WO2013061700A1 - 消泡剤 - Google Patents
消泡剤 Download PDFInfo
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- WO2013061700A1 WO2013061700A1 PCT/JP2012/073121 JP2012073121W WO2013061700A1 WO 2013061700 A1 WO2013061700 A1 WO 2013061700A1 JP 2012073121 W JP2012073121 W JP 2012073121W WO 2013061700 A1 WO2013061700 A1 WO 2013061700A1
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- WIPO (PCT)
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- oil
- dispersion
- fumed silica
- hydrophilic fumed
- antifoaming agent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
- B01D19/0409—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing Si-atoms
Definitions
- the present invention relates to an antifoaming agent.
- An oil-in-water emulsion antifoaming agent in which an antifoaming agent in which amide, wax, hydrophobic silica, etc., which is a reaction product of an alkylene polyamine and a fatty acid, is dispersed in a hydrocarbon oil, is emulsified and dispersed with a surfactant.
- Patent Documents 1 and 2 Known (Patent Documents 1 and 2).
- An object of the present invention is to provide an oil-in-water emulsion antifoaming agent excellent in antifoaming properties (initial defoaming property and antifoaming sustainability) and stability (emulsion stability).
- the present inventors have solved the above problems by using specific hydrophilic silica, and the defoaming property and stability of the oil-in-water emulsion defoaming agent are improved.
- the inventors have found that it is significantly improved and have reached the present invention. That is, the feature of the antifoaming agent of the present invention is that it contains hydrophilic fumed silica (C) and the oil phase (A) is dispersed in the water phase (B).
- a feature of the production method (1) of the present invention is a method for producing the oil-in-water emulsion antifoaming agent described above, Dispersion (BC1) in which the hydrophilic fumed silica (C) is dispersed and crushed in the aqueous phase (B) to obtain a dispersion liquid (BC1) having a median diameter (d50, based on the number) of the hydrophilic fumed silica of 20 to 300 nm.
- the production method (2) of the present invention is characterized in that the median diameter (d50, number of hydrophilic fumed silica) of hydrophilic fumed silica is dispersed and crushed in a part of the aqueous phase (B).
- the gist includes the emulsification / dispersion step (v) of emulsifying and dispersing the mixed dispersion (AB) and the dispersion (BC2) to obtain an oil-in-water emulsion defoamer.
- the production method (3) of the present invention is characterized in that a dispersion (AC) of hydrophilic fumed silica is obtained while dispersing and crushing hydrophilic fumed silica (C) in the oil phase (A). Crushing step (vi);
- the gist is to include an emulsification / dispersion step (vii) of emulsifying and dispersing the dispersion (AC) and the aqueous phase (B) to obtain an oil-in-water emulsion defoamer.
- the antifoaming agent of the present invention exhibits remarkably excellent defoaming properties (initial defoaming property and defoaming sustainability) and stability (emulsion stability).
- the antifoaming agent can be easily produced.
- hydrophilic fumed silica (C) any dry silica synthesized by vapor phase reaction of vaporized silicon chloride in a high-temperature hydrogen flame can be used. Hydrophilic fumed silica (C) can be easily obtained from the market.
- Aerosil series 130, 200, 300, etc., Nippon Aerosil Co., Ltd., “Aerosil” is a registered trademark
- dry silica HDK series S13, V15, N20, T30, etc.
- Leoroseal series QS-10, QS-30, QS-40, QS-102, Co., Ltd.
- Lerosil is a registered trademark
- CAB-O-SIL EH-5, CAB-O-SIL HS-5, CAB-O-SIL M-5 Cabot Corporation, “CAB-O-SIL” Is a registered trademark).
- the hydrophilic fumed silica (C) is considered to have a function of helping to emulsify and disperse the oil phase (A) in the aqueous phase (B) (that is, it is considered to greatly contribute to stability).
- most of the hydrophilic fumed silica (C) is considered to exist between the water phase (B) and the oil phase (A).
- the hydrophilic fumed silica (C) makes the initial defoaming property slightly good and does not deteriorate the defoaming sustainability.
- Silica other than hydrophilic fumed silica (C) for example, fused silica, precipitated silica, and gel silica) cannot achieve the effects of the present invention.
- the BET specific surface area (m 2 / g, by nitrogen gas adsorption) of the hydrophilic fumed silica (C) is preferably 20 to 450, more preferably 30 to 440, particularly preferably 40 to 430, most preferably 50 to 420.
- the BET specific surface area (m 2 / g, by nitrogen gas adsorption) of the hydrophilic fumed silica (C) is based on ISO 5794-1 / Annex D using a BET specific surface area measuring device (eg, TRISTAR 3000, Micromeritics). Measured according to multi-point measurement according to DIN ISO 9277.
- the hydrophilic fumed silica (C) may be used by being dispersed in the oil phase before emulsification, by being dispersed in the aqueous phase before emulsification, or by being dispersed in the emulsion during or after emulsification.
- the method used by dispersing in the aqueous phase before emulsification and the method used by dispersing in the emulsion during or after emulsification are preferred, more preferably the method used by dispersing in the aqueous phase before emulsification, particularly preferably emulsification.
- the median diameter (d50, number basis) is dispersed in the previous aqueous phase so as to be 20 to 300 nm.
- the oil phase (A) is a component for exhibiting defoaming properties (initial defoaming property and defoaming durability), and known oily defoaming agents and the like can be used.
- a preferable oil phase (A) includes a base oil (E) that is liquid at 25 ° C. as an essential component.
- Mineral oil, fats and oils, monoalcohol fatty acid ester, silicone and / or polyether can be used as the base oil (E) which is liquid at 25 ° C.
- Mineral oil can be refined by appropriately combining vacuum distillation, oil removal, solvent extraction, hydrocracking, solvent dewaxing, sulfuric acid washing, clay refining, and hydrorefining.
- Pure Spin G Cosmo Pure Spin E, Cosmo SP-10, Cosmo SP-32 and Cosmo SC22 (Cosmo Oil Co., Ltd., “Cosmo” and “Pure Spin” are registered trademarks of the company), MC Oil P -22, S-10S (above, Idemitsu Kosan Co., Ltd.), and Stanol 40 (Exxon Mobil Corporation).
- Fats and oils include esters of fatty acids having 6 to 22 carbon atoms or mixtures thereof and glycerin, vegetable oils (rapeseed oil, soybean oil, palm oil, coconut oil, olive oil, etc.), medium chain fatty acid glycerides (trade names such as Panaceate 875; NOF Corporation, “Panasate” is a registered trademark of the company), fish oil, and the like.
- monoalcohol fatty acid esters include esters of fatty acids having 6 to 22 carbon atoms or mixtures thereof and monoalcohols having 1 to 22 carbon atoms that are liquid at 25 ° C., such as methyl oleate and butyl oleate. And methyl isostearate.
- Silicone includes silicone oil and modified silicone oil.
- the silicone oil include polydimethylsiloxane having a kinematic viscosity of 10 to 10,000 (mm 2 / s, 25 ° C.), and cyclooctamethyltetrasiloxane is also included.
- the modified silicone include a part of the methyl group of the above dimethylsiloxane, 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 atom (such as chlorine and bromine), an alkoxy group.
- Polyoxyalkyleneoxypropyl group (alkoxy having 1 to 6 carbon atoms, alkylene having 2 to 3 carbon atoms, polymerization degree of 2 to 50, and the weight of the oxyethylene group is less than 20% by weight of the total weight of the oxyalkylene group)
- Oxyalkylene group (alkoxy having 1 to 6 carbon atoms, alkylene having 2 to 3 carbon atoms, degree of polymerization of 2 to 50, and the weight of oxyethylene group being less than 20% by weight of the whole oxyalkylene group) and / or 2 to 6 carbon atoms In which the aminoalkyl group is substituted.
- HLB 0 to 3.4 can be used, preferably HLB 0 to 2.9, more preferably HLB 0 to 2.4, and most preferably HLB 0 to 1.9.
- HLB is “Introduction to New Surfactants” (Takehiko Fujimoto, Sanyo Kasei Kogyo Co., Ltd., published in October 1981), pages 128-131 (corresponding English version, New Introduction to Surface Active Agents, SANYO CHEMICAL INDUSTRIES) , LTD., 1985, p127-130 (the disclosure content disclosed therein is incorporated herein by reference).
- polyether 1 mole of monoalcohol having 1 to 22 carbon atoms, monocarboxylic acid having 1 to 22 carbon atoms or monoamine having 1 to 22 carbon atoms and 1 to 100 moles of alkylene oxide having 2 to 4 carbon atoms.
- a reaction product a reaction product of 1 mol of a polyol having 2 to 6 carbon atoms and 1 to 300 mol of an alkylene oxide having 2 to 4 carbon atoms, “1 mol of a polyol having 2 to 6 carbon atoms and 2 to 4 carbon atoms”
- Examples include an esterified product of a reaction product with 300 mol and a fatty acid having 1 to 22 carbon atoms.
- base oils (E) mineral oils, fats and oils, silicones and polyethers are preferred, and some or all of these are preferred.
- the oil phase (A) preferably further contains a nucleating agent (D).
- the nucleating agent (D) include those that do not dissolve in the liquid base oil (E) at 25 ° C. but can be dispersed in the base oil (E), such as hydrophobic silica (Da), fatty acid amide (Db), One or more selected from the group consisting of petroleum wax (Dc), synthetic wax (Dd), vegetable wax (De), and synthetic resin fine particles (Df) can be used.
- Hydrophobic silica (Da) includes hydrophobic silica obtained by hydrophobizing silica powder with a hydrophobizing agent.
- the hydrophobic silicas available on the market are Nipsil SS-10, SS-40, SS-50 and SS-100 (Tosoh Silica Co., “Nipsil” is a registered trademark of Tosoh Silica Co., Ltd.).
- AEROSIL R972, RX200 and RY200 Nippon Aerosil Co., Ltd., “AEROSIL” is a registered trademark of Evonik Degussa GmbH
- SIPERNAT D10, D13 and D17 Degussa Japan Co., Ltd.
- EPERNATT is Evonik Degussa GmbH
- AEROSIL R202, R805 and R812 Degussa Japan Co., Ltd.
- REOLOSIL MT-10 DM-10 and DM-20S Tokuyama Co., Ltd., “REOLOSIL” is a registered trademark of the company
- SYLOPHOBIC100, 702, 505 and 603 Fluji Silysia Chemical Co., Ltd., “SYLOPHOBIC” is a registered trademark of the company. Etc.).
- Examples of the fatty acid amide (Db) include a reaction product of an alkylenediamine or alkenylenediamine having 1 to 6 carbon atoms and a fatty acid having 10 to 22 carbon atoms (fatty acid diamide) and / or an alkylamine, alkenylamine having 1 to 22 carbon atoms, or A reaction product (fatty acid monoamide) of ammonia and a fatty acid having 10 to 22 carbon atoms is included.
- 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.
- fatty acid monoamides examples include N-stearyl stearyl amide, oleic acid amide, erucic acid amide, and stearyl amide.
- 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 (Db), preferably 50% by weight or more, more preferably 60% by weight or more, and particularly preferably 70% by weight. % Or more, most preferably 80% by weight or more.
- an unreacted amine, an unreacted carboxylic acid and the like are included in addition to the amide other than the above 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, most preferably 20 based on the weight of the fatty acid amide (Db). Is less than.
- the petroleum wax (Dc) includes wax produced as a by-product from petroleum refining that does not dissolve in the oil phase at 40 ° C. and can be dispersed, and includes microcrystalline wax and paraffin wax.
- Synthetic waxes include waxes obtained by chemical synthesis that do not dissolve and disperse in the oil phase at 40 ° C., and include Fischer-Tropsch wax, polyethylene wax, oxidized polyethylene wax, alcohol-modified wax, and maleic acid-modified polyethylene oxide. A wax etc. are mentioned.
- Plant wax (De) includes wax extracted from plants that do not dissolve in the oil phase at 40 ° C. and can be dispersed, and includes carnauba wax and wood wax.
- Synthetic resin fine particles (Df) include synthetic resin fine particles (Df1) having an ethylenically unsaturated monomer (m1) as a structural unit or synthetic resin fine particles (Df2) having a polycondensation / polyaddition monomer (m2) as a structural unit. included.
- Examples of the ethylenically unsaturated monomer (m1) include known ethylenically unsaturated monomers, such as (meth) acrylic acid; (meth) acrylic acid alkyl ester having 1 to 22 carbon atoms ⁇ methyl (meth) acrylate , Ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid (2-ethylhexyl), stearyl (meth) acrylate and behenyl (meth) acrylate ⁇ , etc .; alcohol having 1 to 18 carbon atoms (Meth) acrylate of adduct of alkylene oxide (2 to 4 carbon atoms) ((meth) acrylic acid ester of propylene oxide 30 mol adduct of methanol, (meth) acrylic acid of propylene oxide 30 mol adduct of 2-ethylhexanol) (Meth) acrylic acid of ethylene oxide 30 adduct of ester and steary
- (Meth) acrylic acid means acrylic acid and / or methacrylic acid
- (meth) acrylonitrile means acrylonitrile and / or methacrylonitrile
- (meth) acrylate means acrylate and / or methacrylate. Show.
- Synthetic resin fine particles (Df1) having an ethylenically unsaturated monomer (m1) as a structural unit can be obtained by polymerization by a known method. These may be used as they are after reacting in the base oil (E), or the particles obtained by reacting in advance and the base oil (E) may be mixed.
- the polycondensation / polyaddition monomer (m2) includes known polycondensation / polyaddition monomers, and includes polyisocyanate (m21), polyamine (m22), polyol (m23) and polycarboxylic acid (m24).
- polyisocyanate (m21) examples include diisocyanates having 8 to 16 carbon atoms ⁇ hexamethylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate, 4-4′-methylenebis (cyclohexyl isocyanate), etc. ⁇ and their modified products ⁇ trimethylolpropane of diisocyanate. Adducts, biuret condensates and isocyanurate condensates, etc. ⁇ .
- the polyamine (m22) includes polyamines having 1 to 6 carbon atoms, and examples thereof include urea, melamine, ethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine.
- polyol (m23) examples 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 adducts of polyhydric alcohols, propylene oxide adducts, butylene oxide adducts, ethylene oxide / propylene oxide block adducts, propylene oxide / butylene oxide block adducts, etc. ⁇ Etc. are mentioned.
- the polycarboxylic acid (m24) includes polycarboxylic acids having 4 to 14 carbon atoms, such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, fumaric acid. , Maleic acid, itaconic acid and dimer acid.
- the synthetic resin fine particles (Df2) having the polycondensation / polyaddition monomer (m2) as a structural unit include polyurea, polyurethane, polyester, and the like having the above monomer as a structural unit, and can be obtained by a known method. Can do. These may be used as they are after reacting in the base oil (E), or the particles obtained by reacting in advance and the base oil (E) may be mixed.
- Synthetic resin fine particles are available from the market.
- the following products can be used. Ultiflow FS-7301 (manufactured by Sanyo Chemical Industries, 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, “Dynamic Beads” is a registered trademark of the company), Tuftic F-120, F-167 (Toyobo Co., Ltd., water dispersion of ethylenically unsaturated monomer copolymer) Body; “Toughtic” is a registered trademark of the company)
- the content (% by weight) of the nucleating agent (D) is the nucleating agent (D) and 25 ° C. Based on the weight of the liquid base oil (E), it is preferably 0.01 to 20, more preferably 0.1 to 18, particularly preferably 0.3 to 16, and most preferably 0.5 to 15. .
- the content (% by weight) of the base oil (E) that is liquid at 25 ° C. is 80 to 80% based on the weight of the nucleating agent (D) and the base oil (E) that is liquid at 25 ° C. It is preferably 99.99, more preferably 82 to 99.9, particularly preferably 84 to 99.7, and most preferably 85 to 99.5.
- the hydrophobic silica (Da) is a group that is liquid at 25 ° C. using an emulsifying disperser (bead mill, disper mill, homogenizer, gorin homogenizer, ultrasonic disperser, etc.). It is preferable to disperse in oil (E).
- fatty acid amide (Db), petroleum wax (Dc), synthetic wax (Dd) and / or vegetable wax (De) are included, fatty acid amide (Db), petroleum wax (Dc), synthetic wax (Dd) and / or plant
- the wax (De) is preferably dispersed in the base oil (E) that is liquid at 25 ° C. by the following production method.
- Fatty acid amide (Db), petroleum wax (Dc), synthetic wax (Dd) and / or vegetable wax (De) and a part of base oil (E) which is liquid at 25 ° C. are heated and stirred while fatty acid amide (Db), a dissolving step (di) in which petroleum wax (Dc), synthetic wax (Dd) and / or vegetable wax (De) are dissolved to obtain a solution; While stirring the remainder of the base oil (E) which is liquid at 25 ° C., a mixing step (dii) to obtain a mixture by adding a solution to the remainder, and a homogenization treatment of the mixture to fatty acid amide (Db), A method comprising a dispersion step (diii) to obtain a dispersion of petroleum wax (Dc), synthetic wax (Dd) and / or vegetable wax (De).
- the heating and stirring temperature is not limited as long as the fatty acid amide (Db), petroleum wax (Dc), synthetic wax (Dd) and / or plant wax (De) can be dissolved, but is preferably 100 to 180, more preferably Is 110 to 160, particularly preferably 120 to 150, most preferably 125 to 145.
- the heating and stirring time is not limited as long as the fatty acid amide (Db), petroleum wax (Dc), synthetic wax (Dd) and / or vegetable wax (De) can be dissolved, but oxidation or evaporation of the base oil (E) is not possible. In order to prevent it, it is preferable to make it as short as possible.
- the heating and stirring may be performed in a sealed state (may be under pressure) or may be performed in an open state.
- the solution is heated and stirred while the solution is being added to dissolve the fatty acid amide (Db), petroleum wax (Dc), synthetic wax (Dd) and / or plant wax (De). It is preferable to keep this state.
- the homogenization treatment is not limited as long as the fatty acid amide (Db), petroleum wax (Dc), synthetic wax (Dd) and / or vegetable wax (De) can be homogenized, but an emulsifying disperser (bead mill, disper mill, homogenizer or It is preferable to homogenize using a gorin homogenizer, an ultrasonic emulsifier or the like.
- the synthetic resin fine particles (Df) are contained, the synthetic resin fine particles (Df) are liquid at 25 ° C. using an emulsifying disperser (bead mill, disper mill, homogenizer, gorin homogenizer, ultrasonic disperser, etc.). It is preferable to disperse in the base oil (E).
- the oil phase (A) contains a nucleating agent (D)
- the oil phase contains a surfactant (F), a metal soap (G), and / or an oil-soluble polymer (H). May be.
- Surfactants (F) include anionic surfactants, nonionic surfactants, and mixtures thereof.
- Nonionic surfactants having HLB of 3.5 to 20 can be used, preferably HLB 3.6 to 19, more preferably HLB 3.7 to 18, most preferably HLB 4 to 17. is there.
- 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.
- Sorbitan fatty acid esters include esters of sorbitan and fatty acids having 12 to 22 carbon atoms, such as sorbitan monolaurate (HLB8.6, for example, Nonion LP-20R; NOF Corporation), sorbitan monopalmitate (HLB6).
- sorbitan monolaurate for example, Nonion LP-20R; NOF Corporation
- sorbitan monopalmitate HLB6
- Nonion PP-40R pellets for example, Nonion PP-40R pellets; NOF Corporation, sorbitan monostearate (HLB4.7, for example, Nonion SP-60R pellets; NOF Corporation), sorbitan monooleate (HLB4.3, 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 Kogyo Co., Ltd., “Ionet” It is a registered trademark.), And the like.
- the ethylene oxide adduct of sorbitan fatty acid ester includes an ethylene oxide 1 to 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 same company) and polyoxyethylene (48 mol) polyoxypropylene (35 mol) block polymer (for example, New Pole PE- 75; Sanyo Chemical Industries Ltd.).
- polyoxyethylene alkylaryl ether examples include polyarylethylene ether 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.
- castor oil ethylene oxide adduct eg, UNIOX HC-40; NOF Corporation, “UNIOX” is a registered trademark of the company
- polyoxyethylene fatty acid esters examples include monoesters and diesters of polyoxyethylene having a number average molecular weight of 200 to 4000 and fatty acids having 6 to 22 carbon atoms, and polyoxyethylene glycol having a number average molecular weight of 600, oleic acid, and 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”
- NAROACTY CL-100 (HLB13.3, Sanyo Chemical Industries, Ltd.) and the like.
- glycerin fatty acid ester examples include monoesters of fatty acids having 6 to 22 carbon atoms and glycerin, such as glycerol monostearate (for example, monoglyceride MD, HLB5.5, NOF Corporation).
- Ethylene oxide adducts of glycerin fatty acid esters include 1 to 100 moles of ethylene oxide adducts of glycerin fatty acid esters, and ethylene oxide adducts of glycerin coconut fatty acid esters (for example, UNIGLY MK-207, HLB13.0, NOF Corporation). , “Unigri” is a registered trademark of the company).
- a part of methyl group of dimethylsiloxane is alkoxypolyoxyalkyleneoxypropyl group (alkoxy having 1 to 6 carbon atoms, alkylene having 2 to 3 carbon atoms, polymerization degree of 2 to 50, oxyethylene group weight being 20% by weight or more of the entire oxyalkylene group), an alkoxypolyoxyalkylene group (alkoxy having 1 to 6 carbon atoms, alkylene having 2 to 3 carbon atoms, a polymerization degree of 2 to 50, and the weight of the oxyethylene group is 20% by weight or more) is included.
- 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 surfactant examples include alkyl aryl sulfonates, alkyl biphenyl ether disulfonates, polyoxyethylene alkyl sulfonate esters, and polyoxyethylene alkyl phosphate esters.
- alkyl aryl sulfonate examples include alkyl aryl sulfonate having 6 to 18 carbon atoms, and examples thereof include dodecylbenzene sulfonate.
- the salt is not particularly limited, but alkali metal (sodium, potassium, etc.) salt, alkaline earth metal (calcium, magnesium, etc.) salt, ammonium salt and amine salt having 1 to 18 carbon atoms (triethanolamine, trimethylamine, propylamine) Etc.) (the same shall apply hereinafter).
- alkyl diphenyl ether sulfonate examples include alkyl diphenyl ether disulfonates having an alkyl group of 6 to 18 carbon atoms, such as dodecyl diphenyl ether disulfonate.
- polyoxyethylene alkyl sulfate salts examples include polyoxyethylene alkyl sulfate salts having 6 to 22 carbon atoms, and examples include polyoxyethylene lauryl sulfate salts.
- polyoxyethylene alkyl phosphate ester salt examples include polyoxyethylene alkyl phosphate esters having 6 to 22 carbon atoms, such as polyoxyethylene stearyl phosphate ester salts.
- alkyl aryl sulfonates and alkyl diphenyl ether disulfonates are preferred, more preferably dodecyl benzene sulfonate and dodecyl diphenyl ether disulfonate, particularly preferably calcium dodecyl benzene sulfonate and calcium dodecyl diphenyl ether disulfonate. is there.
- the content (% by weight) of the surfactant (F) is preferably from 0.01 to 20, more preferably from 0.1 to 20, based on the weight of the oil phase (A). It is 02 to 19, particularly preferably 0.03 to 18, and most preferably 0.04 to 16.
- the surfactant (F) When the surfactant (F) is contained and the oily phase (A) contains hydrophobic silica (Da), among the surfactants (F), water-soluble ones (hereinafter referred to as water-soluble surfactants (Fs )) Is preferably 0.01 to 2, more preferably 0.01 to 1.9, particularly preferably 0.01 based on the weight of the oil phase (A). To 1.8, most preferably 0.01 to 1.6.
- the water-soluble surfactant (Fs) means that at least 1 g of the surfactant (F) is completely dissolved in 100 g of ion-exchanged water under the conditions of 25 ° C. and 1 atm. Means something to become.
- the metal soap (G) includes a salt of a fatty acid having 12 to 22 carbon atoms and a metal (alkaline earth metal, aluminum, manganese, cobalt, lead, chromium, copper, iron, nickel, etc.), aluminum stearate, Examples include calcium stearate, zinc laurate, and magnesium behenate.
- the content (% by weight) of the metal soap (G) is preferably 0.1 to 50 based on the weight of the oil phase (A), Preferably it is 0.5 to 45, particularly preferably 1 to 40, most preferably 2 to 35.
- oil-soluble polymer (H) a polymer that can be uniformly dissolved in the base oil (E) that is liquid at 25 ° C. can be used.
- the alkyl (meth) acrylate copolymer, the ⁇ -olefin and the alkyl (meth) acrylate are used. Examples thereof include ester copolymers, petroleum resins, liquid rubber, and block copolymers containing polydiene blocks and polystyrene blocks.
- Oil-soluble polymer (H) can be easily obtained from the market. For example, Sanellis 702, 823, and 934 (poly (meth) acrylate polymers, both of which are Sanyo Chemical Industries, Ltd.
- the content (% by weight) of the oil-soluble polymer (H) is preferably 0.1 to 50 based on the weight of the base oil (E) that is liquid at 25 ° C. More preferably, it is 0.5 to 48, particularly preferably 0.8 to 46, and most preferably 1 to 45.
- the surfactant (F) When the surfactant (F) is contained, the surfactant (F) may be added in any step as long as it can be uniformly mixed with the oil phase (A).
- the oil-soluble polymer (H) may be added in any step as long as it can be uniformly mixed with the oil phase (A).
- Metal soap (G), part of base oil (E) that is liquid at 25 ° C., and part or all of surfactant (F) were heated and mixed to dissolve metal soap (G) uniformly. Then, the liquid mixture cooled to 40 degrees C or less is created, and this is mixed with the remaining base oil (E) etc., and it is the method of setting it as an oil phase (A).
- Metal soap (G) and a base oil (E) that is liquid at 25 ° C. are heated and mixed to uniformly dissolve the metal soap (G), and then cooled to 40 ° C. or lower to obtain the oil phase (A). how to.
- the water phase (B) contains water (I) as an essential component, and examples of the water (I) include tap water, industrial water, deionized water, and distilled water.
- the water phase (B) includes, in addition to water (I), known thickeners, antiseptics (antibacterial / antifungal dictionaries, Japanese Society for Antibacterial and Antifungal Society, 1st edition published in 1986, pages 1-32 etc. ) And / or a cryoprotectant.
- Thickeners include xanthan gum, locust bean gum, guar gum, carrageenan, alginic acid and its salts, tragacanth gum, magnesium aluminum silicate, bentonite, synthetic hydrous silicic acid, and synthetic polymeric thickeners containing carboxyl groups (for example, SN thickener 636, SN thickener 641, etc .; San Nopco Co., Ltd.), associative thickeners containing polyoxyethylene chains (for example, SN thickener 625N, SN thickener 665T, etc.).
- antifreezing agents examples include ethylene glycol, propylene glycol, and glycerin.
- preservative examples include formalin and 5-chloro-2-methyl-4-isothiazolin-3-one.
- the content (% by weight) of the oil phase (A) is preferably 10 to 60, more preferably 12 based on the weight of the oil phase (A), the water phase (B) and the hydrophilic fumed silica (C). To 56, particularly preferably 15 to 54, most preferably 20 to 50. Within this range, the defoaming property (initial defoaming property and defoaming sustainability) and stability (emulsion stability) are further improved.
- the content (% by weight) of the aqueous phase (B) is preferably 34 to 89.9, more preferably based on the weight of the oil phase (A), the aqueous phase (B) and the hydrophilic fumed silica (C). Is 39 to 87.7, particularly preferably 41 to 84.5, and most preferably 44 to 79. Within this range, the defoaming property (initial defoaming property and defoaming sustainability) and stability (emulsion stability) are further improved.
- the content (% by weight) of the hydrophilic fumed silica (C) is preferably 0.1 to 6 based on the weight of the oil phase (A), the aqueous phase (B) and the hydrophilic fumed silica (C). More preferably, it is 0.3 to 5.5, particularly preferably 0.5 to 5, and most preferably 1 to 4.5. Within this range, the defoaming property (initial defoaming property and defoaming sustainability) and stability (emulsion stability) are further improved.
- the median diameter (d50, based on number) ( ⁇ m) of the emulsion particles comprising the oil phase (A) and the hydrophilic fumed silica (C) is preferably 0.3 to 25, more preferably 0.5 to 24, particularly Preferably it is 0.8-23, and most preferably 1-22. Within this range, the defoaming property is even better.
- ⁇ 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, a few drops of a measurement sample (oil-in-water emulsion defoamer) is added and mixed until uniform to create a dispersion. This dispersion is added to the flow cell little by little to adjust to an appropriate transmitted light intensity (blue LED transmitted light intensity is 80 to 90% or red LED transmitted light intensity is 70 to 90%). The measured value is calculated by subtracting the blank measurement value.
- the median diameter (d50, number basis) of the emulsion particles is the ratio of the weight of the oil phase (A) to the hydrophilic fumed silica (C) (A / C), the viscosity of the oil phase (A), the water phase (B ), The dispersion method in the emulsification / dispersion step, and the like. As the weight ratio (A / C) between the oil phase (A) and the hydrophilic fumed silica (C) increases, the median diameter (d50, number basis) of the emulsion particles tends to decrease.
- the median diameter (d50, based on the number) of the emulsion particles tends to decrease.
- the weight ratio (A / C) between the oil phase (A) and the hydrophilic fumed silica (C) is preferably 2 to 100, more preferably 4 to 90, and particularly preferably 6 to 80.
- the antifoaming agent of the present invention can be produced by the following production methods (1) to (3).
- a method comprising an emulsification / dispersion step (ii) in which an oil-in-water emulsion defoamer is obtained by emulsifying and dispersing the dispersion (BC1) prepared in the dispersion / disintegration step (i) and the oil phase (A) ( 1).
- the median diameter (d50, based on number) of the hydrophilic fumed silica in the dispersions (BC1) and (BC2) is preferably 20 to 300 nm, more preferably 24 to 250 nm, particularly preferably 28 to 200 nm, most preferably. 32 to 150 nm.
- step (i) and step (iii) there is no limitation if the hydrophilic fumed silica (C) can be dispersed and pulverized. However, it is preferable to disperse and disintegrate using an emulsifying disperser (bead mill, disper mill, homogenizer or gorin homogenizer, ultrasonic disperser, etc.).
- an emulsifying disperser bead mill, disper mill, homogenizer or gorin homogenizer, ultrasonic disperser, etc.
- step (vi) there is no limitation as long as the hydrophilic fumed silica (C) can be dispersed and pulverized. It is preferable to disperse and crush using a machine (bead mill, disper mill, homogenizer or gorin homogenizer, ultrasonic disperser, etc.).
- the apparatus in the emulsification / dispersion steps (ii), (v) and (vii), there is no limitation on the apparatus to be used as long as the oil phase (A) can be emulsified / dispersed in the aqueous phase (B). You may emulsify and disperse
- the antifoaming agent of the present invention is effective with respect to aqueous foaming liquids.
- antifoaming agents for paints aqueous paints, etc.
- various manufacturing processes paper making process, fermentation process, culture process, wastewater treatment process, monomer
- it is suitable as an antifoaming agent for paints and an antifoaming agent for wastewater treatment
- further suitable as an antifoaming agent for water-based paints Water-based paints (water-based building exterior paints, building interior paints, water-based inks and It is most suitable as an antifoaming agent for emulsion paints among paints for paper coating.
- examples of the binder contained in the emulsion paint include vinyl acetate resin, acrylic resin, styrene resin, halogenated olefin resin, urethane resin, silicone resin, or fluorine atom-containing silicone resin. is there.
- the method of adding the antifoaming agent of the present invention is as follows.
- a method of adding raw materials at the time of blending and / or (5) adding after preparing a paint can be used.
- any of (1) Supply of raw materials, (2) Before heating and / or pressure reduction treatment, and / or (3) Final finishing process etc. may be used.
- 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.
- 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 foam. Particularly preferred is 0.005 to 2.3, most preferred 0.01 to 2.
- the addition amount (% by weight) of the antifoaming agent of the present invention is preferably 0.05 to 3, more preferably 0.1 to 2.7, especially based on the weight of the paint. It is preferably 0.2 to 2.3, and most preferably 0.3 to 2.0.
- the addition amount (% by weight) of the antifoaming agent of the present invention is preferably 0.05 to 3, more preferably 0.1 to 2. 7, particularly preferably 0.2 to 2.3, most preferably 0.3 to 2.
- part means “part by weight” and “%” means “% by weight”.
- surfactants those that are water-soluble are referred to as water-soluble surfactants, and those that are simply referred to as surfactants are surfactants other than the water-soluble surfactant. Unless otherwise specified, the test was performed at 25 to 30 ° C.
- the median diameter (d50, number basis) ( ⁇ m) of the hydrophilic fumed silica (C) in the dispersion liquid (BC1 and BC2) of the hydrophilic fumed silica is a laser diffraction / scattering particle size distribution measuring apparatus Partica.
- a blank measurement is performed while circulating in a flow cell at a circulation strength of 5, and subsequently, an appropriate amount of a measurement sample ⁇ dispersion of hydrophilic fumed silica (BC1 or BC2) ⁇ is added to the flow cell, and measurement is performed.
- the amount of the measurement sample ⁇ hydrophilic fumed silica dispersion (BC1 or BC2) ⁇ put in the flow cell is adjusted so that the transmittance of the blue LED light is 88 to 92%, and the amount of the measurement sample is large. Since the transmittance becomes lower, the adjustment was made to fall within the range depending on the amount of the measurement sample or the dispersion medium when it was out of this range.
- nucleating agent (db1) ⁇ Alflow H-50S, manufactured by NOF Corporation, ethylene bisstearylamide ⁇ 50 parts, base oil (e1) ⁇ mineral oil, Cosmo Pure Spin G, 300 parts of Cosmo Oil Lubricants Co., Ltd., and surfactant (fa1) ⁇ calcium dodecylbenzenesulfonate 70% methanol solution, Teika Power BC-2070M, Teika Co., Ltd., "Taika Power" are registered trademarks of the same company. . ⁇ The temperature was raised to 145 ° C. while stirring 10 parts, and stirring was continued for 15 minutes at this temperature to obtain a solution (1).
- the dispersion liquid (1) was cooled and stirred to 40 ° C. or lower, and homogenized at 3500 psi (24.1 MPa) using a gorin homogenizer at 40 ° C. or lower to obtain an oil phase (1).
- Oil phases (2) to (7) were obtained.
- the oil phase (X) is the solution (X), the receiving solution (X), and ⁇ "X" is a number from 2 to 7, and each of the preparation example, the oil phase, the solution, and the receiving solution is the same number. It is created using
- Nucleating agent (da1) Hydrophobic silica, Nipseal SS-100, Tosoh Silica Co., Ltd.
- nucleating agent (da2) Hydrophobic silica, AEROSIL R972, Nippon Aerosil Co., Ltd.
- nucleating agent (da3) Hydrophobic silica, SIPERNAT D10, Degussa Japan Co., Ltd.
- Nucleating agent (db2) Ethylene bis oleylamide, Alflow AD-281F, Nucleating agent (db3) manufactured by NOF Corporation: Stearylamide, Amide AP-1, Nucleating agent (db4) manufactured by Nippon Kasei Co., Ltd .: Hexamethylenebisstearyl Amide, ITOHWAX J-630, manufactured by Ito Oil Co., Ltd.
- Nucleating agent (dc1) Microcrystalline wax, Hi-Mic-2095, manufactured by Nippon Seiki Co., Ltd.
- Nucleating agent (dd1) Fischer-Tropsch wax, FT-105, Nippon Seika Co., Ltd.
- nucleating agent (dd2) Oxidized polyethylene wax, Epolen E-10, Eastman Chemical Co.
- nucleating agent (dd3) Alcohol-modified wax, OX-3405, manufactured by Nippon Seiki Co., Ltd.
- Nucleating agent (de1) Carnauba wax, Carnauba wax No. 1, manufactured by Hiroyuki Kato
- Nucleating agent (df1) synthetic resin fine particles, prepared according to Example 1 of JP2009-7506 A ⁇ (styrene) / (acrylonitrile) / (divinylbenzene) / (propylene oxide adduct of glycerin and 2 -Copolymers comprising as structural units a reactive dispersant obtained by jointing hydroxyethyl methacrylate with tolylene diisocyanate (TDI) / (polyoxyalkylene ether in which propylene oxide (PO) is added to allyl alcohol) (Particle diameter 0.7 ⁇ m) ⁇
- Base oil (e6): Propylene oxide (43 mol) adduct of glycerin (HLB 0.3, Sannix GP-3000, manufactured by Sanyo Chemical Industries, Ltd .; “Sannix” is a registered trademark of the company.
- Base oil (e13): Stearic acid diester of base oil (e4) (HLB 1.8)
- Base oil (e14): oleic acid monoester of adduct of castor oil with propylene oxide (30 mol) (HLB 0.1)
- Base oil (e15): ethylene oxide (3 mol) / 2-ethylhexyl glycidyl ether (6 mol) block adduct of glycerin (HLB 3.4)
- Base oil (e16): polyoxyethylene (3 mol) polyoxypropylene (14 mol) myristyl ether (HLB 2.3)
- interface Activator Barium petroleum sulfonate solution (barium petroleum sulfonate 30% by weight, oil content 69% by weight, water and unknown content 1% by weight), Sulhol BA-30N, surfactant manufactured by MORESCO Corporation (fa4): calcium petroleum Sulfonate solution (calcium petroleum sulfonate 45% by weight, oil 54% by weight, water and unknown 1% by weight), CA-45N, manufactured by MORESCO
- Water-soluble surfactant (fs1) alkyl (alkyl having 10 to 16 carbon atoms) sodium benzenesulfonate aqueous solution (sodium alkylbenzenesulfonate 50 wt%, water and inorganic salt 50 wt%), Newlex R, NOF Corporation
- Water-soluble surfactant (fs2) Sodium lauryl sulfate aqueous solution (sodium lauryl sulfate 31% by weight, water and inorganic salt 69% by weight), Sandet LNM, manufactured by Sanyo Chemical Industries, Ltd.
- Metal soap (g1) Aluminum stearate, SA-1500, manufactured by Sakai Chemical Industry Co., Ltd.
- Oil-soluble polymer (h1) (meth) acrylic acid alkyl copolymer, Include 728, Sanyo Chemical Industries, Ltd. oil-soluble polymer (h2): Petroleum resin, Alcon M-135, Arakawa Chemical Industries, Ltd. oil-soluble polymer (h3): Liquid rubber, Claprene LIR30, Kuraray Co., Ltd. oil-soluble polymer (h4): Block copolymer containing hydrogenated polydiene block and polystyrene block, Septon 4033, Kuraray Co., Ltd.
- Examples of oil phase preparation (8) to (11)> Other components ⁇ nucleating agent, base oil, oil-soluble polymer ⁇ described in Table 3 are added to the oil phase (1) ⁇ each used amount is a number (part) described in Table 3. ⁇ Stirring was continued for 60 minutes to obtain a uniform oil phase (8) to (11).
- the component of dissolution liquid (1) was changed to the component ⁇ nucleating agent, base oil, surfactant ⁇ described in Table 4, and the component of receiving liquid (1) was the component described in Table 5 ⁇ nucleating agent, base oil
- the oil phases (12) to (16) were obtained in the same manner as in the oil phase preparation example (1), except that the amount used was the number (part) described in Table 4 or 5. is there. ⁇ .
- the oil phase (X) is prepared by using the solution (X), the receiving solution (X), and ⁇ “X” is a number from 12 to 16 ⁇ .
- the median diameter (d50, based on the number) of silica was 83 nm.
- the median diameter of silica in the hydrophilic fumed silica dispersion (3) (D50, number basis) was 91 nm.
- d50 median diameter
- ⁇ Preparation of aqueous solution of thickener (1)> 20 parts of thickener (1) ⁇ xanthan gum, Kelzan, made by Sanki Co., Ltd. ⁇ , preservative (1) ⁇ bio killer LS, made by KEI Kasei Co., Ltd. ⁇ 0.1 part and 980 parts of water (i1) was added and stirred until uniform to obtain a thickener aqueous solution (1).
- ⁇ Preparation of aqueous solution of thickener (2)> In a stirrable container, add 15 parts of thickener (2) ⁇ hydroxypropylmethylcellulose, Metrolose 65SH-15000, Shin-Etsu Chemical Co., Ltd. ⁇ , 0.1 part of preservative (1) and 985 parts of water (i1) The mixture was stirred until uniform to obtain a thickener aqueous solution (2).
- Example 1 300 parts of the oil phase (1) was placed in a container, and 180 parts of the thickener aqueous solution (1) was added dropwise with stirring with a glass stir bar, and the mixture was stirred for 5 minutes to obtain a mixed solution.
- the prepared antifoaming agent is an oil-in-water emulsion.
- Optical microscope ⁇ manufactured by Olympus Corporation, BX-60, eyepiece: WH10X / 22, objective lens: UPlanFI 10X / 0.30 ph1 , Condenser: UPCD-ph1 ⁇ was used to confirm the transmitted light at a magnification of 100 (and so on).
- Example 2 Put 300 parts of the oil phase (2) in a container and stir with a glass stir bar while adding 5 parts of surfactant (fn1), 5 parts of surfactant (fn2), and 5 parts of surfactant (fn3). In addition, the mixture was stirred for 5 minutes to make it uniform, 180 parts of the thickener aqueous solution (1) was added dropwise, and stirred for 5 minutes to make it uniform to obtain a mixed solution.
- Example 3 An antifoaming agent (3) of the present invention was obtained in the same manner as in Example 2 except that the oil phase (2) was changed to the oil phase (3).
- the median diameter (d50, based on number) ( ⁇ m) of the emulsion particles of the antifoaming agent (3) was 1.0.
- Defoamers (4) to (14) of the present invention were obtained in the same manner as in Example 1 except that the oil phase (1) was changed to any of the oil phases (4) to (14).
- the foam number corresponds to the oil phase number ⁇ .
- the median diameter (d50, based on the number) ( ⁇ m) of the emulsion particles of the antifoams (4) to (14) was as described in Table 10.
- the median diameter (d50, based on number) ( ⁇ m) of the emulsion particles of the antifoaming agent (15) was 2.3.
- Example 16 and 17 The antifoaming agents (16) and (17) of the present invention were obtained in the same manner as in Example 1 except that the oil phase (1) was changed to the oil phase (16) or the oil phase (17).
- the agent number corresponds to the oil phase number ⁇ .
- the median diameter (d50, based on the number) ( ⁇ m) of the emulsion particles of the antifoams (16) and (17) was 1.3 and 5.2 in this order.
- Example 18 In a container capable of heating, stirring and cooling, 300 parts of the oil phase (18) is heated and stirred to 90 ° C., and the thickener aqueous solution ( 1) 180 parts were added dropwise and stirred for 5 minutes to make a uniform mixture.
- Defoamers (20) to (22) of the present invention were obtained in the same manner as in Example 19 except that the oil phase (19) was changed to any one of the oil phase (20) to the oil phase (22).
- the defoamer number corresponds to the oil phase number ⁇ .
- the median diameter (d50, based on number) ( ⁇ m) of the emulsion particles of the antifoams (20) to (22) was as described in Table 10.
- Examples 23 to 27 Content of 180 parts of thickener aqueous solution (1) described in Table 7 ⁇ Thickener aqueous solution or a mixture of this and water; each amount used is the number (parts) described in Table 7. ⁇ In the same manner as in Example 1 except that the antifoaming agents (23) to (27) of the present invention were obtained.
- the median diameter (d50, based on the number) ( ⁇ m) of the emulsion particles of the defoamers (23) to (27) was as described in Table 10.
- Example 28 to 32> The antifoaming agent (28) of the present invention was obtained in the same manner as in Example 1 except that the hydrophilic fumed silica dispersion (1) was changed to any one of the hydrophilic fumed silica dispersions (2) to (6). ) To (32) were obtained ⁇ the number of the antifoaming agent corresponds to the number obtained by adding 26 to the number of the hydrophilic fumed silica dispersion ⁇ .
- the median diameters (d50, based on the number) ( ⁇ m) of the emulsion particles of the defoamers (28) to (32) were as shown in Table 10.
- Example 1 except that the amounts of oil phase (1), thickener aqueous solution (1), hydrophilic fumed silica (1) and water (i1) were changed to the amounts (parts) listed in Table 8. Similarly, antifoams (33) to (40) of the present invention were obtained. The median diameters (d50, based on the number) ( ⁇ m) of the emulsion particles of the defoamers (33) to (40) were as shown in Table 10.
- Example 41 The same as in Example 1 except that the oil phase (1) was changed to the oil phase (14) and that the stirring with the glass stirring rod was changed to stirring with an Excel auto homogenizer equipped with a coreless blade.
- an antifoaming agent (41) of the present invention was obtained.
- the median diameter (d50, based on number) ( ⁇ m) of the emulsion particles of the antifoaming agent (41) was 0.5.
- Example 42 The same as in Example 1 except that the oil phase (1) was changed to the oil phase (14), and the stirring with the glass stirring rod was changed to stirring with an Excel auto homogenizer equipped with a coreless blade.
- an antifoaming agent (42) of the present invention was obtained.
- the median diameter (d50, based on number) ( ⁇ m) of the emulsion particles of the antifoaming agent (42) was 0.3.
- Examples 43 to 47> After mixing the surfactant described in Table 9 into 300 parts of the oil phase (1), ⁇ each used amount is the number (part) described in Table 9. ⁇ Defoamers (43) to (47) of the present invention were obtained in the same manner as in Example 1 except that this mixture was used as the oil phase. The median diameter (d50, based on the number) ( ⁇ m) of the emulsion particles of the defoamers (43) to (47) was as described in Table 10.
- Example 48 Place 150 parts of water (i1), 300 parts of hydrophilic fumed silica dispersion (4), and 150 parts of thickener aqueous solution (1) in a container and stir with a glass stir bar while stirring the oil phase (2).
- the median diameter (d50, based on number) ( ⁇ m) of the emulsion particles of the antifoaming agent (48) was 10.3.
- Defoamers (49) to (51) of the present invention were obtained in the same manner as in Example 48 except that the oil phase (2) was changed to the oil phase (6), (12) or (16) ⁇
- the antifoaming agent (49) uses the oil phase (6)
- the antifoaming agent (50) uses the oil phase (12)
- the antifoaming agent (51) uses the oil phase (16) ⁇ .
- the median diameter (d50, based on the number) ( ⁇ m) of the emulsion particles of the defoamers (49) to (51) was as shown in Table 10.
- Example 52 Excel auto homogenizer with 300 parts of oil phase (1), 3 parts of surfactant (fn1), 4 parts of surfactant (fn2) and 3 parts of surfactant (fn3) in a container and equipped with coreless blades While stirring at 3,000 rpm, 40 parts of hydrophilic fumed silica (c1) was added little by little, and the mixture was further stirred for 5 minutes to obtain a hydrophilic silica dispersed oil phase (ac1).
- Example 53 340 parts of water (i1) and 340 parts of thickener aqueous solution (1) are put in a container, and the hydrophilic silica dispersed oil phase (ac1) is stirred at 3,000 rpm with an Excel auto homogenizer equipped with a coreless blade. was added dropwise to obtain an oil-in-water antifoaming agent (53) of the present invention.
- the median diameter (d50, based on number) ( ⁇ m) of the emulsion particles of the antifoaming agent (53) was 3.1.
- Example 54 300 parts of the hydrophilic silica-dispersed oil phase (ac1) is placed in a container, 340 parts of the thickener aqueous solution (1) is added and uniformly mixed while stirring with a glass stirring rod, and then 340 parts of water (i1). was added and stirred for 5 minutes to obtain an oil-in-water antifoaming agent (54) of the present invention.
- the median diameter (d50, based on number) ( ⁇ m) of the emulsion particles of the defoamer (54) was 3.8.
- Example 55 Place 250 parts of base oil (e25) in a container and stir with a glass stir bar while adding 185 parts of water (i1), 50 parts of thickener aqueous solution (1) and 15 parts of hydrophilic fumed silica (c2). After mixing and mixing uniformly, 450 parts of water (i1) and 50 parts of thickener aqueous solution (1) were added and stirred for 5 minutes to obtain an oil-in-water defoamer (55) of the present invention.
- the median diameter (d50, based on number) ( ⁇ m) of the emulsion particles of the defoamer (55) was 5.7.
- Comparative defoamers (H1) to (H19) were obtained in the same manner as in Examples 1 to 19 except that the hydrophilic fumed silica dispersion (1) was changed to water (i1) ⁇ for comparison
- the defoaming agent number corresponds to the example number ⁇ .
- the median diameters (d50, based on the number) ( ⁇ m) of the emulsion particles of the antifoams (H1) to (H19) for comparison were as shown in Table 11.
- hydrophilic sedimentation silica dispersion (1) Hydrophilic sedimentation method silica (1) ⁇ Nip seal NA, manufactured by Tosoh Silica Co., Ltd. ⁇ 50 parts and water (i1) 950 parts are put in a container and treated with an ultrasonic disperser UP400S for 2 minutes at a strength of 20, A hydrophilic precipitated silica dispersion (1) was obtained.
- the median diameter (d50, based on number) of silica in the hydrophilic sedimentation silica dispersion (1) was 13.5 ⁇ m.
- hydrophilic gel silica (1) ⁇ Nipgel AZ-600, manufactured by Tosoh Silica Co., Ltd. ⁇ 50 parts and water (i1) 950 parts are put in a container and treated with an ultrasonic disperser UP400S for 2 minutes at a strength of 20. A hydrophilic gel silica dispersion (1) was obtained. The median diameter (d50, based on number) of silica in the hydrophilic gel method silica dispersion (1) was 4.2 ⁇ m.
- Emulsion paints (1) to (67) were each stored in a sealed sample container at 40 ° C for 1 month and then cooled to 25 ° C for defoaming sustainability evaluation. An emulsion paint was obtained, and the defoaming sustainability (antifoaming property) was similarly evaluated.
- ⁇ Defoaming property initial defoaming property, defoaming sustainability; 1 minute after painting
- 5 No bubbles 4: 4 or less bubbles 3: 5 to 10 bubbles 2: 11 to 20 bubbles 1: 21 or more bubbles
- the emulsion paint using the antifoaming agent of the present invention has an antifoaming property (initial antifoaming property) compared to that using a comparative antifoaming agent prepared using the same oil phase and that using the oil phase as it is. , Antifoaming sustainability) was improved, and repellency was reduced.
- ⁇ No change from before days. ⁇ : Separation occurs but the emulsion state is maintained, and when the bottle is covered and shaken up and down 20 times by hand, it returns to a uniform state. X: Separation occurred and the emulsion state was destroyed, so even if shaken up and down, it does not return.
- the antifoaming agent of the present invention showed much better stability than that using a comparative antifoaming agent.
- the antifoaming agent of the present invention can be used for any application, but is effective for aqueous foaming liquids.
- the paper pulp manufacturing industry pulp manufacturing industry (pulping process, paper making process, coating process, etc.), construction industry ( It can be applied to bubbles generated in various processes such as paper making process, dye industry, dyeing industry, fermentation industry, synthetic resin manufacturing industry, synthetic rubber manufacturing industry, ink, paint industry and textile processing industry.
- it is suitable as an antifoaming agent for paints, an antifoaming agent for wastewater treatment, an antifoaming agent for the paper pulp manufacturing industry, and further suitable as an antifoaming agent for aqueous paints.
- coating materials for building interiors, water-based inks, paper coatings, etc. it is most suitable as an antifoaming agent for emulsion paints.
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Abstract
Description
本発明の目的は、消泡性(初期消泡性及び消泡持続性)及び安定性(エマルション安定性)に優れた水中油型エマルション消泡剤を提供することである。
すなわち、本発明の消泡剤の特徴は、親水性ヒュームドシリカ(C)を含有し、油相(A)を水相(B)に分散してなることを要旨とする。
水相(B)に、親水性ヒュームドシリカ(C)を分散・解砕しながら親水性ヒュームドシリカのメジアン径(d50、個数基準)が20~300nmである分散液(BC1)を得る分散・解砕工程(i)と、
分散・解砕工程(i)で作成した分散液(BC1)と油相(A)とを乳化・分散して水中油型エマルション消泡剤を得る乳化・分散工程(ii)とを含むことを要旨とする。
油相(A)と水相(B)の残部とを混合・分散して混合分散液(AB)を得る混合・分散工程(iv)と、
混合分散液(AB)と分散液(BC2)とを乳化・分散して水中油型エマルション消泡剤を得る乳化・分散工程(v)とを含むことを要旨とする。
分散液(AC)と水相(B)とを乳化・分散して水中油型エマルション消泡剤を得る乳化・分散工程(vii)とを含むことを要旨とする。
親水性ヒュームドシリカ(C)は、市場から容易に入手でき、たとえば、アエロジルシリーズ(130、200、300等、日本アエロジル株式会社、「アエロジル」は登録商標である。)、乾式シリカHDKシリーズ(S13、V15、N20、T30等、旭化成ワッカ-シリコーン株式会社、「HDK」は登録商標である。)、レオロシールシリーズ(QS-10、QS-30、QS-40、QS-102、株式会社トクヤマ、「レオロシール」は登録商標である。)、CAB-O-SIL EH-5、CAB-O-SIL HS-5、CAB-O-SIL M-5(キャボット コーポレーション、「CAB-O-SIL」は登録商標である。)等が挙げられる。
シリコーンオイルとしては、動粘度10~10000(mm2/s、25℃)のポリジメチルシロキサン等が挙げられ、シクロオクタメチルテトラシロキサン等も含まれる。
変性シリコーンとしては、上記のジメチルシロキサンのメチル基の一部を炭素数2~6のアルキル基、炭素数2~4のアルコキシル基、フェニル基、水素原子、ハロゲン(塩素及び臭素等)原子、アルコキシポリオキシアルキレンオキシプロピル基(アルコキシの炭素数1~6、アルキレンの炭素数2~3、重合度2~50、オキシエチレン基の重量がオキシアルキレン基全体の重量の20重量%未満)、アルコキシポリオキシアルキレン基(アルコキシの炭素数1~6、アルキレンの炭素数2~3、重合度2~50、オキシエチレン基の重量がオキシアルキレン基全体の20重量%未満)及び/又は炭素数2~6のアミノアルキル基等に置き換えたもの等が含まれる。
核剤(D)としては、25℃で液状の基油(E)に溶解せず、この基油(E)に分散できるものが含まれ、疎水性シリカ(Da)、脂肪酸アミド(Db)、石油ワックス(Dc)、合成ワックス(Dd)、植物ワックス(De)及び合成樹脂微粒子(Df)からなる群から選ばれる1種以上を用いることができる。
市場から入手できる疎水性シリカとしては、商品名として、Nipsil SS-10、SS-40、SS-50及びSS-100(東ソー・シリカ株式会社、「Nipsil」は東ソー・シリカ株式会社 の登録商標である。)、AEROSIL R972、RX200及びRY200(日本アエロジル株式会社、「AEROSIL」はエボニック デグサ ゲーエムベーハーの登録商標である。 )、SIPERNAT D10、D13及びD17(デグサジャパン株式会社、「SIPERNAT」はエボニック デグサ ゲーエムベーハーの登録商標である。 )、TS-530、TS-610、TS-720(キャボットカーボン社)、AEROSIL R202,R805及びR812(デグサジャパン株式会社)、REOLOSIL MT-10、DM-10及びDM-20S (株式会社トクヤマ、「REOLOSIL」は同社の登録商標である。)、並びにSYLOPHOBIC100、702、505及び603(富士シリシア化学株式会社、「SYLOPHOBIC」は同社の登録商標である。)等が挙げられる。
アルティフロー FS-7301(三洋化成工業(株)製、エチレン性不飽和モノマー共重合物のポリエーテル分散体、「アルティーフロー」は同社の登録商標である)、ダイミックビーズ UCN-8070CMクリヤー(大日精化工業(株)製、ポリウレタンビーズ、「ダイナミックビーズ」は同社の登録商標である)、タフチック F-120、F-167(東洋紡(株)製、エチレン性不飽和モノマー共重合物の水分散体;「タフチック」は同社の登録商標である)
25℃で液状である基油(E)の残部を攪拌しながら、この残部に溶解液を投入して混合物を得る混合工程(dii)、並びに
混合物を均質化処理して脂肪酸アミド(Db)、石油ワックス(Dc)、合成ワックス(Dd)及び/又は植物ワックス(De)の分散液を得る分散工程(diii)を含む方法。
非イオン型界面活性剤としては、HLB3.5~20のものが使用でき、好ましくはHLB3.6~19のもの、さらに好ましくはHLB3.7~18のもの、最も好ましくはHLB4~17のものである。
塩としては特に制限されないが、アルカリ金属(ナトリウム、カリウム等)塩、アルカリ土類金属(カルシウム、マグネシウム等)塩、アンモニウム塩及び炭素数1~18のアミン塩(トリエタノールアミン、トリメチルアミン、プロピルアミン等)等が含まれる(以下同じ)。
<方法1>
金属石鹸(G)と25℃で液状である基油(E)の一部を加熱混合し、金属石鹸(G)を均一に溶解させた後、40℃以下に冷却した混合液を作成し、これと残りの基油(E)等と混合して油相(A)とする方法。
金属石鹸(G)と25℃で液状である基油(E)の一部と、界面活性剤(F)の一部又は全部とを加熱混合し、金属石鹸(G)を均一に溶解させた後、40℃以下に冷却した混合液を作成し、これと残りの基油(E)等と混合して油相(A)とする方法。
金属石鹸(G)と25℃で液状である基油(E)等とを加熱混合し、金属石鹸(G)を均一に溶解させた後、40℃以下に冷却して油相(A)とする方法。
イオン交換水をフローセルに入れて循環(循環強度5)しながら、ブランク測定を行う。100mLガラスビーカーにイオン交換水を約10mL入れ、測定試料(水中油型エマルション消泡剤)を数滴加えて均一になるまで混合して分散液を作成する。この分散液をフローセルに少しずつ加えて、適切な透過光強度(青色LEDの透過光強度が80~90%又は赤色LEDの透過光強度が70~90%)に調整して測定を行う。
なお、測定値はブランク測定の値が差し引かれて算出される。
<製造方法(1)>
水相(B)に、親水性ヒュームドシリカ(C)を分散・解砕しながら親水性ヒュームドシリカのメジアン径(d50、個数基準)が20~300nmである分散液(BC1)を得る分散・解砕工程(i)と、
分散・解砕工程(i)で作成した分散液(BC1)と油相(A)とを乳化・分散して水中油型エマルション消泡剤を得る乳化・分散工程(ii)とを含む方法(1)。
水相(B)の一部に親水性ヒュームドシリカ(C)を分散・解砕しながら親水性ヒュームドシリカのメジアン径(d50、個数基準)が20~300nmである分散液(BC2)を得る分散・解砕工程(iii)と、
油相(A)と水相(B)の残部とを混合・分散して混合分散液(AB)を得る混合・分散工程(iv)と、
混合分散液(AB)と分散液(BC2)とを乳化・分散して水中油型エマルション消泡剤を得る乳化・分散工程(v)とを含む方法(2)。
油相(A)に親水性ヒュームドシリカ(C)を分散・解砕しながら親水性ヒュームドシリカの分散液(AC)を得る分散・解砕工程(vi)と、
分散液(AC)と水相(B)とを乳化・分散して水中油型エマルション消泡剤を得る乳化・分散工程(vii)とを含む方法(3)。
これらのうち、塗料用消泡剤、排水処理用消泡剤として適しており、さらに水性塗料用消泡剤として好適であり、水性塗料(水性建築外装用塗料、建築内装用塗料、水性インキ及び紙塗工用塗料等)のうち、エマルション塗料用消泡剤として最適である。
ただし、フローセルに入れる測定試料{親水性ヒュームドシリカの分散液(BC1又はBC2)}の量は、青色LED光の透過率が88~92%になるように調整し、測定試料の量が多いほど透過率が低くなるので、この範囲から外れている場合、測定試料又は分散媒の量により、範囲内に入るように調整した。
加熱、攪拌、冷却の可能な容器内で核剤(db1){アルフローH-50S、日油株式会社製、エチレンビスステアリルアミド}50部、基油(e1){鉱物油、コスモピュアスピン G、コスモ石油ルブリカンツ(株)}300部、及び界面活性剤(fa1){ドデシルベンゼンスルホン酸カルシウム70%メタノール溶液、テイカパワー BC-2070M、テイカ(株)、「テイカパワー」は同社の登録商標である。}10部を加熱攪拌しながら145℃まで昇温し、この温度にてさらに15分間加熱攪拌を続けて溶解液(1)を得た。
溶解液(1)の成分及び使用量(部)を表1のように、受け液(1)の成分を表2のように変えた以外、油相の作成例(1)と同様にして、油相(2)~(7)を得た。なお、油相(X)は、溶解液(X)と受け液(X)と{「X」は2~7の数字であり、作成例、油相、溶解液、受け液のそれぞれが同じ数字となる}を用いて作成したものである。
核剤(da2):疎水性シリカ、AEROSIL R972、日本アエロジル株式会社製
核剤(da3):疎水性シリカ、SIPERNAT D10、デグサジャパン株式会社製
核剤(da4):疎水性シリカ、ニップシール G-0251、東ソー・シリカ株式会社製
核剤(db3):ステアリルアミド、アマイドAP-1、日本化成株式会社製
核剤(db4):ヘキサメチレンビスステアリルアミド、ITOHWAX J-630、伊藤製油株式会社製
核剤(dd2):酸化ポリエチレンワックス、エポレンE-10、イーストマンケミカル社製
核剤(dd3):アルコール変性ワックス、OX-3405、日本精鑞株式会社製
基油(e5):蔗糖ポリオキシプロピレン80モル付加物(HLB=1.4)。
基油(e6):グリセリンのプロピレンオキシド(43モル)付加体(HLB=0.3、サンニックスGP-3000、三洋化成工業株式会社製;「サンニックス」は同社の登録商標である。
基油(e7):トリメチロールプロパンのエチレンオキシド(10モル)/プロピレンオキシド(68モル)ブロック付加体(HLB=2.0)、ニューポールTL-4500N、三洋化成工業株式会社製
基油(e8):グリセリンのプロピレンオキシド(9モル)付加体(HLB=1.5)、ニューポールGP-600、三洋化成工業株式会社製
基油(e9):ブタノールポリオキシプロピレン(40モル)付加体(HLB=0.1、ニューポールLB-1715、三洋化成工業株式会社製
基油(e10):ブタノールポリオキシプロピレン(33モル)付加体(HLB=0.2、ニューポールLB-625、三洋化成工業株式会社製
基油(e11):ポリプロピレングリコール(34モル)(HLB=0.3)、ニューポールPP-2000、三洋化成工業株式会社製
基油(e12):ポリオキシプロピレン(40モル)グリコールモノブチルエーテルのオレイン酸エステル(HLB=0)
基油(e13):基油(e4)のステアリン酸ジエステル(HLB=1.8)
基油(e14):ひまし油のプロピレンオキシド(30モル)付加体のオレイン酸モノエステル(HLB=0.1)
基油(e15):グリセリンのエチレンオキシド(3モル)/2-エチルヘキシルグリシジルエーテル(6モル)ブロック付加体(HLB=3.4)
基油(e16):ポリオキシエチレン(3モル)ポリオキシプロピレン(14モル)ミリスチルエーテル(HLB=2.3)
基油(e17):ポリオキシプロピレン(34モル)グリコール200部と、ポリオキシプロピレン(14モル)ミリスチルエーテル231部と、ヘキサメチレンジイソシアネート16.8部とを反応させて得たポリエーテル化合物(HLB=0)
基油(e18):ペンタエリスリトールにプロピレンオキシド-エチレンオキシド(エチレンオキシドの割合12重量%)の順にアルキレンオキシドをブロック付加させた水酸基価32のポリオール(HLB=2.5)
基油(e19):特開2000-344881号公報{対応米国特許:US6,531,566B1(これに開示された開示内容を参照により本出願に取り込む。)}に準じて作成したグリセリンプロピレンオキシド付加体、水酸基価56(HLB=0.1)
基油(e20):食用菜種油、ニッコー製油株式会社製
基油(e21):オレイン酸メチル、エキセパール M-OL、花王株式会社製;「エキセパール」は同社の登録商標である。
基油(e22):ジメチルシリコーンオイル(動粘度50(mm2/s、25℃))、KF-96L-5CS、信越化学工業株式会社製
基油(e23):ジメチルシリコーンオイル、(動粘度3000(mm2/s、25℃))、KF-96-3,000CS、信越化学工業株式会社製
基油(e24):ジメチルシリコーン(数平均分子量1800)のメチル基のうち、平均して1分子あたり4つがポリオキシプロピレン(25モル)オキシプロピル基に置換されたシリコーン化合物。
基油(e25):シリコーンコンパウンド、PULPSIL245C、旭化成ワッカーシリコーン株式会社製。
界面活性剤(fn2):ポリオキシエチレンアルキレンエーテル(HLB=10.7、ナロアクティー CL-70、三洋化成工業株式会社製
界面活性剤(fn3):ソルビタンモノオレート(HLB=4.3)、イオネット S-80、三洋化成工業株式会社製
界面活性剤(fn4):ポリオキシエチレンアルキレンエーテル(HLB=8.9、ナロアクティー CL-40、三洋化成工業株式会社製
界面活性剤(fn5):ポリオキシエチレンモノオレート(HLB=11.8)、イオネット MO-400、三洋化成工業株式会社製
界面活性剤(fn6):グリセロールモノオレート(HLB=3.5)、エキセルO-95N、花王株式会社製
界面活性剤(fa2):ナトリウム石油スルホネート溶液(ナトリウム石油スルホネート62重量%、油分34重量%、水及び無機塩類4重量%)、スルホール430A、MORESCO株式会社製
界面活性剤(fa3):バリウム石油スルホネート溶液(バリウム石油スルホネート30重量%、油分69重量%、水及び不明分1重量%)、スルホールBA-30N、MORESCO株式会社製
界面活性剤(fa4):カルシウム石油スルホネート溶液(カルシウム石油スルホネート45重量%、油分54重量%、水及び不明分1重量%)、CA-45N、MORESCO株式会社製
水溶性界面活性剤(fs2):ラウリル硫酸ナトリウム水溶液(ラウリル硫酸ナトリウム31重量%、水及び無機塩69重量%)、サンデットLNM、三洋化成工業株式会社製
油溶性ポリマー(h2):石油樹脂、アルコンM-135、荒川化学工業株式会社製
油溶性ポリマー(h3):液状ゴム、クラプレンLIR30、株式会社クラレ製
油溶性ポリマー(h4):水添ポリジエンブロックとポリスチレンブロックとを含むブロックコポリマー、セプトン4033、株式会社クラレ製
油相(1)に、表3に記載した他の成分{核剤、基油、油溶性ポリマー}を加え{各使用量は、表3に記載した数字(部)である。}、60分間攪拌を続けて均一にして、油相(8)~(11)を得た。
溶解液(1)の成分を表4に記載の成分{核剤、基油、界面活性剤}に変えたこと、受け液(1)の成分を表5に記載の成分{核剤、基油}に変えたこと以外、油相の作成例(1)と同様にして、油相(12)~(16)を得た{各使用量は、表4又は5に記載した数字(部)である。}。なお、油相(X)は、溶解液(X)と受け液(X)と{「X」は12~16の数字}を用いて作成したものである。
加熱、攪拌、冷却の可能な容器内で基油(e1)890部、基油(e16)60部、界面活性剤(fa1)30部、及び金属石鹸(g1)50部を加熱攪拌しながら145℃まで昇温し、この温度にてさらに15分間加熱攪拌を続けて均一に溶解させた後、30℃になるまで冷却攪拌して油相(17)を得た。
使用する原料を表6に記載したもの{核剤、基油、界面活性剤、金属石鹸、油溶性ポリマー}に変えたこと以外、油相の作成例(17)と同様にして、油相(18)~(22)を得た{各使用量は、表6に記載した数字(部)である。}。
親水性ヒュームドシリカ(c1){AEROSIL 130(BET比表面積=130(m2/g)、日本アエロジル株式会社製}60部及び水(i1){上水}940部を容器に入れ、コーレス型羽根を装着したエクセルオートホモジナイザー{株式会社日本精機製作所製}にて4000rpmにて30分間攪拌し、親水性ヒュームドシリカ分散液(1)を得た。親水性ヒュームドシリカ分散液(1)中のシリカのメジアン径(d50、個数基準)は、83nmだった。
親水性ヒュームドシリカ(c2){AEROSIL 300(BET比表面積=300(m2/g)、日本アエロジル株式会社製}60部及び水(i1)920部を容器に入れ、超音波分散機UP400S{Hielscher Ultrasonic GmbH製}にて、1分間、強度20で処理し、親水性ヒュームドシリカ分散液(2)を得た。親水性ヒュームドシリカ分散液(2)中のシリカのメジアン径(d50、個数基準)は、71nmだった。
親水性ヒュームドシリカ(c3){CAB-O-SIL L-90(BET比表面積=90(m2/g)、キャボット コーポレーション製}80部及び水(i2){イオン交換水}920部を容器に入れ、超音波分散機UP400Sにて、2分間、強度20で処理し、親水性ヒュームドシリカ分散液(3)を得た。親水性ヒュームドシリカ分散液(3)中のシリカのメジアン径(d50、個数基準)は、91nmだった。
親水性ヒュームドシリカ(c4){アエロジル380(BET比表面積=380(m2/g)、日本アエロジル株式会社製}50部及び水(i1)950部を容器に入れ、超音波分散機UP400Sにて、10分間、温度が50℃以上にならないように冷却しながら、強度50で処理し、親水性ヒュームドシリカ分散液(4)を得た。親水性ヒュームドシリカ分散液(4)中のシリカのメジアン径(d50、個数基準)は、34nmだった。
親水性ヒュームドシリカ(c5){レオロシールQS-10(BET比表面積=140(m2/g)、株式会社トクヤマ製}50部及び水(i1)950部を容器に入れ、超音波分散機UP400Sにて、2分間、強度20で処理し、親水性ヒュームドシリカ分散液(5)を得た。親水性ヒュームドシリカ分散液(5)中のシリカのメジアン径(d50、個数基準)は、79nmだった。
親水性ヒュームドシリカ(c6){アエロジル50(BET比表面積=50(m2/g)、日本アエロジル株式会社製}60部及び水(i1)940部を容器に入れ、超音波分散機UP400Sにて、2分間、強度20で処理し、親水性ヒュームドシリカ分散液(6)を得た。親水性ヒュームドシリカ分散液(6)中のシリカのメジアン径(d50、個数基準)は、98nmだった。
攪拌のできる容器内に、増粘剤(1){キサンタンガム、ケルザン、三晶株式会社製}20部、防腐剤(1){バイオキラーLS、ケイ・アイ化成株式会社製}0.1部及び水(i1)980部を加え、均一になるまで攪拌して増粘剤水溶液(1)を得た。
攪拌のできる容器内に、増粘剤(2){ヒドロキシプロピルメチルセルロース、メトローズ65SH-15000、信越化学工業株式会社}15部、防腐剤(1)0.1部及び水(i1)985部を加え、均一になるまで攪拌して増粘剤水溶液(2)を得た。
容器に油相(1)300部を入れ、ガラス製の攪拌棒で攪拌しながら、増粘剤水溶液(1)180部を滴下し、5分攪拌して均一にして、混合液を得た。
容器に油相(2)300部を入れ、ガラス製の攪拌棒で攪拌しながら、界面活性剤(fn1)5部、界面活性剤(fn2)5部、及び界面活性剤(fn3)5部を加えて5分攪拌して均一にし、増粘剤水溶液(1)180部を滴下し、5分攪拌して均一にして、混合液を得た。
油相(2)を油相(3)に変更したこと以外、実施例2と同様にして、本発明の消泡剤(3)を得た。消泡剤(3)のエマルション粒子のメジアン径(d50、個数基準)(μm)は、1.0であった。
油相(1)を油相(4)~(14)のいずれかに変更したこと以外、実施例1と同様にして、本発明の消泡剤(4)~(14)を得た{消泡剤の番号は油相の番号と対応する}。消泡剤(4)~(14)のエマルション粒子のメジアン径(d50、個数基準)(μm)は、表10に記載した通りであった。
容器に油相(15)300部を入れ、ガラス製の攪拌棒で攪拌しながら、界面活性剤(fn7){ポリオキシエチレンポリオキシプロピレングリコール(HLB=8.0)、 ニューポールPE-74、三洋化成工業株式会社製}5部、界面活性剤(fn2)5部、及び界面活性剤(fn3)5部を加えて5分攪拌して均一にし、そこに増粘剤水溶液(1)180部を滴下し、5分攪拌して均一にして、混合液を得た。
油相(1)を油相(16)又は油相(17)に変更したこと以外、実施例1と同様にして、本発明の消泡剤(16)、(17)を得た{消泡剤の番号は油相の番号に対応する}。消泡剤(16)、(17)のエマルション粒子のメジアン径(d50、個数基準)(μm)は、順に、1.3、5.2であった。
加熱、攪拌、冷却の可能な容器内で油相(18)300部を90℃に加熱攪拌し、油相の温度が75℃~90℃になるように加熱攪拌しながら、増粘剤水溶液(1)180部を滴下し、5分攪拌して均一にして、混合液を得た。
加熱、攪拌、冷却の可能な容器内で油相(19)300部を90℃に加熱攪拌し、界面活性剤(fn8){ポリオキシエチレンひまし油(HLB=6.4)、ブラウノンBR-410、青木油脂工業株式会社製}5部、界面活性剤(fn2)5部、及び界面活性剤(fn3)5部を加えて均一にした後、滴下中の温度が75℃~90℃になるように加熱攪拌しながら、増粘剤水溶液(1)180部を滴下し、5分攪拌して均一にして、混合液を得た。
油相(19)を油相(20)~油相(22)のいずれかに変更したこと以外、実施例19と同様にして、本発明の消泡剤(20)~(22)を得た{消泡剤の番号は油相の番号と対応する}。消泡剤(20)~(22)のエマルション粒子のメジアン径(d50、個数基準)(μm)は、表10に記載した通りであった。
増粘剤水溶液(1)180部を表7に記載した内容{増粘剤水溶液又はこれと水との混合物;各使用量は表7に記載した数字(部)である。}に変更したこと以外、実施例1と同様にして、本発明の消泡剤(23)~(27)を得た。消泡剤(23)~(27)のエマルション粒子のメジアン径(d50、個数基準)(μm)は、表10に記載した通りであった。
親水性ヒュームドシリカ分散液(1)を親水性ヒュームドシリカ分散液(2)~(6)のいずれかに変更したこと以外、実施例1と同様にして、本発明の消泡剤(28)~(32)を得た{消泡剤の番号は親水性ヒュームドシリカ分散液の番号に26を加算した数値に対応する}。消泡剤(28)~(32)のエマルション粒子のメジアン径(d50、個数基準)(μm)は、表10に記載した通りであった。
油相(1)、増粘剤水溶液(1)、親水性ヒュームドシリカ(1)及び水(i1)の量を、表8に記載した量(部)に変更したこと以外、実施例1と同様にして、本発明の消泡剤(33)~(40)を得た。消泡剤(33)~(40)のエマルション粒子のメジアン径(d50、個数基準)(μm)は、表10に記載した通りであった。
油相(1)を油相(14)に変更したこと、ガラス製の攪拌棒による攪拌をコーレス型羽根を装着したエクセルオートホモジナイザー1,000rpmによる攪拌に変更したこと以外、実施例1と同様にして、本発明の消泡剤(41)を得た。消泡剤(41)のエマルション粒子のメジアン径(d50、個数基準)(μm)は、0.5であった。
油相(1)を油相(14)に変更したこと、ガラス製の攪拌棒による攪拌をコーレス型羽根を装着したエクセルオートホモジナイザー4,000rpmによる攪拌に変更したこと以外、実施例1と同様にして、本発明の消泡剤(42)を得た。消泡剤(42)のエマルション粒子のメジアン径(d50、個数基準)(μm)は、0.3であった。
油相(1)300部に表9に記載した界面活性剤を混合してから{各使用量は表9に記載した数字(部)である。}、この混合物を油相として用いたこと以外、実施例1と同様にして、本発明の消泡剤(43)~(47)を得た。消泡剤(43)~(47)のエマルション粒子のメジアン径(d50、個数基準)(μm)は、表10に記載した通りであった。
容器に水(i1)150部、親水性ヒュームドシリカ分散液(4)300部、及び増粘剤水溶液(1)150部を入れ、ガラス製の攪拌棒で攪拌しながら、油相(2)を滴下して、本発明の水中油型消泡剤(48)を得た。消泡剤(48)のエマルション粒子のメジアン径(d50、個数基準)(μm)は、10.3であった。
油相(2)を油相(6)、(12)又は(16)に変更したこと以外、実施例48と同様にして、本発明の消泡剤(49)~(51)を得た{消泡剤(49)は油相(6)、消泡剤(50)は油相(12)、消泡剤(51)は油相(16)を用いたものである}。消泡剤(49)~(51)のエマルション粒子のメジアン径(d50、個数基準)(μm)は、表10に記載した通りであった。
容器に油相(1)300部、界面活性剤(fn1)3部、界面活性剤(fn2)4部、及び界面活性剤(fn3)3部、を入れ、コーレス型羽根を装着したエクセルオートホモジナイザーにて3,000rpmで攪拌しつつ、親水性ヒュームドシリカ(c1)40部を少しずつ加え、さらに5分攪拌して均一にして、親水性シリカ分散油相(ac1)を得た。
容器に水(i1)340部、及び増粘剤水溶液(1)340部を入れ、コーレス型羽根を装着したエクセルオートホモジナイザーにて3,000rpmで攪拌しながら、親水性シリカ分散油相(ac1)を滴下して、本発明の水中油型消泡剤(53)を得た。消泡剤(53)のエマルション粒子のメジアン径(d50、個数基準)(μm)は、3.1であった。
容器に親水性シリカ分散油相(ac1)300部を入れ、ガラス製の攪拌棒で攪拌しながら、増粘剤水溶液(1)340部を入れて均一に混合した後、水(i1)340部を加えて5分間攪拌して、本発明の水中油型消泡剤(54)を得た。消泡剤(54)のエマルション粒子のメジアン径(d50、個数基準)(μm)は、3.8であった。
容器に基油(e25)250部を入れ、ガラス製の攪拌棒で攪拌しながら、水(i1)185部、増粘剤水溶液(1)50部及び親水性ヒュームドシリカ(c2)15部を入れて均一に混合した後、水(i1)450部及び増粘剤水溶液(1)50部を加えて5分間攪拌して、本発明の水中油型消泡剤(55)を得た。消泡剤(55)のエマルション粒子のメジアン径(d50、個数基準)(μm)は、5.7であった
親水性ヒュームドシリカ分散液(1)を水(i1)に変更したこと以外、実施例1~19と同様にして、比較用の消泡剤(H1)~(H19)を得た{比較用の消泡剤の番号は実施例の番号に対応する}。比較用の消泡剤(H1)~(H19)のエマルション粒子のメジアン径(d50、個数基準)(μm)は、表11に記載した通りであった。
容器に油相(1)300部を入れ、コーレス型羽根を装着したエクセルオートホモジナイザーにて3,000rpmで攪拌しながら、界面活性剤(fn1)4.8部、界面活性剤(fn2)6.4部、及び界面活性剤(fn3)4.8部を加えて1分攪拌して均一にし、攪拌しながら増粘剤水溶液(1)180部を滴下し、1分攪拌して均一にして、混合液を得た。
親水性沈降法シリカ(1){ニップシールNA、東ソー・シリカ株式会社製}50部及び水(i1)950部を容器に入れ、超音波分散機UP400Sにて、2分間、強度20で処理し、親水性沈降シリカ分散液(1)を得た。親水性沈降法シリカ分散液(1)中のシリカのメジアン径(d50、個数基準)は、13.5μmだった。
親水性ゲル法シリカ(1){ニップゲルAZ-600、東ソー・シリカ株式会社製}50部及び水(i1)950部を容器に入れ、超音波分散機UP400Sにて、2分間、強度20で処理し、親水性ゲル法シリカ分散液(1)を得た。親水性ゲル法シリカ分散液(1)中のシリカのメジアン径(d50、個数基準)は、4.2μmだった。
親水性ヒュームドシリカ分散液(1)を親水性沈降法シリカ分散液(1)に変更したこと以外、実施例1と同様にして、水中油型エマルションの作成を試みたが、油相が正常に乳化されず、水中油型エマルションは得られなかった。
親水性ヒュームドシリカ分散液(1)を親水性ゲル法シリカ分散液(1)に変更したこと以外、実施例1と同様にして、水中油型エマルションの作成を試みたが、油相が正常に乳化されず、水中油型エマルションは得られなかった。
実施例1~55及び比較例1~22で得た消泡剤(1)~(55)及び(H2)、(H3)、(H6)、(H12)、(H13)及び(H20)を用いて、以下のようにして調製したエマルション塗料に対する消泡性を評価し、評価結果を表13~14に示した。
また、油相(1)~(3)、(18)及び(19)を用いて、同様にエマルション塗料を調製し、消泡性を評価し、評価結果を表14に示した。
以下の原料組成にて、インペラー型羽根を装着したエクセルオートホモジナイザー(日本精器株式会社製、モデルED)を用いて、グラインディング及びレットダウンして塗料化した。得られた塗料を、ストマー粘度計(JIS K5600-2-2)で80KU(25℃)になるように水(i1)で希釈してエマルションベース塗料を得た。
注2:サンノプコ(株)製増粘剤
注3:竹原化学工業(株)製炭酸カルシウム
注4:石原産業(株)製二酸化チタン
注5:BASF社製アクリルエマルション、「ACRONAL」は、ビ-エ-エスエフ アクチエンゲゼルシヤフトの登録商標である。
注6:サンノプコ(株)製防腐剤
注7:イーストマンケミカル社製造膜調整剤、「テキサノール」は吉村油化学株式会社の登録商標である。
注8:サンノプコ(株)製増粘剤
エマルションベース塗料に、評価試料(消泡剤)を対エマルションベース塗料で消泡剤の油相(A)の添加量が、0.3重量%となるように加えて、インペラー型羽根を装着したエクセルオートホモジナイザーにて25℃、2000rpm、5分間攪拌混合し、さらに5重量%(エマルション塗料に対して)の水(i1)を加えて均一に混合して、エマルション塗料(1)~(66)を得た。また、ブランク用として消泡剤を加えないこと以外、上記と同様にして、エマルション塗料(67)を得た。
25℃、60%相対湿度に調整したコントロールルームにて、ブリキ板{厚さ0.5mm、10×15cmにカット}をアセトン/布にて脱脂した後、ウェット膜厚250μmとなるようにエマルション塗料(1)~(67)をローラー塗装して塗装1分後の泡量と、1日間乾燥させた(コントロールルームに放置)後の泡跡の量を評価した。
25℃、60%相対湿度に調整したコントロールルームにて、ブリキ板{厚さ0.5mm、10×15cmにカット}をアセトン/布にて脱脂した後、ウェット膜厚250μmとなるようにエマルション塗料(1)~(67)をローラー塗装して、1日間乾燥させた(コントロールルームに放置)後、塗膜表面を観察して、ハジキの個数を評価した。
エマルション塗料(1)~(67)をそれぞれ密閉サンプル容器にて、40℃にて1ケ月静置保管した後、25℃に冷却し消泡持続性評価用のエマルション塗料を得、同様に消泡持続性(消泡性)を評価した。
5:泡がない
4:泡が4個以下ある
3:泡が5~10個ある
2:泡が11~20個ある
1:泡が21個以上ある
5:泡痕がない
4:泡痕が2個以下ある
3:泡痕が3~5個ある
2:泡痕が6~10個ある
1:泡痕が11個以上ある
実施例及び比較例で得た消泡剤(1)~(55)及び(H2)、(H3)、(H6)、(H12)、(H13)及び(H20)を、密閉ガラス容器に入れて40℃の雰囲気下に1週間、静置した後、サンプルの外観を確認し、以下の基準で評価した。評価結果を表15及び16に示した。
△:分離が発生しているがエマルション状態は維持しており、瓶の蓋をして手で上下に20回振とうすると均一状態に戻る。
×:分離が発生し、エマルション状態が破壊されているため、上下に振とうしても元に戻らない。
Claims (12)
- 親水性ヒュームドシリカ(C)を含有し、油相(A)を水相(B)に乳化・分散してなることを特徴とする水中油型エマルション消泡剤。
- 油相(A)、親水性ヒュームドシリカ(C)、水相(B)の重量に基づいて、油相(A)の含有量が10~60重量%、親水性ヒュームドシリカ(C)の含有量が0.1~6重量%、水相(B)の含有量が34~89.9重量%である請求項1に記載の水中油型エマルション消泡剤。
- 油相(A)と親水性ヒュームドシリカ(C)との重量の比(A/C)が、2~100である請求項1又は2に記載の水中油型エマルション消泡剤。
- 親水性ヒュームドシリカ(C)のBET比表面積(m2/g)が20~450である請求項1~3のいずれかに記載の水中油型エマルション消泡剤。
- 油相(A)が、25℃で液状である基油(E)を必須構成成分としてなる請求項1~4のいずれかに記載の水中油型エマルション消泡剤。
- 油相(A)が、疎水性シリカ(Da)、脂肪酸アミド(Db)、石油ワックス(Dc)、合成ワックス(Dd)、植物ワックス(De)及び合成樹脂微粒子(Df)からなる群より選ばれる少なくとも1種の核剤(D)を含んでなる請求項1~5のいずれかに記載の水中油型エマルション消泡剤。
- 核剤(D)及び25℃で液状である基油(E)の重量に基づいて、核剤(D)の含有量が0.01~20重量%、25℃で液状である基油(E)の含有量が80~99.99重量%である請求項6に記載の水中油型エマルション消泡剤。
- 界面活性剤(F)を含有してなり、界面活性剤(F)の含有量が、油相(A)の重量に基づいて、0.01~20重量%である請求項1~7のいずれかに記載の水中油型エマルション消泡剤。
- 油相(A)及び親水性ヒュームドシリカ(C)からなるエマルション粒子のメジアン径(d50、個数基準)が、0.3~25μmである請求項1~8のいずれかに記載の水中油型エマルション消泡剤。
- 請求項1~9のいずれかに記載された水中油型エマルション消泡剤を製造する方法であって、
水相(B)に、親水性ヒュームドシリカ(C)を分散・解砕しながら親水性ヒュームドシリカのメジアン径(d50、個数基準)が20~300nmである分散液(BC1)を得る分散・解砕工程(i)と、
分散・解砕工程(i)で作成した分散液(BC1)と油相(A)とを乳化・分散して水中油型エマルション消泡剤を得る乳化・分散工程(ii)とを含むことを特徴とする製造方法。 - 請求項1~9のいずれかに記載された水中油型エマルション消泡剤を製造する方法であって、
水相(B)の一部に親水性ヒュームドシリカ(C)を分散・解砕しながら親水性ヒュームドシリカのメジアン径(d50、個数基準)が20~300nmである分散液(BC2)を得る分散・解砕工程(iii)と、
油相(A)と水相(B)の残部とを混合・分散して混合分散液(AB)を得る混合・分散工程(iv)と、
混合分散液(AB)と分散液(BC2)とを乳化・分散して水中油型エマルション消泡剤を得る乳化・分散工程(v)と
を含むことを特徴とする製造方法。 - 請求項1~9のいずれかに記載された水中油型エマルション消泡剤を製造する方法であって、
油相(A)に親水性ヒュームドシリカ(C)を分散・解砕しながら親水性ヒュームドシリカの分散液(AC)を得る分散・解砕工程(vi)と、
分散液(AC)と水相(B)とを乳化・分散して水中油型エマルション消泡剤を得る乳化・分散工程(vii)とを含むことを特徴とする製造方法。
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US14/346,608 US10252189B2 (en) | 2011-10-24 | 2012-09-11 | Defoaming agent |
JP2013540697A JP5990667B2 (ja) | 2011-10-24 | 2012-09-11 | 消泡剤 |
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JP2011232664 | 2011-10-24 | ||
JP2011-232664 | 2011-10-24 |
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PCT/JP2012/073121 WO2013061700A1 (ja) | 2011-10-24 | 2012-09-11 | 消泡剤 |
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JP (1) | JP5990667B2 (ja) |
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Cited By (1)
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WO2018047443A1 (ja) * | 2016-09-09 | 2018-03-15 | 花王株式会社 | ジカルボン酸結晶及びその製造方法 |
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RU2660116C2 (ru) * | 2013-08-13 | 2018-07-05 | Дау Силиконз Корпорейшн | Способ приготовления противовспенивающей гранулы |
CN104941259A (zh) * | 2015-06-16 | 2015-09-30 | 眉山华瑞科技开发有限责任公司 | 一种泡沫排水用有机硅消泡剂及其制备方法 |
CA2997090C (en) | 2015-09-03 | 2019-01-29 | Phillips 66 Company | Antifoam compositions for use in oils |
CN111484630A (zh) * | 2020-03-23 | 2020-08-04 | 江苏四新科技应用研究所股份有限公司 | 一种聚合物乳液型消泡剂及其制备方法 |
CN114225477B (zh) * | 2021-12-16 | 2023-02-28 | 杭州崇耀科技发展有限公司 | 一种复合水性有机硅消泡剂及其制备方法 |
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US10252189B2 (en) | 2019-04-09 |
JPWO2013061700A1 (ja) | 2015-04-02 |
US20140221508A1 (en) | 2014-08-07 |
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