on the weight of the dispersion (Z). It is.

The dispersion (Z) is a dispersion in which the particles (X) are dispersed in water. Therefore, the dispersion (Z) contains water (E) in addition to the particles (X).
Examples of water (E) include tap water, industrial water, deionized water, and distilled water.

  The content (% by weight) of water (E) is preferably 40 to 90, more preferably 42 to 89, particularly preferably 44 to 88, and most preferably 46 to 87, based on the weight of the dispersion (Z). is there.

  In addition to the particles (X) and water (E), the dispersion (Z) includes a surfactant (Fz), a thickener, an antiseptic (antibacterial / antifungal dictionary, Japanese Society for Antibacterial and Fungal Society, Showa 61 Year 1st edition, pages 1-32 etc.) and / or antifreeze agents.

Surfactants (Fz) include nonionic surfactants, anionic surfactants, and mixtures thereof.
As the nonionic surfactant, those having an HLB of 3.5 to 20 can be used, preferably those of HLB 3.6 to 19.5, more preferably those of HLB 3.7 to 19, and most preferably HLB 4 to 18. Five.

  Nonionic surfactants include sorbitan fatty acid esters, ethylene oxide adducts of sorbitan fatty acid esters, polyoxyethylene polyoxypropylene block polymers, polyoxyethylene alkylaryl ethers, vegetable oil ethylene oxide adducts, polyoxyethylene fatty acid esters, Examples include polyoxyethylene alkyl ether, glycerin fatty acid ester, ethylene oxide adduct of glycerin fatty acid ester, and modified silicone.

  Examples of sorbitan fatty acid esters include esters of sorbitan and fatty acids having 12 to 22 carbon atoms, including sorbitan monolaurate (HLB 8.6, for example, Nonion LP-20R; NOF Corporation), sorbitan monopalmitate (HLB6). .7, for example, Nonion PP-40R pellets; NOF Corporation), sorbitan monostearate (HLB 4.7, for example, Nonion SP-60R pellets; NOF Corporation), sorbitan monooleate (HLB 4.3, for example) Nonionic OP-80R; NOF Corporation), sorbitan trioleate (HLB1.8, for example, Nonion OP-85R; NOF Corporation), sorbitan monooleate (HLB4.3, for example, Ionette S-80; Sanyo) Kasei Co., Ltd., “Ionet” It is a trademark.), And the like.

  The ethylene oxide adduct of sorbitan fatty acid ester includes an ethylene oxide 1-40 mol adduct of sorbitan fatty acid ester, and polyoxyethylene sorbitan monolaurate (HLB16.7, for example, Nonion LT-221; NOF Corporation), Polyoxyethylene sorbitan monostearate (HLB15.7, for example, Nonion ST-221; NOF Corporation), polyoxyethylene sorbitan monooleate (HLB15.7, for example, Nonion OT-221; NOF Corporation), etc. Is mentioned.

  The polyoxyethylene polyoxypropylene block polymer includes a copolymer of 5 to 200 mol of ethylene oxide and 5 to 200 mol of propylene oxide, and a polyoxyethylene (25 mol) polyoxypropylene (30 mol) block polymer (for example, , New Pole PE-64; Sanyo Chemical Industries, Ltd., "New Pole" is a registered trademark of the company) and polyoxyethylene (48 mol) polyoxypropylene (35 mol) block polymer (for example, New Pole PE- 75; Sanyo Chemical Industries Ltd.).

  Examples of the polyoxyethylene alkylaryl ether include polyarylethylene ethers of alkylaryl having an alkyl group having 6 to 18 carbon atoms, such as polyoxyethylene (4 mol) nonylphenol ether (for example, Nonipol 40; Sanyo Chemical Industries, Ltd.). , “Nonipol” is a registered trademark of the same company), polyoxyethylene (10 mol) nonylphenol ether (for example, Nonipol 100; Sanyo Chemical Industries, Ltd.), and the like.

  The ethylene oxide adduct of vegetable oil includes 1 to 200 mol of ethylene oxide adduct of vegetable oil, such as castor oil ethylene oxide adduct (eg, UNIOX HC-40; NOF Corporation, “UNIOX” is a registered trademark of the company) And the like.

  Examples of the fatty acid ester of polyoxyethylene include monoesters and diesters of polyoxyethylene having a number average molecular weight of 200 to 4000 and a fatty acid having 6 to 22 carbon atoms, and polyoxyethylene glycol having a number average molecular weight of 600 and oleic acid, Diesters (for example, Ionette DO-600; Sanyo Chemical Industries, Ltd.) and monoesters of polyoxyethylene glycol having a number average molecular weight of 600 and oleic acid (for example, Ionet MO-600; Sanyo Chemical Industries, Ltd.) It is done.

  Polyoxyethylene alkyl ethers include 1 to 100 moles of alkanol oxyethylene adducts of 6 to 22 carbon atoms. Narrow Acty CL-40 (HLB8.9, Sanyo Chemical Industries, Ltd., "Narrow Acty" Naloacty CL-100 (HLB13.3, Sanyo Chemical Industries, Ltd.) and the like.

  Examples of the glycerin fatty acid ester include monoesters of fatty acids having 6 to 22 carbon atoms and glycerin, and include glycerol monostearate (for example, monoglyceride MD, HLB5.5, NOF Corporation).

  The ethylene oxide adduct of glycerin fatty acid ester includes 1 to 100 mol of ethylene oxide adduct of glycerin fatty acid ester, and ethylene oxide adduct of glycerin coconut fatty acid ester (for example, UNIGLY MK-207, HLB13.0, NOF Corporation). , “Unigri” is a registered trademark of the company).

  As the modified silicone, a part of methyl group of dimethylsiloxane is alkoxypolyoxyalkyleneoxypropyl group (1-6 carbon atoms of alkoxy, 2-3 carbon atoms of alkylene, polymerization degree 2-50), alkoxypolyoxyalkylene group (Alkoxy having 1 to 6 carbon atoms, alkylene having 2 to 3 carbon atoms, polymerization degree of 2 to 50) and the like are included.

  Among these, sorbitan fatty acid ester, ethylene oxide adduct of sorbitan fatty acid ester, polyoxyethylene alkyl ether, monoester and diester of polyoxyethylene and fatty acid, glycerin fatty acid ester and ethylene oxide adduct of glycerin fatty acid ester are preferable.

  Anionic surfactants include alkyl aryl sulfonates, alkyl diphenyl ether disulfonates, petroleum sulfonate salts, polyoxyethylene alkyl sulfonate salts and polyoxyethylene alkyl phosphate salts.

Examples of the alkyl aryl sulfonate include alkyl aryl sulfonates having 7 to 24 carbon atoms, and examples thereof include p-toluene sulfonate and dodecylbenzene sulfonate.
Although it does not restrict | limit especially as a salt, Alkali metal (sodium, potassium, etc.) salt, alkaline earth metal (calcium, magnesium, etc.) salt, ammonium salt, and C1-C18 amine salt (triethanolamine, trimethylamine, propylamine) Etc.) (the same shall apply hereinafter).

  Examples of the alkyl diphenyl ether sulfonate include alkyl diphenyl ether disulfonates having an alkyl group of 6 to 18 carbon atoms, such as dodecyl diphenyl ether disulfonate.

  The petroleum sulfonate salt includes a sulfonated petroleum-based lubricating oil fraction.

  Examples of the polyoxyethylene alkyl sulfate salt include polyoxyethylene alkyl sulfate salts having 6 to 22 carbon atoms, and include polyoxyethylene lauryl sulfate salts.

  Examples of the polyoxyethylene alkyl phosphate ester salt include polyoxyethylene alkyl phosphate esters having 6 to 22 carbon atoms, such as polyoxyethylene stearyl phosphate ester salts.

  Of these, alkyl aryl sulfonates, petroleum sulfonate salts and alkyl diphenyl ether disulfonates are preferred, more preferably dodecylbenzene sulfonate and petroleum sulfonate salts, particularly preferably dodecylbenzene sulfonate calcium salt and petroleum sulfonate calcium salt. It is.

  When the surfactant (Fz) is contained, the content (% by weight) of the surfactant (Fz) is preferably 0.01 to 10 based on the weight of the dispersion (Z), more preferably 0.8. 1-8, particularly preferably 0.2-7, most preferably 0.3-5.

  Thickeners include xanthan gum, locust bean gum, guar gum, carrageenan, alginic acid and its salts, tragacanth gum, magnesium aluminum silicate, bentonite, polyvinyl alcohol, methylcellulose, hydroxyethylcellulose, gelatin, agar and carboxyl group Sticking agents (trade names such as SN thickener 636, SN thickener 641, SN thickener 617, etc .; San Nopco Corporation), associative thickeners containing polyoxyethylene chains (trade names such as SN thickener 625N, SN Thickener 665T, etc.).

  Examples of the antifreezing agent include ethylene glycol, propylene glycol, and glycerin.

  Examples of preservatives include formalin and 5-chloro-2-methyl-4-isothiazolin-3-one.

  The content (% by weight) of the dispersion (Z) is preferably 65 to 95, more preferably 67 to 93, particularly preferably based on the weight of the dispersion (Z) and the nucleating agent-containing polyether (Y). 69-91, most preferably 70-90.

  The nucleating agent (C) can be used without limitation as long as it is at least one selected from the group consisting of fatty acid metal salts, fatty acid amides, waxes, hydrophobic metal compounds and synthetic resins.

  Examples of fatty acid metal salts include salts of fatty acids having 12 to 22 carbon atoms and metals (such as alkaline earth metals, aluminum, manganese, cobalt, copper, iron, zinc and nickel), and include aluminum stearate, manganese stearate, Examples include cobalt stearate, copper stearate, iron stearate, nickel stearate, calcium stearate, zinc laurate and magnesium behenate.

  About fatty acid metal salt, the quantity relationship between a metal and a fatty acid may be any of 1 to 3 moles of fatty acid (mono, di, and tri) per mole of metal. A mixture of From the viewpoint of defoaming property and the like, when the metal is aluminum and iron, di- and tri-isomers are preferable, and when alkaline metal (such as calcium), zinc, cobalt, manganese, nickel and copper, di-isomers are preferable.

  As fatty acid amide, the same thing as the other structural component (fatty acid amide) which comprises particle | grains (X) is contained, and a preferable thing is also the same.

  As the wax, the same components as the other constituent components (wax) constituting the particles (X) are included, and preferable ones are also the same.

  As a hydrophobic metal oxide, the same thing as the other structural component (hydrophobic metal oxide) which comprises particle | grains (X) is contained, and a preferable thing is also the same.

  The synthetic resin includes a synthetic resin having an ethylenically unsaturated monomer (m1) as a structural unit and a synthetic resin having a polycondensation / polyaddition monomer (m2) as a structural unit.

  Examples of the ethylenically unsaturated monomer (m1) include known monomers, such as (meth) acrylic acid; (meth) acrylic acid alkyl ester having 1 to 22 carbon atoms {methyl (meth) acrylate, (meth) Ethyl acrylate, butyl (meth) acrylate, (meth) acrylic acid (2-ethylhexyl), stearyl (meth) acrylate and behenyl (meth) acrylate}, etc .; alkylene oxide of carbon having 1 to 18 carbon atoms (carbon (Math. 2-4) (meth) acrylate of adduct {(meth) acrylic acid ester of 30 mol of propylene oxide of methanol, (meth) acrylic acid ester of 30 mol of propylene oxide of 2-ethylhexanol, and stearyl alcohol (Meth) acrylic acid ester of ethylene oxide 30 adduct of ) Acrylonitrile; styrene {styrene, methylstyrene and hydroxystyrene}; diaminoethyl (meth) acrylate; polyfunctional vinyl monomer {divinylbenzene, ethylene di (meth) acrylate, trimethylolpropane tri (meth) acrylate and polyethylene glycol (degree of polymerization) 14) di (meth) acrylate}; allyl alcohol; alkylene oxide (2 to 4 carbon atoms) adduct of allyl alcohol {propylene oxide 2-mole adduct of allyl alcohol, etc.}; 2-buten-1-ol; (meth) acrylic Acid (2-hydroxyethyl); alkylene oxide (2 to 4 carbon atoms) adduct of (meth) acrylic acid (2-hydroxyethyl) {propylene oxide 4 mol adduct of (meth) acrylic acid (2-hydroxyethyl) etc}; Fine vinyl acetate and the like can be used.

  These may be used singly or in combination of two or more. However, monomers containing at least one polyoxyalkylene group {alkylene oxide of an alcohol having 1 to 18 carbon atoms (2 to 2 carbon atoms) 4) Adduct (meth) acrylate; polyethylene glycol (degree of polymerization 14) di (meth) acrylate; alkylene oxide (carbon number 2 to 4) adduct of allyl alcohol; and (meth) acrylic acid (2-hydroxyethyl) It is preferable to use an adduct of an alkylene oxide (having 2 to 4 carbon atoms).

  (Meth) acrylic acid means acrylic acid and / or methacrylic acid, (meth) acrylonitrile means acrylonitrile and / or methacrylonitrile, and (meth) acrylate means acrylate and / or methacrylate. Show.

  A synthetic resin having an ethylenically unsaturated monomer (m1) as a structural unit can be obtained by polymerization by a known method.

  The polycondensation / polyaddition monomer (m2) includes known monomers, and includes polyisocyanate (m21), polyamine (m22), polyol (m23), and polycarboxylic acid (m24).

  Examples of the polyisocyanate (m21) include diisocyanates having 8 to 16 carbon atoms (hexamethylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate, 4-4′-methylenebis (cyclohexyl isocyanate), etc.) and modified products thereof (trimethylolpropane of diisocyanate). Adducts, biuret condensates and isocyanurate condensates, etc.}.

  Examples of the polyamine (m22) include polyamines having 2 to 6 carbon atoms, such as ethylenediamine, hexamethylenediamine, and triethylenetetramine.

  Examples of the polyol (m23) include polyhydric alcohols having 2 to 6 carbon atoms (ethylene glycol, propylene glycol, butylene glycol, glycerol, diglycerin, pentaerythritol, etc.); and these polyhydric alcohols having 2 to 4 carbon atoms. Adducts obtained by adding 1 to 50 moles of oxide per hydroxyl group {ethylene oxide adduct of polyhydric alcohol, propylene oxide adduct, butylene oxide adduct, ethylene oxide / propylene oxide block adduct, propylene oxide / butylene oxide block adduct, etc. } Etc. are mentioned.

  Examples of the polycarboxylic acid (m24) include C4-C14 polycarboxylic acids, including terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, and fumaric acid. , Maleic acid, itaconic acid and dimer acid.

  The synthetic resin (A2) having the polycondensation / polyaddition monomer (m2) as a structural unit includes polyurea, polyurethane, polyester and the like having the above monomer as a structural unit, and can be obtained by polymerization by a known method. it can.

For the synthetic resin, fine particles obtained by emulsion polymerization or suspension polymerization of the above monomer in the polyether compound (D) may be used, or particles obtained by solution polymerization or the like are dried by a method such as spray drying. -You may use what was atomized (it grind | pulverizes further if necessary), and may use the grinding | pulverization microparticles | fine-particles obtained by grind | pulverizing the bulk resin obtained by bulk polymerization.
Further, classification may be performed in order to make the particle diameters of these particles uniform, and the obtained classified particles may be used.

  When pulverizing, the pulverization may be performed using a jet mill, a bead mill or the like.

Synthetic resins are also available from the market. For example, the following products can be used.
Ultiflow FS-7301 (manufactured by Sanyo Kasei Kogyo Co., Ltd., polyether dispersion of ethylenically unsaturated monomer copolymer, “Altiflow” is a registered trademark of the company), Dimic beads UCN-8070CM clear (large Nissei Kagaku Kogyo Co., Ltd., polyurethane beads, “Dymic Beads” is a registered trademark of the company), Tuftic F-120, F-167 (Toyobo Co., Ltd., ethylenically unsaturated monomer copolymer water) Dispersion; “Toughtic” is a registered trademark of the company)

  The content (% by weight) of the nucleating agent (C) is preferably 0.1 to 10, more preferably 0.2 to 9.5, based on the weight of the nucleating agent (C) and the polyether compound (D). Particularly preferably, it is 0.3 to 9, most preferably 0.5 to 8. Within this range, the antifoaming property is further improved.

  The melting point (° C.) of the nucleating agent (C) is preferably at least 60 ° C., more preferably 60 to 2000, particularly preferably 70 to 1850, and most preferably 75 to 1650.

  Examples of the polyether compound (D) include a polymer having HLB 0 to 3.4 and an oxyalkylene group having 2 to 4 carbon atoms as a unit, and a polyether compound (D1) represented by the general formula (1), Polyether compound (D2) represented by general formula (2), polyether compound (D3) represented by general formula (3), polyether compound (D4) represented by general formula (4), and general formula Preferable examples include at least one selected from the group consisting of the polyether compound (D5) represented by (5). These polyether compounds (D) are the same as the polyether compounds represented by the general formulas (1) to (5).

The content (% by weight) of the polyether compound (D) is preferably 90 to 99.9, more preferably 90.5 to 99.99, based on the weight of the nucleating agent (C) and the polyether compound (D). 8, particularly preferably 91 to 99.7, most preferably 92 to 99.5. Within this range, the antifoaming property is further improved.

  The number average particle size (μm) of the nucleating agent (C) in the nucleating agent-containing polyether (Y) is preferably 0.05 to 20, more preferably 0.07 to 18, particularly preferably 0.08 to 16. Most preferably, it is 0.1-14.

  In addition, the number average particle diameter of the nucleating agent (C) in the nucleating agent-containing polyether (Y) is determined based on the polyether compound (D without dissolving and aggregating the dispersoid (nucleating agent) in the measurement sample. ) That dissolves uniformly. For example, methanol, polyoxypropylene glycol, acetone, propylene oxide adduct of glycerin or hexane can be used, and an appropriate one is selected according to the dispersoid and the polyether compound (D). }, And a laser diffraction particle size distribution measuring apparatus (for example, manufactured by Shimadzu Corporation) having the measurement principle described in JIS Z8825-1-2001 “Particle Size Analysis—Laser Diffraction Method—Part 1: Measurement Principle” SALD-1100, LA-950 manufactured by HORIBA, Ltd., LA-950V2 manufactured by HORIBA, Ltd., Microtrack particle size distribution analyzer UPA-ST150 manufactured by Nikkiso Co., Ltd. Etc.) and the like.

  The nucleating agent-containing polyether (Y) is composed of the nucleating agent (C) and the polyether compound (D). In addition to these, other constituents include mineral oil, animal / vegetable oil, silicone oil and / or A modified silicone oil may be included.

  Mineral oils and animal / vegetable oils include those used for the hydrophobic component (C), and preferred ones are also the same.

Examples of the silicone oil include polydimethylsiloxane having a kinematic viscosity of 5 to 10,000 (mm ² / s, 25 ° C.), and also includes cyclooctamethyltetrasiloxane.

  As the modified silicone oil, a part of the methyl group of the above dimethylsiloxane is an alkyl group having 2 to 6 carbon atoms, an alkoxyl group having 2 to 4 carbon atoms, a phenyl group, a hydrogen atom, a halogen (such as chlorine and bromine) atom, C2-C6 aminoalkyl group and / or alkoxy polyoxyalkyleneoxypropyl group (alkoxy having 1 to 6 carbon atoms, alkylene having 2 to 3 carbon atoms, polymerization degree of 2 to 50), alkoxy polyoxyalkylene group (alkoxy 1 to 6 carbon atoms, 2 to 3 carbon atoms of alkylene, a degree of polymerization of 2 to 50) and the like are included.

  The content (% by weight) of the nucleating agent-containing polyether (Y) is preferably 5 to 35, more preferably 7 to 33, based on the weight of the dispersion (Z) and the nucleating agent-containing polyether (Y). Especially preferably, it is 9-31, Most preferably, it is 10-30.

  The antifoaming agent of the present invention can be produced by a method in which a dispersion (Z) in which particles (X) are dispersed in water and a polyether (Y) containing a nucleating agent are mixed by stirring and homogenized.

  The dispersion (Z) is easily obtained by uniformly mixing the alcohol (A) and the hydrophobic component (B) to prepare a mixture, and then emulsifying and dispersing the mixture in water by a known method or the like.

  The nucleating agent-containing polyether (Y) can be easily obtained by emulsifying and dispersing the nucleating agent (C) in the polyether compound (D) by a known method or the like. The following methods (P1) to (P3) ).

<Method (P1); When a nucleating agent (C) contains a fatty acid metal salt, a fatty acid amide and / or a wax>
A dissolving step (p11) of dissolving a fatty acid metal salt, a fatty acid amide and / or a wax while heating and stirring a fatty acid metal salt, a fatty acid amide and / or a wax and a part of the polyether compound (D). ),

  A mixing step (p12) in which the remaining portion of the polyether compound (D) is stirred and a solution is added to the remaining portion to obtain a mixture; and

  A method comprising a dispersion step (p13) of homogenizing the mixture to obtain a dispersion of fatty acid metal salt, fatty acid amide and / or wax.

  The heating and stirring temperature (° C.) is not limited as long as the fatty acid metal salt, fatty acid amide and / or wax can be dissolved, but is preferably 100 to 180, more preferably 103 to 170, particularly preferably 105 to 160, most preferably. 110-150.

  The heating and stirring time is not limited as long as the fatty acid metal salt, fatty acid amide and / or wax can be dissolved, but it is preferably as short as possible in order to prevent decomposition and evaporation of the polyether compound (D).

  Heating and stirring may be performed under sealed conditions (may be under pressure) or under open conditions.

In the mixing step (p12), it is preferable to keep the solution in which the fatty acid metal salt, fatty acid amide and / or wax are dissolved by heating and stirring the solution while the solution is being added.
The temperature of the remainder of the polyether compound (D) is preferably maintained at 0 to 60 ° C., more preferably 0 to 50 ° C., particularly preferably 0 to 45 ° C., most preferably from the viewpoint of defoaming properties. Is 0 to 40 ° C. That is, it is preferable to stir the remaining portion of the polyether compound (D) cooled to 0 to 60 ° C., and add the solution little by little while maintaining the temperature of the remaining portion at 0 to 60 ° C. to obtain a mixture.

  The homogenization treatment is not limited as long as the mixture containing the fatty acid metal salt, fatty acid amide and / or wax can be homogenized, but an emulsifying and dispersing machine (bead mill, disper mill, homogenizer or gorin homogenizer, ultrasonic emulsifier, etc.) is used. And homogenizing.

  As a nucleating agent (C), when multiple types of fatty acid metal salts, fatty acid amides and waxes are included (this includes cases where multiple types of fatty acid metal salts are included), multiple types of nucleating agents are dissolved and dissolved. After obtaining the liquid {dissolution step (p11)}, a dispersion of the nucleating agent {polyether containing the nucleating agent (Y)} may be obtained, or dispersions of fatty acid metal salts, fatty acid amides or waxes may be obtained. Then, these dispersions may be uniformly mixed to obtain a nucleating agent dispersion {polyether containing nucleating agent (Y)}.

<Method (P2); When fatty acid metal salt is contained as nucleating agent (C)>
A dissolving step (p21) of dissolving a fatty acid metal salt to obtain a solution while heating and stirring the fatty acid metal salt and the polyether compound (D);
A method comprising a dispersion step (p22) of cooling a solution and then stirring and mixing to obtain a dispersion of a fatty acid metal salt.

  The heating and stirring temperature (° C.) is not limited as long as the fatty acid metal salt can be dissolved, but is preferably 100 to 180, more preferably 103 to 170, particularly preferably 105 to 160, and most preferably 110 to 150.

  The heating and stirring time is not limited as long as the fatty acid metal salt can be dissolved, but is preferably as short as possible in order to prevent decomposition or evaporation of the polyether compound (D).

  Heating and stirring may be performed under sealed conditions (may be under pressure) or under open conditions.

  The stirring and mixing in the dispersion step (p22) is not limited as long as it can be stirred and mixed until there are no coarse particles (particle length of 50 μm or more) in the mixed solution, but using a disper mill, a homogenizer, a homomixer or the like at 5 to 40 ° C. Preferably it is done. Presence or absence of coarse particles is confirmed with an optical microscope (for example, Olympus BX-60, Cytoviva HRA nanoimaging adapter, objective lens: UPlanAPO 100x / 1.35 oil, eyepiece: WH10x / 22) can do.

  When a nucleating agent (C) includes a plurality of types of fatty acid metal salts, a plurality of types of fatty acid metal salts are dissolved to obtain a solution {dissolution step (p21)}, and a nucleating agent dispersion {with a nucleating agent Polyether (Y)} may be obtained, or after obtaining each dispersion for each type of fatty acid metal salt, these dispersions are uniformly mixed to obtain a nucleating agent dispersion {polyether containing nucleating agent (Y)} may be obtained.

<Method (P3); When a nucleating agent (C) includes a hydrophobic metal oxide and / or a synthetic resin>
A method comprising a dispersion step (p31) in which a hydrophobic metal oxide and / or synthetic resin and a polyether compound (D) are stirred and mixed to obtain a dispersion, or a hydrophobic metal oxide and / or synthetic resin and a polyether compound A mixing step (p32) for stirring and mixing with (D), and a dispersion step (p33) for homogenizing the mixture to obtain a dispersion of a hydrophobic metal oxide and / or a synthetic resin .

  In the mixing step (p31), if the hydrophobic metal oxide and / or the synthetic resin and the polyether compound (D) can be uniformly mixed, the temperature and time of stirring and mixing are not limited, and stirring and mixing can be performed under normal conditions. .

  As long as the mixing step (p32) can uniformly mix the hydrophobic metal oxide and / or the synthetic resin and the polyether compound (D), the temperature and time for stirring and mixing are not limited, and stirring and mixing can be performed under normal conditions. .

  The dispersion step (p33) is not limited as long as the mixed liquid containing the hydrophobic metal oxide and / or the synthetic resin and the polyether compound (D) can be homogenized, but an emulsifying disperser (bead mill, disper mill, homogenizer or gorin) Homogenization is preferably performed using a homogenizer, an ultrasonic emulsifier, or the like.

  As a nucleating agent (C), when a plurality of types of hydrophobic metal oxides and synthetic resins are included (including cases where a plurality of types of hydrophobic metal oxides are included), a plurality of types of nucleating agents are stirred and mixed. To obtain a dispersion or mixed solution {dispersion step (p31) or mixing step (p32)} to obtain a dispersion of nucleating agent {polyether containing nucleating agent (Y)}, or a hydrophobic metal After obtaining a dispersion of each oxide or synthetic resin, these dispersions may be uniformly mixed to obtain a dispersion of a nucleating agent {polyether containing a nucleating agent (Y)}.

  As the nucleating agent (C), among fatty acid metal salts, fatty acid amides, waxes, hydrophobic metal compounds, and synthetic resins, a case where a plurality of types of nucleating agents are included (a case where a plurality of types of fatty acid metal salts are included also applies). The nucleating agent-containing polyether (Y) may be produced by appropriately combining the above methods (P1) to (P3), or produced by only one of the methods (P1) to (P3). May be.

The antifoaming agent of the present invention is effective with respect to aqueous foaming liquids. For example, antifoaming agents for paints (aqueous paints, etc.) and various manufacturing processes (paper making process, fermentation process, culture process, wastewater treatment process, monomer) It can be used as an antifoaming agent for stripping step and polymer polymerization step).
Among these, it is suitable as an antifoaming agent for various manufacturing processes and an antifoaming agent for wastewater treatment, and is optimal as an antifoaming agent for papermaking processes.

  When the antifoaming agent addition method of the present invention is applied to various production processes, (1) the supply of raw materials, (2) before heating and / or decompression treatment, and / or (3) the final finishing process, etc. Any of the methods of adding may be used. For example, when applied to a wastewater treatment process, it can be added to the inflow of wastewater (before the aeration tank), before separation (before the settling tank), final finishing (discharge), and the like.

  When applied to various production processes, the addition amount (% by weight) of the antifoaming agent of the present invention is preferably 0.0001 to 3, more preferably 0.001 to 2.7, based on the weight of the aqueous foaming liquid. Particularly preferably, it is 0.005 to 2.3, and most preferably 0.01 to 2.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this. Unless otherwise specified, “part” means “part by weight” and “%” means “wt%”. Moreover, unless otherwise specified, it is performed at 25-30 degreeC.

<Production Example 1; Production Example 1 of Dispersion (z1)>
In a container that can be heated, stirred and cooled, 250 parts of alcohol (a1) {alcohol mixture of 16 to 26 carbon atoms, NAFOL20 + A, manufactured by SASOL, melting point 58 ° C} and hydrophobic component (b1) {tallow fatty acid methyl ester 50 parts of Nippon Shin-Rika Co., Ltd., melting point 15 ° C.} were heated to 70 ° C. and stirred and mixed to obtain a solution (ab1).

  Surfactant (fz1) {Polyoxyethylene alkyl ether, NAROACTY CL-400, Sanyo Chemical Co., Ltd. while stirring 694 parts of water (e1) {clean water} in a container that can be heated, stirred and cooled Company made} 3 parts, surfactant (fz2) {Polyoxyethylenediolate, Ionette DO-600, Sanyo Chemical Industries, Ltd.} 0.7 part, surfactant (fz3) {Polyoxyethylene monooleate, Ionette MO-400, Sanyo Chemical Industries, Ltd.} 0.7 parts, thickener (1) {xanthan gum, Kelzan, Sansho Co., Ltd.} 1.5 parts and preservative (1) {Biokiller LS, Kei Made by Ai Kasei Co., Ltd.} 0.1 part was added, and stirring was continued for 4 hours to make the aqueous phase (1) uniform.

  While heating and stirring the aqueous phase (1), the temperature was raised to 70 ° C., and the solution (ab1) at 70 ° C. was added while stirring, and the mixture was treated with a homomixer at 3000 rpm for 3 minutes at the same temperature. The mixture was cooled to ° C. to obtain a dispersion (z1) in which particles (x1) were dispersed.

  Volume average particle size of particle (x1) {Laser diffraction / scattering type particle size distribution measuring device (Partica LA-950V2, flow cell type, refractive index of dispersoid = 1.45, refractive index of dispersion medium = 1.33, repetition) No. 15, HORIBA, Ltd.), using water as the dispersion medium, putting water into the flow cell, performing blank measurement while circulating at a circulation strength of 5, and then adding an appropriate amount of measurement sample to this flow cell and measuring The blank measurement value was subtracted from this measurement value. The same applies hereinafter was 7 μm.

<Production Examples 2 to 7; Preparation Examples of Dispersions (z2) to (z7)>
Except that the composition of the dissolution liquid (ab1) was changed to the composition described in Table 1, and the composition of the aqueous phase (1) was changed to the composition described in Table 2, {Production Example 1 {Dispersion (z1)] Dispersions (z2) to (z7) were prepared in the same manner as in Preparation Example}.

Alcohol (a2): Cetanol, Conol 1670, manufactured by Shin Nippon Chemical Co., Ltd., melting point 50 ° C.

Hydrophobic component (b2): Palm fatty acid methyl ester, manufactured by Carotech, melting point 15 ° C.
Hydrophobic component (b3): oleic acid ester of polyoxypropylene (40 mol) glycol monobutyl ether, pour point -30 ° C
Hydrophobic component (b4): dimethyl silicone oil (kinematic viscosity 10 (mm ² / s, 25 ° C)), KF-96-10CS, manufactured by Shin-Etsu Chemical Co., Ltd., pour point -65 ° C
Hydrophobic component (b5): propylene oxide (43 mol) adduct of glycerin, Sannix GP-3000, manufactured by Sanyo Chemical Industries, Ltd., pour point -35 ° C .; “Sannix” is a registered trademark of the company.
Hydrophobic component (b6): Edible rapeseed oil, manufactured by Nikko Oil Co., Ltd., pour point -5 ° C
Hydrophobic component (b7): Refined beef tallow, ITR, made by Miyoshi oil, melting point 45 ° C
Hydrophobic component (b8): mineral oil, Cosmo SP-10, manufactured by Cosmo Oil Lubricants Co., Ltd., pour point -12 ° C

Surfactant (fz4): polyoxyethylene (2 mol) alkyl ether sulfosuccinic acid half ester sodium salt 40% aqueous solution, VIEWLITE ESS

Hydrophobic silica (1): Hydrophobic silica, SIPERNAT D10, manufactured by Degussa Japan

<Production Example 8; Preparation Example of Dispersion (z8)>
In a container capable of heating, stirring and cooling, 235 parts of alcohol (a1), 50 parts of hydrophobic component (b1) and wax (1) {alcohol-modified wax, OX-3405, manufactured by Nippon Seiki Co., Ltd.} 10 parts were heated to 110 ° C. and stirred to obtain a solution (ab8).

  While stirring 696 parts of water (e1) in a container that can be heated, stirred and cooled, 6 parts of surfactant (d1), 0.7 part of surfactant (d2), and surfactant (d3) 0 7 parts, 1.5 parts of thickener (1) and 0.1 part of preservative (1) were added, and stirring was continued for 4 hours to make uniform a receiving liquid (8).

  The temperature of the receiver liquid (8) was raised to 70 ° C. while stirring with heating, and the dissolution liquid (ab8) at 70 ° C. was added while continuing stirring, and the mixture was treated with a homomixer at 3000 rpm for 3 minutes at the same temperature. The mixture was cooled to ° C to obtain a dispersion (z8) in which particles (x8) were dispersed.

<Production Example 9; Preparation Example of Dispersion (z9)>
In a container that can be heated, stirred, and cooled, 39 parts of alcohol (a3) {behenyl alcohol, Conol 2265, manufactured by Shin Nippon Rika Co., Ltd., melting point 73 ° C.}, 61 parts of hydrophobic component (b1), hydrophobic component (b7 ) 200 parts and 20 parts of wax (2) {polyethylene oxide wax, Epolene E-10, manufactured by Eastman Chemical Co., Ltd.} were heated to 110 ° C. and stirred to obtain a solution (ab9).

  While stirring 674 parts of water (e1) in a container capable of heating, stirring and cooling, 3 parts of surfactant (d1), 0.7 part of surfactant (d2), and surfactant (d3) 0 7 parts, 1.5 parts of thickener (1) and 0.1 part of preservative (1) were added, and stirring was continued for 4 hours to prepare a receiver liquid (9).

  The temperature of the receiver liquid (9) was increased to 70 ° C. while stirring with heating, and the dissolution liquid (ab9) at 70 ° C. was added while continuing stirring, and the mixture was treated at 3000 rpm for 3 minutes with a homomixer at the same temperature. The mixture was cooled to ° C. to obtain a dispersion (z9) in which particles (x9) were dispersed.

<Production Example 10; Preparation Example of Dispersion (z10)>
In a container that can be heated, stirred and cooled, 94 parts of alcohol (a3), 15 parts of hydrophobic component (b1) and 15 parts of hydrophobic component (b7) are heated to 90 ° C., stirred and mixed to obtain a solution ( ab10) was obtained.

  While stirring 870 parts of water (e1) in a container that can be heated, stirred and cooled, 3 parts of surfactant (d1), 0.7 part of surfactant (d2), and surfactant (d3) 0 7 parts, 1.5 parts of thickener (1) and 0.1 part of preservative (1) were added, and stirring was continued for 4 hours to prepare a receiver liquid (10).

  The temperature of the receiving liquid (10) was raised to 70 ° C. while stirring with heating, and the dissolution liquid (ab10) at 70 ° C. was added while continuing stirring, and the mixture was treated with a homomixer at 3000 rpm for 3 minutes at the same temperature. The mixture was cooled to ° C. to obtain a dispersion (z10) in which particles (x10) were dispersed.

  The volume average particle diameters (μm) of the particles (x2) to (x10) in the dispersions (z2) to (z10) were as shown in Table 3, respectively.

<Production Example 11; Preparation Example of Polyether (y1) with Nucleating Agent>
In a container capable of heating, stirring and cooling, 30 parts of nucleating agent (c1) {ethylene bisstearylamide, Alfro H-50S, manufactured by NOF Corporation}, polyether compound (d1) {butanol polyoxypropylene (40 Mol) adduct, New Pole LB-1715, Sanyo Chemical Industries, Ltd.} 200 parts and polyether compound (d2) {polyoxyethylene (5 mol) polyoxypropylene (30 mol), New Pole PE-61, Sanyo Kasei Kogyo Co., Ltd.)} was heated to 150 ° C. while stirring with heating, and stirring was continued for 15 minutes at this temperature to obtain a uniform mixed solution (cd1).

  Next, 600 parts of polyether compound (d1) adjusted to 10 ° C. and polyether compound (d3) {trimethylolpropane ethylene oxide (10 mol) / propylene oxide (68 mol) block adduct, Newpol TL-4500N, Sanyo After 70 parts of Kasei Kogyo Co., Ltd. were stirred and mixed to obtain a receiver liquid (1), the receiver liquid (1) was cooled and stirred and adjusted so as not to rise to 40 ° C. or higher. cd1) was added to obtain a nucleating agent dispersion (cd1).

  The nucleating agent dispersion (cd1) was cooled to 25 ° C. with stirring and then homogenized at 3500 psi (24.1 MPa) using a gorin homogenizer to obtain a nucleating agent-containing polyether (y1). The number average particle diameter (μm) of the nucleating agent in the nucleating agent-containing polyether (y1) was 0.1.

  The number average particle size (μm) is a laser diffraction / scattering type particle size distribution measuring device Partica LA-950V2 manufactured by HORIBA, Ltd. (batch cell type, refractive index of dispersoid = 1.45, refractive index of dispersion medium). = 1.36, number of repetitions 15), and acetone was used as the solvent (the same applies hereinafter). The amount of the measurement sample (polyether containing nucleating agent) is adjusted so that the transmittance of the blue LED light is 89 to 91%. The larger the amount of the measurement sample, the lower the transmittance. If the measurement sample is not within the range, the measurement sample or acetone was added to adjust the concentration of the measurement sample.

<Production Examples 12 to 17; Preparation Examples of Polyethers (y2) to (y7) with Nucleating Agent>
The composition and heating temperature of the mixed liquid (cd1) were changed to the compositions and heating temperatures described in Table 4, and the composition and cooling temperature of the receiving liquid (1) (the maximum temperature of the receiving liquid during the charging of the mixed liquid) are shown. Except having changed into the composition and cooling temperature which were described in 5, it carried out similarly to manufacture example 11 {preparation example of polyether (y1) containing a nucleating agent}, and produced nucleating agent-containing polyether (y2)-(y7). .

Nucleating agent (c2): Ethylene bis oleylamide, Alflow AD-281F, NOF Corporation nucleating agent (c3): Oxidized polyethylene wax, Epolen E-10, Eastman Chemical Co. nucleating agent (c4): Alcohol-modified wax , OX-3405, Nippon Seiki Co., Ltd. nucleating agent (c5): Aluminum stearate, SA-1500, Sakai Chemical Industry Co., Ltd. nucleating agent (c6): Carnauba wax, Carnauba wax No. 1, stock Company Kato Yoko nucleating agent (c7): maleic acid-modified polyethylene oxide, PED-136, manufactured by Nippon Seiki Co., Ltd.

Polyether compound (d4): propylene oxide (43 mol) adduct of glycerin, Sanniks GP-3000, polyether compound (d5) manufactured by Sanyo Chemical Industries, Ltd .: oleic acid of polyoxypropylene (40 mol) glycol monobutyl ether Ester polyether compound (d6): Polypropylene glycol (34 mol), Newpol PP-2000, Sanyo Kasei Kogyo Co., Ltd. polyether compound (d7): Polyoxyethylene (5 mol) Polyoxypropylene (30 mol) stearin Acid diester

Polyether compound (d8): glycerin ethylene oxide (3 mol) / 2-ethylhexyl glycidyl ether (6 mol) block adduct polyether compound (d9): 200 parts of polyoxypropylene (34 mol) glycol and polyoxyethylene ( 3 mol) Polyether compound polyether compound (d10) obtained by reacting 231 parts of polyoxypropylene (14 mol) myristyl ether and 16.8 parts of hexamethylene diisocyanate: propylene oxide (9 mol) adduct of glycerin , New Pole GP-600, polyether compound (d11) manufactured by Sanyo Chemical Industries, Ltd .: 80 mol adduct of sucrose polyoxypropylene

<Production Example 18: Preparation Example of Nucleating Agent-Containing Polyether (y8)>
In a container capable of stirring, 30 parts of nucleating agent (c8) {hydrophobic silica, SIPERNAT D10, manufactured by Degussa Japan Co., Ltd.}, 900 parts of polyether compound (d5) and 70 parts of polyether compound (d10) for 15 minutes The mixture was stirred to obtain a nucleating agent dispersion (cd8).

  The nucleating agent dispersion (cd8) was homogenized at 3500 psi (24.1 MPa) using a gorin homogenizer to obtain a nucleating agent-containing polyether (y8).

<Manufacture example 19; Preparation example of polyether (y9) containing nucleating agent>
Polymer polyol [nucleating agent (c9) {(styrene) / (acrylonitrile) / (divinylbenzene) / (propylene of glycerin) prepared in accordance with Example 1 of JP2009-7506 A in a stirrable container Structural unit: Reactive dispersant obtained by jointing oxide adduct and 2-hydroxyethyl methacrylate with tolylene diisocyanate (TDI) / (polyoxyalkylene ether in which propylene oxide (PO) is added to allyl alcohol) Copolymer (particle diameter 0.7 μm)} 52%, polyether compound (d11) {polyol obtained by block addition of alkylene oxide in the order of propylene oxide-ethylene oxide (ethylene oxide ratio 12% by weight) to pentaerythritol, HLB = 2.5} 45% and Reether compound (d12) {mixture of glycerin propylene oxide adduct, HLB = 0.3} 3% prepared according to Japanese Patent Laid-Open No. 2000-344881] 153 parts, polyether compound (d1) 300 parts, polyether 300 parts of compound (d3) and polyether compound (d7) 247 were stirred for 15 minutes to obtain a nucleating agent-containing polyether (y9).

  The number average particle diameters (μm) of the nucleating agents in the nucleating agent-containing polyethers (y2) to (y9) were as shown in Table 6, respectively.

<Example 1>
In a container capable of stirring, 800 parts of the dispersion (z1) and 200 parts of polyether (y1) containing a nucleating agent were stirred and mixed for 15 minutes to obtain the antifoaming agent (1) of the present invention.

<Examples 2 to 24>
The antifoaming agents (2) to (2) of the present invention were used in the same manner as in Example 1 except that the dispersion (z1) and the nucleating agent-containing polyether (y1) were changed to the types and amounts used shown in Table 7. 24) was obtained.

<Comparative Examples 1-10>
Dispersions (z1) to (z10) were used as antifoaming agents (H1) to (H10) for comparison.

<Comparative Examples 11-13>
Example 1 except that the amount of the dispersion (z1) used was changed to the amount shown in Table 8, and the nucleating agent-containing polyether (y1) was changed to the nucleating agent or the polyether compound shown in Table 8. In the same manner, antifoaming agents (H11) to (H13) for comparison were obtained.

  Using the antifoaming agents (1) to (24) and (H1) to (H13) obtained in Examples 1 to 24 and Comparative Examples 1 to 13, the antifoaming property was evaluated as follows, and the evaluation results Are shown in Table 9.

<Creation of evaluation liquid>
Elemiol MON-2 (sodium dodecyl diphenyl ether disulfonate 50.3% by weight aqueous solution; Sanyo Chemical Industry Co., Ltd., “Eleminol” is a registered trademark of the same company) 0.172 g was added to a 500 ml graduated cylinder, In addition, after mixing uniformly, an antifoaming agent was added so that an active ingredient (components other than water) might be 0.006g, and the test liquid was created.
In addition, the test liquid for blanks was prepared like the above except not adding an antifoamer.

<Evaluation of antifoaming property at 25 ° C.>
A Kinoshita glass ball filter was submerged in the bottom of a 500 mL graduated cylinder containing 60 ml of the test solution, and the test solution and test apparatus (graduated cylinder, Kinoshita glass ball filter, etc.) were adjusted to 25 ° C. Subsequently, using a Kinoshita type glass ball filter, the liquid volume (mL) after aeration of nitrogen gas at 20 m 3 / min for 1 minute from the bottom of the cylinder was read, and the defoaming value at 25 ° C. was obtained. It can be said that the smaller the liquid volume, the more the bubbles are destroyed and the better the defoaming property.

<Evaluation of antifoaming property at 60 ° C.>
A Kinoshita glass ball filter was submerged in the bottom of a 500 mL graduated cylinder containing 60 ml of the test solution, and the test solution and test apparatus (graduated cylinder, Kinoshita glass ball filter, etc.) were adjusted to 60 ° C. Subsequently, using a Kinoshita type glass ball filter, the liquid volume (mL) after aeration of nitrogen gas at 20 m 3 / min for 1 minute from the bottom of the cylinder was read, and the defoaming value at 60 ° C. was obtained. It can be said that the smaller the liquid volume, the more the bubbles are destroyed and the better the defoaming property.

  The antifoaming agent of the present invention was extremely good in antifoaming properties (antifoaming properties at 25 ° C. and 60 ° C.) as compared with a comparative antifoaming agent. That is, by using the dispersion (Z) and the polyether (Y) containing a nucleating agent in combination, it exhibits excellent defoaming properties, and when the dispersion (Z) is used alone or with the nucleating agent (C). When the dispersion (Z) was used in combination and when the polyether compound (D) and the dispersion (Z) were used together, the antifoaming property was poor.

Claims (8)

It is at least one selected from the group consisting of an alcohol (A) having 12 to 30 carbon atoms, mineral oil, animal / vegetable oil, fatty acid ester, polyorganosiloxane and polyether compound, and having a melting point higher than that of the alcohol (A). A dispersion (Z) in which particles (X) composed of a hydrophobic component (B) having a low melting point or pour point as an essential component are dispersed in water;
A nucleating agent comprising, as essential components, at least one nucleating agent (C) selected from the group consisting of fatty acid metal salts, fatty acid amides, waxes, hydrophobic metal oxides, and synthetic resins, and a polyether compound (D). only contains a poly ether (Y) enters,
Based on the weight of the dispersion (Z) and the polyether (Y) containing the nucleating agent, the weight of the dispersion (Z) is 65 to 95% by weight, and the weight of the polyether (Y) containing the nucleating agent is 5 to 35% by weight. anti-foaming agent, characterized in that it is. The antifoaming agent according to claim 1, wherein the volume average particle diameter of the particles (X) is 1 to 50 μm. The content of the alcohol (A) is 10 to 90% by weight and the content of the hydrophobic component (B) is 10 to 90% by weight based on the weight of the alcohol (A) and the hydrophobic component (B). The antifoaming agent according to 1 or 2. The antifoaming agent according to any one of claims 1 to 3, wherein the nucleating agent (C) has a melting point of 60 to 2000 ° C. The content of particles (X) is 10 to 60% by weight, and the content of water (E) in the dispersion (Z) is 40 to 90% by weight based on the weight of the dispersion (Z). The antifoamer in any one of -4. The polyether compound (D) is a polyether compound (D1) represented by the general formula (1), a polyether compound (D2) represented by the general formula (2), and a poly compound represented by the general formula (3). It is at least one selected from the group consisting of an ether compound (D3), a polyether compound (D4) represented by the general formula (4), and a polyether compound (D5) represented by the general formula (5). The antifoamer in any one of 1-5 .

R ¹ is a reaction residue of an active hydrogen compound having 1 to 25 carbon atoms, R ² and R ³ are monovalent organic groups having 1 to 24 carbon atoms, R ⁴ is a divalent organic group having 1 to 24 carbon atoms, R ⁵ is a hydroxyl group or a monovalent organic group having 1 to 24 carbon atoms, AO and OA are oxyalkylene groups having 2 to 18 carbon atoms, or glycidol, a reaction residue of an alkyl glycidyl ether or alkenyl glycidyl ether having 4 to 18 carbon atoms. In the case where (OA) _n or (AO) n represents a group, the proportion of the oxyethylene group is 0 to 20% by weight, and n is an integer of 1 to 100, and a plurality of n is present in one molecule. S is an integer of 1 to 10, p is an integer of 0 to 10, q is an integer of 0 to 9, r is an integer of 0 to 9, m is an integer of 0 to 9, p + r is an integer of 1 to 10, p + q + r is an integer of 1 to 10, p q + r + m is 2 to 10. Based on the weight of the nucleating agent (C) and the polyether compound (D), the weight of the nucleating agent (C) is 0.1 to 10% by weight, and the weight of the polyether compound (D) is 90 to 99.9% by weight. The antifoaming agent according to any one of claims 1 to 6 . The antifoaming agent according to any one of claims 1 to 7 , wherein the nucleating agent (C) in the nucleating agent-containing polyether (Y) has a number average particle diameter of 0.05 to 20 µm.