JP5540171B2 - Antifoam composition - Google Patents

Description

  The present invention relates to an antifoam composition.

  Conventionally, as an antifoam composition having excellent storage stability, an oil-in-water emulsion composition containing an oil phase component containing a higher alcohol having 12 to 30 carbon atoms and poorly water-soluble hydrophilic inorganic fine particles has been known. (Patent Document 1).

JP 2006-272162 A

However, the conventional antifoaming agent composition has insufficient storage stability after being added to the liquid to be added which is a foamable liquid, and after storing the mixture of the antifoaming composition and the liquid to be added for a long period of time. There is a problem that the defoaming property (sustained defoaming property) is not sufficient.
That is, the object of the present invention is to provide an antifoaming agent composition having excellent sustained defoaming properties.

  A feature of the antifoam composition of the present invention is an antifoam composition comprising amphiphilic particles (a) and an oily component (b), wherein the amphiphilic particles (a) are silica and / or alumina. The gist is that the surface of the secondary aggregated particles is divided into a hydrophilic surface and a hydrophobic surface.

  The antifoam composition of the present invention is excellent in storage stability and sustained defoaming property in the liquid to be added, and is excellent in defoaming even after storing the mixture of the antifoam composition and the liquid to be added for a long period of time. The ability to demonstrate. Accordingly, the antifoaming composition of the present invention is a defoaming composition for paper pulp industry, food industry, textile industry, paint industry, ink industry, adhesive industry, petroleum industry, latex production process and wastewater treatment process. It is suitable as.

  The hydrophilic fine particles composed of silica and / or alumina include fine particles composed of silica, alumina or alumina silicate.

  Silica includes synthetic silica (amorphous synthetic silica and crystalline synthetic silica (artificial quartz and artificial quartz)), natural silica (crystalline silica (quartz, silica sand, silica, etc.)) and amorphous silica (diatomaceous earth and acidic silica). Etc.) and amorphous synthetic silica includes precipitated silica, gel silica, pyrogenic silica and fused silica.

  Precipitated silica is silica obtained by neutralizing sodium silicate with an acid in an alkaline environment, and filtering and drying the resulting precipitate. Gel silica is a silica obtained by neutralizing sodium silicate with an acid in an acidic environment and filtering and drying the resulting precipitate. Pyrolytic silica is silica obtained by burning a silicon compound such as silicon tetrachloride in an oxyhydrogen flame. The fused silica is silica obtained by melting and spheroidizing silica powder in a flame.

  Alumina includes crystalline alumina (γ-alumina, δ-alumina, η-alumina, θ-alumina, α-alumina and a mixture of these crystalline aluminas) and amorphous alumina. The mixture of these crystalline aluminas includes alumina obtained by a known method (flame combustion method alumina, firing method alumina, etc.), and crystalline aluminas having different crystal systems have a firing temperature during the production of the firing alumina. It can be obtained by changing.

  Flame combustion method alumina is alumina obtained by burning an aluminum compound such as aluminum tetrachloride in an oxyhydrogen flame. The calcined alumina is alumina obtained by calcining alumina and aluminum hydroxide obtained by calcining a hydrolyzate of aluminum alkoxide.

  The alumina silicate includes composite fine particles synthesized by a hydrolysis method using aluminum alkoxide and silicon alkoxide.

  Of these, amorphous synthetic silica {precipitation silica, gel silica, pyrolysis silica, fused solid silica, etc.} and flame combustion alumina are preferable, amorphous synthetic silica is more preferable, and precipitation is particularly preferable. Silica, gel silica and pyrogenic silica, most preferably precipitated silica.

  The hydrophilic fine particles are fine particles having a fine particle surface having a hydrophilic property (a property of getting wet with distilled water). It can be confirmed that the fine particles have hydrophilicity when the fine particles and 25 ± 3 ° C. distilled water are mixed and the fine particles are easily dispersed in water.

  The hydrophilic fine particles composed of silica and / or alumina can be easily obtained from the market, and the trade names are exemplified below.

<Precipitated silica>
Nipsil series {Tosoh Silica Co., Ltd., “Nipsil” is a registered trademark of Tosoh Silica Co., Ltd. }, Sipernat series {Evonik Degussa Japan Co., Ltd., "Sipernat" is a registered trademark of Evonik Degussa GmbH. }, Carplex series {DSL. Japan Corporation, “Carplex” is a DSL. It is a registered trademark of Japan Corporation. }, FINESIL series {Tokuyama Corporation, "FINESIL" is a registered trademark of Tokuyama Corporation. }, TOKUSIL {Tokuyama Corporation, “TOKUSIL” is a registered trademark of Tokuyama Corporation. }, Zeosil {Rhodia, "Zeosil" is a registered trademark of Rhodia Simi. }, MIZUKASIL series {Mizusawa Chemical Industry Co., Ltd., "MIZUKASIL" is a registered trademark of Mizusawa Chemical Industry Co., Ltd. }etc.

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

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

<Fused silica>
Admafine series {Admatechs, "Admafine" is a registered trademark of Toyota Motor Corporation. }, Fuselex series {Tatsumori Co., Ltd.}, Denka fused silica series {Electrochemical Industry Co., Ltd.}, etc.

<Crystalline synthetic silica>
CRYSTALITE series {Tatsumori Corporation, “CRYSTALITE” is a registered trademark of Tatsumori Corporation. }, Imsil series {UNIMIN, "Isil" is a registered trademark of Unimin Specialty Minerals, Inc. }etc.

<Natural silica>
Mizuka Ace Series {Mizusawa Chemical Co., Ltd.} etc.

<Flame combustion method alumina>
Aerosil Al series {Nippon Aerosil Co., Ltd. and Evonik Degussa, "Aerosil" is a registered trademark of Evonik Degussa GmbH. }, SpectrAl series {Cabot Corporation}, etc.

<Baking alumina>
High-purity alumina AKP series {Sumitomo Chemical Co., Ltd.}, alumina A series {Nihon Light Metal Co., Ltd.}, etc.

  As the hydrophilic fine particles, in addition to the hydrophilic fine particles composed of silica and / or alumina, known hydrophilic fine particles can be used. For example, hydrophilic resin fine particles (fine particles made of polyacrylamide, chitosan or alginate, etc.), Metal oxide fine particles other than silica and alumina (fine particles comprising titania or zirconia), metal hydroxide fine particles (fine particles comprising magnesium hydroxide or calcium hydroxide), carbonate fine particles (fine particles comprising calcium carbonate or magnesium carbonate) Etc.), layered mineral fine particles {kaolinite, halloysite, talc, smectite (montmorillonite, beidellite, hectorite, saponite, etc.), vermiculite, mica (mica), chlorite, hydrotalcite, layered polysilicate (kanemite, macatite) Fine particles made of ialite, magadiite, or Kenyaite)} and fine particles obtained by hydrophilizing hydrophobic fine particles (hydrophobic fine particles, surface-modified fine particles with hydrophilic compounds (hydrophilic fine particles, hydrophilic resins, etc.), oxidizing agents Fine particles obtained by oxidizing the surface of hydrophobic fine particles) can also be used.

  The hydrophobic fine particles for preparing the fine particles obtained by hydrophilizing the hydrophobic fine particles include hydrophobic fine particles other than the fine particles obtained by hydrophobizing the hydrophilic fine particles among the hydrophobic fine particles described later.

  Among the hydrophilic compounds used for the surface modification of the hydrophobic fine particles, the hydrophilic fine particles include hydrophilic resin fine particles, metal oxide fine particles, metal hydroxide fine particles, carbonate fine particles, and layered mineral fine particles. Among the hydrophilic compounds used for surface modification of hydrophobic fine particles, hydrophilic resins include polyurethane, nylon, polyester, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polycaprolactone, lactic acid polymer, poly (meta). ) Acrylic acid and polyacrylamide. Examples of the oxidizing agent include hypochlorite and hydrogen peroxide.

The method for hydrophilizing the hydrophobic fine particles can be performed by the following known methods.
<Hydrophilic method 1> A dry coating method in which hydrophobic fine particles and hydrophilic fine particles are simultaneously mixed in a fluidized bed container (pin mill or the like) to adhere the hydrophilic fine particles to the surface of the hydrophobic fine particles.

<Hydrophilic method 2> An aqueous solution (aqueous solution or a solution of water and a low molecular alcohol, etc.) in which a hydrophilic resin is dissolved is sprayed while stirring the hydrophobic fine particles in a fluidized bed container, and then dried to make the surface hydrophilic. Wet coating method.

<Hydrophilic method 3> A method of hydrophilizing the surface by physically vapor-depositing a metal oxide film on the surface of hydrophobic fine particles using metal oxide fine particles such as silica and alumina.

<Hydrophilic method 4> A method of oxidizing the surface of hydrophobic fine particles using an oxidizing agent such as hypochlorite.

  When hydrophilization is performed using a hydrophilic compound, the amount of use (% by weight) of the hydrophilic compound is preferably 2 to 80, more preferably 5 to 50, and particularly preferably 10 based on the weight of the hydrophobic fine particles. ~ 30. When it exists in this range, the continuous defoaming property of an antifoamer composition will become further favorable. This is presumably because the storage stability of the defoamer composition is further improved by further improving the surface activity of the amphiphilic particles (a).

The specific surface area (m ² / g) of the hydrophilic fine particles by BET method is preferably 50 to 800, more preferably 100 to 500, and particularly preferably 120 to 400. Within this range, the continuous defoaming property is further improved.
The specific surface area is a value measured in accordance with JIS R1626-1996 (one-point method) {measurement sample: 50 mg (a sample heat-treated at 200 ° C. for 15 minutes), adsorption amount measurement method: constant dissolution method Adsorbate: mixed gas (70% by volume of N _2, 30% by volume of He), measurement equilibrium relative pressure: 0.3, device: for example, fully automated powder surface measurement device AMS-8000 manufactured by Okura Riken Co., Ltd.

  Hydrophobic fine particles are fine particles whose surface does not have hydrophilicity. It can be confirmed that the fine particles do not have hydrophilicity when the fine particles and 25 ± 3 ° C. distilled water are mixed, the fine particles cannot be dispersed in water and the fine particles float on the water surface.

Hydrophobic fine particles include known hydrophobic fine particles, carbon black, hydrophobic organic fine particles (fine particles made of amide wax, polyethylene, polypropylene, modified polyethylene, polystyrene, polymethacrylic acid methyl ester, cross-linked silicone resin or fluororesin) Etc.) and fine particles obtained by hydrophobizing hydrophilic fine particles (fine particles obtained by modifying the surface of hydrophilic fine particles with lipophilic compounds or hydrophobic fine particles).
Among these, fine particles obtained by hydrophobizing hydrophilic fine particles are preferable from the viewpoint of the continuous defoaming property of the antifoaming agent composition.

  Examples of the lipophilic compound used for hydrophobizing hydrophilic fine particles include halosilane, alkoxysilane, fatty acid having 4 to 28 carbon atoms, aliphatic alcohol having 4 to 36 carbon atoms, aliphatic amine having 12 to 22 carbon atoms, carbon Included are fatty acid amides of 24 to 38 and silicone compounds.

  Examples of the halosilane include alkylhalosilanes and arylhalosilanes having an alkyl group or aryl group having 1 to 12 carbon atoms, such as methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, trimethylbromosilane, ethyltrichlorosilane, and phenyltrichlorosilane. , Diphenyldichlorosilane, t-butyldimethylchlorosilane, and the like.

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

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

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

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

  Examples of the fatty acid amide having 24 to 38 carbon atoms include oleic acid lauryl monoamide, N, N′-ethylenebisstearylamide, and the like.

  Examples of silicone compounds include dimethylpolysiloxane, aryl-modified polysiloxane (aryl group having 6 to 10 carbon atoms), alkyl group-modified polysiloxane (modified alkyl group having 2 to 6 carbon atoms), hydroxyl group-modified polysiloxane, and amino group-modified polysiloxane. Examples thereof include siloxane, polyether-modified polysiloxane, and methyl hydrogen polysiloxane.

As dimethylpolysiloxane, kinematic viscosity at 25 ° C. {hereinafter referred to as “kinematic viscosity (25 ° C.)”. } Having ¹ to 10,000 mm ² / s can be used.

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

As the polyether-modified polysiloxane, one having a viscosity at 25 ° C. of 1 to 10,000 mm ² / s and an HLB of 2 to 5 can be used.

  HLB is a concept that represents the balance between hydrophilic groups and hydrophobic groups in a molecule. The HLB value of polyether-modified polysiloxane is "the nature and application of surfactants" (author Takao Karime, publisher, Inc.) Using the “Measurement method of HLB by an emulsification test” described on pages 89 to 90 of Koshobo, issued on September 1, 1980).

<Measurement method of HLB by emulsification test of polyether-modified polysiloxane>
The polyether-modified polysiloxane X whose HLB is unknown and the emulsifier A whose HLB is known are mixed in different ratios, and an oil agent whose HLB is known is emulsified. The HLB of the polyether-modified polysiloxane X is calculated from the mixing ratio when the thickness of the emulsified layer becomes maximum using the following formula.

Oil HLB = {(W _A × HLB _A ) + (W _X × HLB _X )} ÷ (W _A + W _X )

W _A is the weight fraction of emulsifier A based on the total weight of polyether-modified polysiloxane X and emulsifier A, W _X is the weight fraction of polyether-modified polysiloxane X based on the total weight of polyether-modified polysiloxane X and emulsifier A HLB _A is the HLB of the emulsifier A, and HLB _X is the HLB of the polyether-modified polysiloxane X.

As the hydroxyl group-modified polysiloxane, amino group-modified polysiloxane, and methyl hydrogen dimethyl polysiloxane, those having a viscosity at 25 ° C. of 1 to 10,000 mm ² / s and a functional group equivalent of 300 to 8000 g / mol can be used. .

  In addition to the above, known coupling agents (silane coupling agents other than the above, titanate coupling agents, zircoaluminate coupling agents, etc.) are also used as lipophilic compounds used to hydrophobize hydrophilic fine particles. it can.

Of these lipophilic compounds, halosilanes, alkoxysilanes, and silicone compounds are preferred from the standpoint of sustained defoaming properties of the antifoaming agent composition, more preferably silicone compounds, and particularly preferably kinematic viscosity (25 ° C.) of 10 A dimethylpolysiloxane having a molecular weight of ˜3000 mm ² / s and an alkyl group-modified polysiloxane obtained by modifying the dimethylpolysiloxane, most preferably a dimethylpolysiloxane having a kinematic viscosity (25 ° C.) of 20 to 100 mm ² / s.

  The hydrophobic fine particles used for hydrophobizing the hydrophilic fine particles are preferably hydrophobic organic fine particles.

When hydrophilic fine particles are hydrophobized, the specific surface area (m ² / g) of the hydrophobic fine particles by the BET method is the same as that of the hydrophilic fine particles, and the preferred range is also the same.

  Hydrophobization of hydrophilic fine particles with a lipophilic compound can be carried out by a known method, for example, by the methods described in the following <Hydrophobicization Method 1> and <Hydrophobicization Method 2>.

<Hydrophobicization method 1>
Hydrophilic fine particles dispersed in hydrophilic fine particles and a solvent {paraffin oil / mineral oil and organic solvent having a kinematic viscosity at 40 ° C. (hereinafter referred to as “kinematic viscosity (40 ° C.)”) of 5 to 30 mm ² / s} A method of hydrophobizing by adsorbing or reacting a lipophilic compound or hydrophobic fine particles on the surface of hydrophilic fine particles while stirring the compound or hydrophobic fine particles with a stirrer (wet method).

<Hydrophobicization method 2>
A method of hydrophobizing by adsorbing or reacting a lipophilic compound or hydrophobic fine particles on the surface of hydrophilic fine particles while stirring a mixture of hydrophilic fine particles and lipophilic compound or hydrophobic fine particles with a stirrer (dry method).

  Among these methods, the dry method of <Hydrophobicization Method 2> is preferable. When <Hydrophobicization method 2> is applied, the surface activity of the amphiphilic particles (a) is further improved, and the sustained defoaming property of the defoamer composition is further improved. This is considered because the secondary aggregate (pa) described later can be easily crushed.

  As a stirrer used in the wet method, a stirrer with a saddle type blade, a planetary mixer or the like can be used. As a stirrer used in the dry method, a vertical single-shaft powder stirrer {Henschel mixer (Mitsui Mining Co., Ltd., “Henschel mixer” is a registered trademark of Mitsui Mining Co., Ltd.)}, horizontal single-shaft stirring Machine (ribbon mixer, etc.), vertical single-shaft mixer (universal mixer, rakai machine, etc.) can be used.

In the method of adsorbing or reacting the lipophilic compound on the surface of the fine particles, (1) condensation reaction between the functional group on the surface of the hydrophilic fine particle and the functional group of the lipophilic compound, (2) to the pores of the hydrophilic fine particle And (3) electrical adsorption between the surface charge of the hydrophilic fine particles and the ionic functional group of the lipophilic compound.
Of these, (2) the method by physical adsorption to the pores of the hydrophilic fine particles is preferable because it can be uniformly hydrophobized.

  When a lipophilic compound is used, heat treatment can be performed. When heat-processing, as heating temperature (degreeC), 100-400 are preferable, More preferably, it is 150-350, Especially preferably, it is 200-300.

  When using hydrophobic organic fine particles as the lipophilic compound, the mixture may be stirred with a stirrer while being heated to a temperature higher than the melting point of the hydrophobic organic fine particles for the purpose of stronger adsorption, and then cooled to the melting point or lower.

  In the method of reacting a lipophilic compound on the surface of fine particles, the reaction may be performed in the presence of a reaction catalyst (sulfuric acid, nitric acid, hydrochloric acid, hydroxyacetic acid, trifluoroacetic acid, p-nitrobenzoic acid, potassium hydroxide, lithium hydroxide, etc.). it can.

  When hydrophobizing using a lipophilic compound, the amount (% by weight) of the lipophilic compound is preferably 2 to 80, more preferably 5 to 50, and particularly preferably 10 based on the weight of the hydrophilic fine particles. ~ 30. Within this range, the hydrophobic treatment is uniformly performed and the amount of unadsorbed lipophilic compound is reduced, so that the surface activity is further improved and the continuous defoaming property of the defoamer composition is further improved.

  When hydrophobizing using hydrophobic fine particles, the amount (% by weight) of the hydrophobic fine particles used is preferably 1 to 70, more preferably 10 to 65, based on the weight of the hydrophilic fine particles. If it is within this range, the hydrophobization treatment is uniformly performed, and unadsorbed hydrophobic fine particles are also reduced. And the surface activity of the amphiphilic particles (a) is further improved, and the continuous defoaming property of the defoamer composition is further improved.

  Among the hydrophobic fine particles obtained by hydrophobizing the hydrophilic fine particles, the hydrophobic fine particles obtained by hydrophobizing the precipitation method silica, the pyrolysis method silica, and the flame combustion method alumina can be easily obtained from the market.

<Fine particles with hydrophobized precipitated silica>
Nipsil SS series, Sipernat D and C series, and SYLOPHOBIC series {Fuji Silysia Chemical Co., Ltd., "SYLOPHOBIC" is a registered trademark of Fuji Silysia Chemical Co., Ltd. }etc.

<Fine particles of hydrolyzed silica hydrophobized>
Aerosil C series {Nippon Aerosil Co., Ltd. and Evonik Degussa}, Reolosil MT and DM series {Tokuyama Co., Ltd.}

<Fine particles made by hydrophobizing flame combustion method alumina>
Aerosil C805 {Nippon Aerosil Co., Ltd. and Evonik Degussa Co.}, SpectrAl TA series, TG series {Cabot Corp.}, etc.

The M value of the hydrophobic fine particles is preferably 30 to 90, more preferably 35 to 85, particularly preferably 30 to 70, and most preferably 45 to 70.
The M value is a concept representing the degree of hydrophobicity. The higher the M value, the lower the hydrophilicity. When the hydrophobic fine particles are uniformly dispersed in a water / methanol mixed solution, the minimum amount of methanol is required. It is expressed as a volume ratio and can be determined by the following method.

<M value calculation method>
0.2 g of hydrophobic microparticles are added to 50 mL of water in a 250 mL beaker, followed by dropwise addition of methanol from the burette until all of the hydrophobic microparticles are suspended. At this time, the solution in the beaker is constantly stirred with a magnetic stirrer, and when the total amount of the hydrophobic fine particles is uniformly suspended in the solution, the end point is set, and the volume percentage of methanol in the beaker liquid mixture at the end point becomes the M value.

  The hydrophilic fine particles and the hydrophobic fine particles are preferably amorphous fine particles. When amorphous fine particles are used, they are more easily crushed than crystalline fine particles, and are considered to be easily divided into two surfaces, a hydrophilic surface and a hydrophobic surface. The emulsion dispersion stability is further improved. Whether the fine particles are amorphous fine particles can be confirmed by performing powder diffraction X-ray diffraction analysis in accordance with JIS K0131-1996 and analyzing the obtained diffraction peak profile. Specifically, the profile of the amorphous fine particles is broad, and it can be confirmed that a clear diffraction peak cannot be obtained.

  Secondary agglomerated particles composed of hydrophilic fine particles composed of silica and / or alumina and hydrophobic fine particles are formed by agglomeration of primary particles of at least one hydrophilic fine particle and at least one hydrophobic fine particle. Fine particles. The secondary aggregated particles formed by aggregating at least two primary particles can be confirmed by an image obtained by enlarging the particles by 50,000 to 1,000,000 times with a transmission electron microscope.

  The surface of the secondary agglomerated particles is divided into a hydrophilic surface and a hydrophobic surface. Bi-segmentation means that the hydrophilic surface and the hydrophobic surface are localized on the surface of one secondary agglomerated particle as if the positive electrode and the negative electrode were localized in one magnet. Unlike those scattered on the surface of two secondary agglomerated particles). Of the surfaces of the secondary agglomerated particles, the hydrophilic surface is the surface of the hydrophilic fine particles, and the hydrophobic surface is the surface of the hydrophobic fine particles.

  It can be confirmed by the following method that the surface of the secondary agglomerated particles is divided into a hydrophilic surface and a hydrophobic surface.

<Confirmation method that the surface is divided into two>
Ion-exchanged water 5 cm ³ and n-hexane 5 cm ³ were put in a test tube, and a dispersion in which a measurement sample (amphiphilic particles of the present invention, etc.) was dispersed in 2-propanol at a concentration of 1 wt. 02 g is added and left to stand for 60 minutes (the purity of each measuring reagent is 99% by weight or more).
When the surface of the secondary agglomerated particles is divided into a hydrophilic surface and a hydrophobic surface, an aggregated layer of measurement samples (amphiphilic particles) is formed at the interface between water and n-hexane, The lower layer forms a clean layer that does not contain the measurement sample (amphiphilic particles).
On the other hand, when the surface of the secondary agglomerated particles is not divided into a hydrophilic surface and a hydrophobic surface (in the case of particles in which the hydrophilic surface and the hydrophobic surface are uniformly dispersed (scattered) on the particle surface) The sample (particles) is dispersed in the n-hexane layer and does not form a clean layer in the n-hexane layer.

  The volume average particle diameter (μm) of the amphiphilic particles (a) is preferably 0.1 to 10, more preferably 0.1 to 5, particularly preferably 0.2 to, from the viewpoint of emulsion dispersion stability. 1, most preferably 0.2 to 0.5.

  In addition, the volume average particle diameter of the amphiphilic particles (a) is a laser diffraction particle size analyzer in accordance with JIS Z8825-1: 2001 (for example, Microtrac series manufactured by Lees & Northrup, Partica LA series manufactured by Horiba, Ltd.). A measurement dispersion was prepared by adding a measurement sample to 1000 parts by weight of 2-propanol {purity 99% by weight or more} so that the measurement sample concentration was 0.1% by weight, and the measurement temperature was 25 ± 5 ° C. After the measurement, the refractive index of 2-propanol is 1.3749, and the refractive index of the measurement sample is 50 using a literature value (“A GUIDE FOR ENTERING MICROTRAC“ RUN INFORMATION ”(F3) DATA”, produced by Leeds & Northrup). Calculated as% cumulative volume average particle size It is.

  The amphiphilic particles (a) can be produced by the following methods (Production Method 1) to (Production Method 4).

<Manufacturing method 1>
A method in which a secondary aggregate (pa) composed of hydrophilic fine particles is hydrophobized and then crushed.
The method of hydrophobizing the secondary agglomerates (pa) comprising hydrophilic fine particles includes the above-mentioned fine particles obtained by hydrophobizing the hydrophilic fine particles (fine particles obtained by modifying the surface of hydrophilic fine particles with lipophilic compounds or hydrophobic fine particles). A similar method can be applied.

<Manufacturing method 2>
A method in which a secondary aggregate (pb) composed of hydrophobic fine particles is hydrophilized and then crushed.
The method of hydrophilizing the secondary aggregate (pb) composed of hydrophobic fine particles is to modify the surface of the hydrophobic fine particles (hydrophobic fine particles by hydrophilic compounds (hydrophilic fine particles, hydrophilic resins, etc.)). For example, the same method as the fine particles obtained by oxidizing the surface of the hydrophobic fine particles with an oxidizing agent) can be applied.

<Manufacturing method 3>
A method in which hydrophobic fine particles smaller than the above are adsorbed on the entire surface of the hydrophilic fine particles, and then the hydrophilic fine particles are crushed together with the hydrophobic fine particles.
The method of adsorbing hydrophobic fine particles smaller than this on the entire surface of the hydrophilic fine particles is the same as the fine particles obtained by hydrophobizing the hydrophilic fine particles (the fine particles obtained by modifying the surface of the hydrophilic fine particles with hydrophobic fine particles). Methods etc. can be applied.

<Manufacturing method 4>
A method in which hydrophilic fine particles smaller than this are adsorbed on the entire surface of the hydrophobic fine particles, and then the hydrophobic fine particles are crushed together with the hydrophilic fine particles.
The method for adsorbing hydrophilic fine particles smaller than this on the entire surface of the hydrophobic fine particles is the same method as the fine particles obtained by hydrophilizing the above-mentioned hydrophobic fine particles (fine particles obtained by modifying the surface of hydrophobic fine particles with hydrophilic fine particles). Etc. are applicable.

  Secondary aggregates (pa) and (pb) are used in distinction from the term secondary aggregate particles. The volume average particle diameter (μm) of the secondary aggregate (pa) or (pb) is preferably 1 to 100, more preferably 1.5 to 40, and particularly preferably 2 to 30. Within this range, the secondary aggregates (pa) or (pb) can be easily crushed, the surface activity of the amphiphilic particles (a) is further improved, and the defoaming composition has a sustained defoaming property. Even better.

  The volume average particle diameter of the secondary aggregate (pa) or (pb) is a dispersion obtained by dispersing the secondary aggregate (pa) or (pb) in ion-exchanged water so as to have a concentration of 1% by weight. Using a laser diffraction particle size analyzer conforming to JIS Z8825-1: 2001 (for example, Microtrac series manufactured by Lees & Northrup, Partica LA series manufactured by Horiba, Ltd., etc.) and having an electric conductivity (25 ° C.) of 0.1 mS / m or less. A measurement dispersion is prepared by adding a measurement sample to 1000 parts by weight of ion-exchanged water so that the measurement sample concentration is 0.1% by weight, and measured at a measurement temperature of 25 ± 5 ° C. 1.333 is a literature value ("A GUIDE FOR ENTERING MICROTRAC" RUN INFORMATION "( 3) DATA ", Leeds & Northrup Co. created) using a determined as a 50% cumulative volume-average particle diameter.

  Of these production methods, <Production Method 1> and <Production Method 2> are preferred, and <Production Method 1> is more preferred.

  Secondary agglomerated particles (pa) or (pb) are hydrophilic fine particles having a primary particle size of 1 to 80 (preferably 5 to 30, more preferably 10 to 25) nm from the viewpoint of sustained defoaming property or the like. It is preferably made of hydrophobic fine particles.

  The primary particle size of the hydrophilic fine particles or hydrophobic fine particles was prepared by a sprinkling method in accordance with JIS Z8901-2006 “Test powder and test particles”, 5.44 particle diameter distribution (c) microscopy. An image obtained by observing a sample with a transmission electron microscope at a magnification of 50,000 to 1,000,000 times is in accordance with JIS Z8827-1 “Particle size—Image analysis method—Part 1: Static image analysis method”. It is a number average value of equivalent circle diameters calculated using computer software for image processing {for example, WinRoof manufactured by Mitani Shoji Co., Ltd.}.

  In <Production Method 1>, as a method of crushing the hydrophobized secondary aggregate (hydrophobized aggregate), after the dispersion step of dispersing the hydrophobized aggregate in an organic solvent, the hydrophobized aggregate is converted into volume average particles. Including a crushing step of crushing so that the diameter (μm) is 0.1 to 10 (preferably 0.1 to 5, more preferably 0.2 to 1, particularly preferably 0.2 to 0.5). Is preferred. In addition, the volume average particle diameter (micrometer) after a crushing process can be calculated | required by the method similar to the measurement of the volume average particle diameter of the said amphiphilic particle (a).

  As the organic solvent for dispersing the hydrophobized secondary aggregate (hydrophobized aggregate), it is preferable to use an organic solvent having a relative dielectric constant of 5 to 50.

  As an organic solvent having a relative dielectric constant of 5 to 50 {the numerical values in parentheses indicate relative dielectric constants}, nonpolar solvents {such as ethyl acetate (6) and methylene chloride (9)}, protic polarity Solvent {acetic acid (6.2), 1-butanol (18), 2-propanol (18), 1-propanol (20), ethanol (24), methanol (33), etc.}} and aprotic polar solvent {tetrahydrofuran ( 7.5), acetone (21), acetonitrile (37), N, N-dimethylformamide (38), dimethyl sulfoxide (47), etc.} can be used.

  Among these, a protic polar solvent and an aprotic polar solvent having a relative dielectric constant of 5 to 50 are preferable, more preferably a protic solvent having a relative dielectric constant of 5 to 50, particularly preferably 1-butanol (18 ), 2-propanol (18), 1-propanol (20) and ethanol (24), most preferably 1-butanol (18), 2-propanol (18) and 1-propanol (20). When these organic solvents are used, since the reaggregation of the hydrophobized aggregate is further reduced in the crushing step, the surface activity of the amphiphilic particles (a) is further improved, and the defoaming composition has a sustained defoaming property. Even better. Of these, one type may be used, or two or more types may be mixed and used.

  The following <dispersion method 1> to <dispersion method 3> and the like can be applied to the dispersion step of dispersing the hydrophobized secondary aggregate (hydrophobized aggregate) in an organic solvent.

<Dispersion method 1>
A method in which a hydrophobized aggregate and an organic solvent are simultaneously placed in a dispersion vessel and uniformly dispersed.
<Dispersion method 2>
A method in which an organic solvent is added to a dispersion vessel in which a hydrophobized agglomerate is previously contained to perform uniform dispersion.
<Dispersion method 3>
A method in which a hydrophobic aggregate is added to a dispersion container containing an organic solvent in advance and uniformly dispersed.

  Among these, <dispersion method 1> and <dispersion method 3> are preferable, and <dispersion method> is more preferable in that the surface activity of the amphiphilic particles (a) is likely to be further improved and the emulsion stability is likely to be further improved. Method 3>.

In the dispersion process of the hydrophobized aggregate, a known disperser {feather stirrer, high-speed rotary homomixer, high-pressure homogenizer, dissolver, ball mill, kneader, sand mill, three rolls, ultrasonic disperser, planetary mixed dispersion Machines (planetary mixers, etc.) and 3-axis planetary mixers, etc.} can be used.
Among these dispersers, a blade-type stirrer, a high-speed rotating homomixer, a high-pressure homogenizer, and a dissolver are preferable, a high-speed rotating homomixer, a high-pressure homogenizer, and a dissolver are more preferable, and a high-speed rotating homomixer is particularly preferable. According to these dispersers, since the dispersibility of the hydrophobized aggregate is further improved, the surface activity of the amphiphilic particles (a) is further improved, and the continuous antifoaming property of the antifoaming agent composition is improved. This is preferable.

  The ratio (% by weight) of the hydrophobized aggregate dispersed in the organic solvent is preferably 1 to 30, more preferably 3 to 25, particularly preferably 5 to 5, based on the total weight of the hydrophobized aggregate and the organic solvent. 20. Within this range, the viscosity of the dispersion liquid is low, the dispersion is further facilitated, and the crushing in the crushing process, which is the next process, proceeds further favorably, so that the surface activity of the amphiphilic particles (a) is further improved. Thus, the continuous defoaming property is further improved.

  The temperature of the dispersion step is not particularly limited, but is preferably 0 to 50 ° C, more preferably 10 to 45 ° C, and particularly preferably 15 to 35 ° C. The time required for the dispersion step is preferably 5 minutes to 10 hours, more preferably 10 minutes to 5 hours, and particularly preferably 15 minutes to 3 hours.

In the crushing process, a known crushing and dispersing machine can be used. Wet medium type crushing and dispersing machine {Bead Mill, Sand Grinder, Colloid Mill, Attritor (manufactured by Nihon Coke Industries Co., Ltd., “Attritor” is a registered trademark of Nippon Coke Industries, Ltd. DISPERMAT (manufactured by VMA-GETAMANN GMBH), etc.}, high-pressure jet crushing and dispersing machine {Nanomizer (manufactured by Yoshida Kikai Co., Ltd., “Nanomizer” is a registered trademark of SG Engineering Co., Ltd.), Starburst (manufactured by Sugino Machine Co., Ltd., “Starburst” is a registered trademark of Sugino Machine Co., Ltd.), Gorin homogenizer (manufactured by APV), etc.} can be used.
Among these, the wet medium type pulverization disperser is less likely to cause reaggregation of the amphiphilic particles (a), the surface activity of the amphiphilic particles (a) is further improved, and the defoaming composition has a continuous defoaming property. Is preferable in that it becomes favorable.

  In <Production Method 2>, as a method of crushing the hydrophilized secondary aggregate (hydrophilic aggregate), after the dispersion step of dispersing the hydrophilized aggregate in water and / or an organic solvent, the hydrophilized aggregate Crushing so that the volume average particle diameter (μm) is 0.1 to 10 (preferably 0.1 to 5, more preferably 0.2 to 1, particularly preferably 0.2 to 0.5). It is preferable to include a process. In addition, the volume average particle diameter (micrometer) after a crushing process can be calculated | required by the method similar to the measurement of the volume average particle diameter of the said amphiphilic particle (a).

  As the organic solvent used in the dispersion step, the organic solvent of <Production Method 1> can be used. Among organic solvents, a protic solvent having a relative dielectric constant of 5 to 50 is preferable, more preferably 1-butanol, 2-propanol, 1-propanol and ethanol, particularly preferably 1-butanol, 2-propanol and 1-propanol. It is. When these organic solvents are used, since the reaggregation of the hydrophilized aggregate is further reduced in the crushing step, the surface activity of the amphiphilic particles (a) is further improved and the sustained defoaming property is further improved. Of these, one type may be used, or two or more types may be mixed and used.

  As the water used in the dispersion step, the same water as water (c) described later can be used, and preferable water is also the same.

  For the dispersion step of dispersing the hydrophilized secondary aggregate (hydrophilic aggregate) in water or an organic solvent, the same dispersion method and disperser as in <Production Method 1> can be applied. The same. However, “hydrophobized aggregate” is read as “hydrophilic aggregate” and “organic solvent” is read as “water and / or organic solvent”, respectively.

  The ratio of the hydrophilized aggregate dispersed in water and / or the organic solvent is preferably 1 to 30, more preferably 3 to 25, based on the total weight of the hydrophilized aggregate and water and / or the organic solvent. Especially preferably, it is 5-20. Within this range, the viscosity of the dispersion liquid is low, the dispersion is further facilitated, and the crushing in the crushing process, which is the next process, proceeds further favorably, so that the surface activity of the amphiphilic particles (a) is further improved. Thus, the continuous defoaming property is further improved.

  In <Production Method 3>, as a method of crushing the hydrophilized fine particles (hydrophobized aggregate) having adsorbed hydrophobic fine particles, the hydrophilized fine particles (hydrophobized aggregate) having adsorbed hydrophobic fine particles are used as an organic solvent. After the dispersion step, the hydrophilized fine particles (hydrophobized aggregates) adsorbed with the hydrophobic fine particles have a volume average particle diameter (μm) of 0.1 to 10 (preferably 0.1 to 5, more preferably 0). It is preferable to include a crushing step of crushing so as to be 0.2 to 1, particularly preferably 0.2 to 0.5). In addition, the volume average particle diameter (micrometer) after a crushing process can be calculated | required by the method similar to the measurement of the volume average particle diameter of the said amphiphilic particle (a).

  As the organic solvent used in the dispersion step, the same organic solvent as in <Production Method 1> can be used, and the preferred organic solvent is also the same.

  In the dispersion step of dispersing the hydrophilic fine particles (hydrophobized aggregates) adsorbing the hydrophobic fine particles in the organic solvent, the same dispersion method and disperser as those in <Production Method 1> can be applied. Is the same.

  The ratio of the hydrophobized aggregate is preferably from 1 to 30, more preferably from 3 to 25, particularly preferably from 5 to 20, based on the total weight of the hydrophobized aggregate and the organic solvent. Within this range, the viscosity of the dispersion liquid is low, the dispersion is further facilitated, and the crushing in the crushing process, which is the next process, proceeds further favorably, so that the surface activity of the amphiphilic particles (a) is further improved. Thus, the continuous defoaming property is further improved.

  In <Production Method 4>, as a method for crushing hydrophobic fine particles (hydrophilic aggregates) adsorbing hydrophilic fine particles, hydrophobic fine particles (hydrophilic aggregate) adsorbing hydrophilic fine particles are mixed with water and / or Further, after the dispersion step of dispersing in the organic solvent, the hydrophilized aggregate has a volume average particle diameter (μm) of 0.1 to 10 (preferably 0.1 to 5, more preferably 0.2 to 1, particularly preferably. It is preferable to include a crushing step of crushing to be 0.2 to 0.5). In addition, the volume average particle diameter (micrometer) after a crushing process can be calculated | required by the method similar to the measurement of the volume average particle diameter of the said amphiphilic particle (a).

  As the organic solvent used in the dispersion step, the same organic solvent as in <Production Method 2> can be used, and the preferred organic solvent is also the same.

  As the water used in the dispersion step, the same water as water (c) described later can be used, and preferable water is also the same.

  In the dispersion step of dispersing the hydrophobic fine particles (hydrophilic aggregates) adsorbing the hydrophilic fine particles in water and / or an organic solvent, the same dispersion method and disperser as in <Production Method 1> can be applied. The preferable disperser is the same. However, “hydrophobized aggregate” is read as “hydrophilic aggregate” and “organic solvent” is read as “water and / or organic solvent”, respectively.

  The ratio of the hydrophobic fine particles (hydrophilic aggregate) to which the hydrophilic fine particles are adsorbed is based on the total weight of the hydrophobic fine particles (hydrophilic aggregate) to which the hydrophilic fine particles are adsorbed and water and / or an organic solvent. 1 to 30 is preferable, 3 to 25 is more preferable, and 5 to 20 is particularly preferable. Within this range, the viscosity of the dispersion liquid is low, the dispersion is further facilitated, and the crushing in the crushing process, which is the next process, proceeds further favorably, so that the surface activity of the amphiphilic particles (a) is further improved. Thus, the continuous defoaming property is further improved.

  In the method for producing the amphiphilic particles (a), a classification step may be provided after the pulverization step. In the classification step, the following known classification methods of <wet classification> and <dry classification> can be used.

<Wet classification>
After the crushing process, the dispersion liquid containing amphiphilic particles is classified by filtering with a wire mesh etc., the dispersion liquid containing amphiphilic particles is allowed to settle and the large particles are precipitated and separated, and the sedimentation speed due to the difference in particle diameter The sedimentation velocity method using the difference.

<Dry classification>
A method of classifying amphiphilic particles obtained by removing the solvent after the crushing step with an air classifier (jet mill) or a sieve.

  In the method for producing the amphiphilic particles (a), a desolvation step and a concentration step of water and / or an organic solvent contained in the dispersion may be provided after the pulverization step. The desolvation step and the concentration step can be performed by a known method such as a method using a reaction vessel with a reduced pressure with a heating, stirring, cooling, or carbonization apparatus, a rotary evaporator, or the like.

  In the method for producing the amphiphilic particles (a), a step of drying the amphiphilic particles may be provided. A drying process can be performed by a well-known method, and heat drying (for example, heating for 10 to 120 minutes in the drying furnace heated at 30-150 degreeC), reduced pressure drying, etc. are applicable.

  The amphiphilic particles (a) are used in the antifoaming agent composition of the present invention in the following <Use Form 1> to <Use Form 3>.

<Usage form 1>
A form in which the amphiphilic particles obtained by removing the organic solvent and / or water from the dispersion containing the amphiphilic particles (a) obtained in the crushing step and drying are used as a powder.

<Usage form 2>
The water and / or organic solvent of the dispersion liquid containing the amphiphilic particles (a) obtained in the crushing step is replaced with water (c) described later contained in the antifoaming agent composition, and the amphiphilic particle aqueous dispersion How to use as.

<Usage pattern 3>
The water and / or organic solvent of the dispersion liquid containing the amphiphilic particles (a) obtained in the crushing step is replaced with the oily component (b) contained in the antifoaming agent composition to obtain an amphiphilic particle oily dispersion. How to use.

<Usage form 4>
A method in which an aqueous dispersion containing amphiphilic particles (a) obtained in the crushing step is concentrated or diluted and used as an aqueous dispersion of amphiphilic particles.

  The removal and replacement of the organic solvent can be performed by a known method such as a method using a depressurizable reaction vessel equipped with a heating device and a stirring device, a rotary evaporator, or the like.

  In <Usage Mode 2> and <Usage Mode 3>, the temperature at which the water and / or organic solvent (hereinafter referred to as the dispersion medium) in the dispersion is replaced with the oil component (b) or water (c) described later. Is not particularly limited and is appropriately selected depending on the boiling point and decomposition temperature of the dispersion medium and the oil component (b). For example, when the oil component (b) is replaced with silicone oil, 40 to 100 ° C. is preferable. More preferably, it is 50-80 degreeC, Most preferably, it is 60-70 degreeC. Moreover, when replacing with water (c), 40-90 degreeC is preferable, More preferably, it is 50-80 degreeC, Most preferably, it is 60-70 degreeC.

  In <Usage Mode 2> and <Usage Mode 3>, the pressure when replacing the dispersion medium with the oil component (b) or water (c) described later is not particularly limited, and the dispersion medium and the oil component (b) The pressure (kPa) when replacing with a silicone oil as the oil component (b) is preferably 5 to 101, more preferably 10 to 70, and particularly preferably 20 to. 50. Moreover, 7-101 are preferable, as for the pressure (kPa) in the case of substituting with water (c), More preferably, it is 12-70, Most preferably, it is 20-50.

  In <Use Form 1>, drying after removing the dispersion medium can be performed by a known method, such as heat drying (for example, heating for 10 to 120 minutes in a drying furnace heated to 30 to 150 ° C.) or reduced pressure. Drying etc. can be applied. In addition, it dries under stirring in that the re-aggregation of the amphiphilic particles (a) is small, the surface activity of the amphiphilic particles is further improved, and the continuous defoaming property of the defoamer composition is further improved. It is preferable.

  In <Use Form 1>, the amphiphilic particles obtained by removing the dispersion medium can be crushed and / or classified. The pulverization performed here is to return the tertiary aggregate obtained by reaggregating the amphiphilic particles to the secondary aggregated particle, and crush the hydrophobic particles (hydrophobized secondary aggregate). Is different. Crushing can be performed by a known method, and using a jaw crusher, hammer mill, roller mill, impact pulverizer, jet pulverizer, etc., the rotation speed and pressure of the pulverizer are appropriately adjusted so that crushing does not occur. It is done with adjustment.

  As the oil component (b), liquid fats and oils, solid fats and oils, waxes, mineral oils, higher fatty acids, fatty acid amides derived from higher fatty acids, ester oils, higher alcohols, silicone oils and polyoxyalkylene oxides can be used.

  Liquid oils include vegetable oils (Avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, sasanca oil, castor oil, linseed oil , Safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnagar oil, Japanese kiri oil, jojoba oil and germ oil, etc., synthetic fats and oils (triglycerin, glycerin trioctanoate) And glycerin triisopalmitate).

  Solid fats and oils include cocoa butter, coconut oil, horse fat, hydrogenated coconut oil, palm oil, beef tallow, sheep fat, hardened beef tallow, palm kernel oil, pork fat, beef bone fat, owl kernel oil, hydrogenated oil, cow leg fat , Owl and hydrogenated castor oil.

  The waxes include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ibota wax, whale wax, montan wax, nuka wax, lanolin, kapok wax, lanolin acetate, liquid lanolin, sugar cane wax, lanolin fatty acid isopropyl, lauryl hexyl, reduced lanolin, jojojo Examples thereof include a wax, hard lanolin, shellac wax, lanolin alcohol ethylene oxide adduct, acetic ester of lanolin alcohol ethylene oxide adduct, cholesterol ethylene oxide adduct, fatty acid ester of lanolin alcohol ethylene oxide adduct and hydrogenated lanolin alcohol ethylene oxide adduct.

  Examples of mineral oils include hydrocarbon oils obtained by refining petroleum and refined mineral oils obtained by hydrogenation thereof, such as lubricating oil, spindle oil, paraffin oil {liquid paraffin (n-paraffin, isoparaffin, etc.), Ozokerite, squalene, pristane, paraffin, ceresin, squalene, petrolatum, etc.} and mixtures thereof can be used.

  Among the above fatty acids having 4 to 28 carbon atoms, fatty acids having 8 to 28 carbon atoms (lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, 12-hydroxystearic acid) Acid, undecylenic acid, and montanic acid).

  Examples of fatty acid amides derived from higher fatty acids include acid amides of the above higher fatty acids (such as lauric acid amide, stearic acid amide and erucic acid amide) and N-substituted acid amides (N, N′-ethylenebislauric acid amide), N, N′-methylenebisstearic acid amide, N, N′-ethylene bisstearic acid amide, N, N′-ethylene bisoleic acid amide, N, N′-ethylene bisbehenic acid amide, N, N′-butylene Bistearic acid amide, N, N′-hexamethylene bisstearic acid amide, N, N′-hexamethylene bisoleic acid amide, N, N′-xylylene bisstearic acid amide, stearic acid monomethylolamide, stearic acid diethanolamide N-oleyl stearamide, N-oleyl oleamide, N Stearyl stearic acid amide, N- stearyl oleic acid amide, N- oleyl palmitic acid amide and N- stearyl erucic acid amide, etc.) and the like.

  Ester oils include isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyloctanoate, cetyl lactate, myristyl lactate, Lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearylate, ethylene glycol di-2-ethylhexylate, dipentaerythritol fatty acid ester, monoisostearic acid N-alkyl glycol, dicaprate neopentyl glycol, malic acid diacid Isostearyl, glycerin di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexylate, triisostearyl Acid trimethylolpropane, penta-2-erythritol tetra-2-ethylhexylate, glycerol tri-2-ethylhexylate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, glyceryl trimyristate, tri- 2-heptylundecanoic acid glyceride, castor oil fatty acid methyl ester, oleyl oleate, cetostearyl alcohol, acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, Di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexylde palmitate Le, diisopropyl like 2-hexyldecyl adipate and sebacic acid.

  Examples of the higher alcohol include aliphatic alcohols having 12 to 36 carbon atoms (such as cetyl alcohol, stearyl alcohol, behenyl alcohol, and myristyl alcohol) among the aliphatic alcohols having 4 to 36 carbon atoms.

  Examples of the silicone oil include the aforementioned silicone compounds and cyclic silicones (such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane).

  As the polyoxyalkylene oxide, polyoxypropylene glycol having a number average molecular weight of 950 to 4000 can be used.

  The oil component (b) is preferably liquid oil, mineral oil or silicone oil, more preferably mineral oil or dimethylpolysiloxane from the viewpoint of sustained defoaming properties.

The kinematic viscosity (40 ° C .; mm ² / s) of the mineral oil is preferably 4 to 146, more preferably 4 to 30, particularly preferably 10 to 28, and most preferably 15 to 25. The kinematic viscosity (25 ° C .; mm ² / s) of dimethylpolysiloxane is preferably 10 to 100,000, more preferably 20 to 5,000, and particularly preferably 50 to 3,000. Within these ranges, the continuous defoaming property is further improved.

  These mineral oils and dimethylpolysiloxane can be easily obtained from the market, and trade names are exemplified below.

<Mineral oil>
Cosmo SC22 (21 mm ² / s), Cosmo SP10 (10 mm ² / s), Cosmo RC spindle oil (10 mm ² / s), Cosmo RB spindle oil (15 mm ² / s), Cosmo neutral 150 (32 mm ² / s), Cosmo Pure Spin G (21 mm ² / s) and Cosmo Pure Spin E (5 mm ² / s) (Cosmo Oil Lubricants Co., “Cosmo” is a registered trademark of Cosmo Oil Co., Ltd.); Nisseki Super Oil C (93 mm ² / s), Nisseki Super Oil D (141 mm ² / s) and Nisseki Super Oil B (54 mm ² / s) (Shin Nippon Oil Co., Ltd.); Stanol 43N (27 mm ² / s), Stanol 52 ( 56mm ² / s), stanol 69 (145mm ² / s), stanol 35 (9mm ² / s) and stanols LP35 11mm ² / s) (Esso Oil Co., Ltd.); and Fukkoru SH spin (9mm ² / s), Fukkoru NT100 (21mm ² / s), Fukkoru NT150 (28mm ² / s), Fukkoru NT200 (39mm ² / s), Fukkor NT60 (10 mm ² / s) and Fukkor ST machine (9 mm ² / s) (Fuji Kosan Co., Ltd., “Fukkor” is a registered trademark of Nippon Oil Corporation) etc. (numbers in parentheses are “kinematic viscosity” (40 ° C.) ”).

<Dimethylpolysiloxane>
KF96-10cs, KF96-20cs, KF96-30cs, KF96-50cs, KF96-100cs, KF96-200cs, KF96-300cs, KF96-350cs, KF96-500cs, KF96-1, 000cs, KF96-3,000cs, KF96- 5,000cs, KF96H-6,000cs, KF96H-10,000cs, KF96H-12,500cs, KF96H-30,000cs, KF96H-50,000cs, KF96H-60,000cs and KF96H-100,000cs (Shin-Etsu Chemical Co., Ltd.) Company); SH200-10cs, SH200-20cs, SH200-50cs, SH200-100cs, SH200-200cs, SH200-350cs, SH200-500cs, SH200-1, 000cs, SH200 3,000 cs, SH200-5,000 cs, SH200H-10,000 cs, SH200H-125 thousand cs, SH200H-30,000 cs, SH200H-60,000 cs and SH200H-100,000 cs (manufactured by Toray Dow Corning Silicone Co., Ltd.) ); Bisoni TSF451-10, TSF451-20, TSF451-30, TSF451-50, TSF451-100, TSF451-200, TSF451-300, TSF451-350, TSF451-500, TSF451-1000, TSF451-1500, TSF451-2000 , TSF451-3000, TSF451-5000, TSF451-6000, TSF451H-1M, TSF451H-12500, TSF451H-2M, TTSF451H-3M, TSF451 -5M, TSF451H-6M and TSF451H-10M (or more, GE Toshiba Silicone Co., Ltd.), and the like (the number after the hyphen represents a "kinematic viscosity (25 ℃)." However, 1M represents 10,000.).

  As the oil component (b), in addition to the above oil components, surfactants having an HLB of 4 or less according to the theoretical formula of Griffin can be used, for example, sorbitan fatty acid ester, polyethylene glycol fatty acid ester, pluronic surfactant, etc. it can.

  The values of HLB based on Griffin's theoretical formula are described on pages 90-91 of "Surfactant Properties and Applications" (author Takao Karime, publisher Koyukibo, published September 1, 1980). It can be calculated by the calculation formula described in “Measurement method of HLB by analytical value of emulsifier”.

  The oil component (b) can be appropriately selected depending on the type and temperature of the liquid to be added, and one of these may be used, or two or more may be used in combination.

  The oil component (b) can also be used as a mixture with the hydrophobic fine particles (hereinafter referred to as an oil compound). When used as an oil compound, from the viewpoint of initial defoaming properties, the hydrophobic fine particles are preferably hydrophobic fine particles obtained by hydrophobizing precipitated silica. As the hydrophobic fine particles obtained by hydrophobizing the precipitation method silica, the precipitation method silica hydrophobized by the above-mentioned method and the fine particles obtained by hydrophobizing the commercially available precipitation method silica can be used.

  The content (% by weight) of the hydrophobic fine particles contained in the oil compound is preferably from 1 to 50, particularly preferably from 3 to 25, based on the total weight of the oil component (b) and the hydrophobic fine particles. Within this range, the initial defoaming property is further improved, which is preferable.

  The oil compound can be obtained by a method in which the oil component (b) and the hydrophobic fine particles are stirred and dispersed using the stirrer and the disperser.

  Oil compounds can be easily obtained from the market, and DK Q1-049, SH 5500 COMPOUND, SC 5540 COMPOUND, 8590 ADDITIVE (Toray Dow Corning) are oil compounds using dimethylpolysiloxane as the oil component (b). Silicone Co., Ltd.).

  The content (% by weight) of the amphiphilic particles (a) contained in the antifoam composition of the present invention is 0.1 to 0.1, based on the weight of the amphiphilic particles (a) and the oil component (b). 15 is preferable, more preferably 0.2 to 10, and particularly preferably 0.5 to 5. Within this range, the sustained defoaming property is further improved.

  The content (% by weight) of the oil component (b) contained in the antifoam composition of the present invention is 85 to 99.9 based on the weight of the amphiphilic particles (a) and the oil component (b). More preferably, it is 90-99.8, Most preferably, it is 95-99.5. Within this range, the sustained defoaming property is further improved.

  It is preferable that the antifoamer composition of this invention contains water (c) from a viewpoint of initial stage antifoaming property. As water (c), tap water, industrial water, distilled water, ion exchange water, distilled water, ground water, sea water, hot spring water, and the like can be used. One of these may be used, or two or more may be mixed and used. Of these, soft water such as distilled water, ion exchange water, tap water and industrial water is preferable from the viewpoint of the initial defoaming property of the antifoaming agent composition, and more preferably purified water such as distilled water and ion exchange water. is there.

  When water (c) is contained, the content (% by weight) is preferably 5 to 400, more preferably 10 to 250, based on the total weight of the amphiphilic particles (a) and the oil component (b). It is. Within this range, the initial defoaming property is further improved.

  If necessary, the antifoaming composition of the present invention may further contain other components (hydrophilic silica, thickener, antifungal agent, antiseptic, rust inhibitor, and the like described in JP-A-2004-305882). Antioxidants, anti-skinning agents, and the like).

  When other components are contained, the total content (% by weight) of the other components is 0.01 to based on the total weight of the amphiphilic particles (a), the oily component (b) and the water (c). 20 (more preferably 0.05 to 10, particularly preferably 0.1 to 1) is preferable.

The antifoaming agent composition of the present invention can be obtained by a method of uniformly mixing the amphiphilic particles (a) and the oily component (b) and, if necessary, water (c) and other components.
The amphiphilic particles (a) can be used in the forms described in <Use Form 1> to <Use Form 4>, but are used in the form described in <Use Form 2> and <Use Form 3>. It is preferable. When used in these usage forms, the surface activity of the amphiphilic particles (a) is further improved, and the sustained defoaming property is further improved.

  The temperature for uniformly mixing the antifoam composition is not particularly limited, but may be heated to facilitate mixing. From the viewpoint of initial defoaming property, the temperature for uniform mixing is preferably 0 to 90 ° C, more preferably 10 to 50 ° C, and particularly preferably 15 to 40 ° C. This is considered to be because the efficiency of stirring and mixing is good within this temperature range, and the uniformity of the antifoaming agent composition becomes good.

  For the uniform mixing of the defoamer composition, the above-mentioned known dispersers can be used. Among these dispersers, a blade-type stirrer, a high-speed rotating homomixer, a high-pressure homogenizer, and a dissolver are preferable, a high-speed rotating homomixer, a high-pressure homogenizer, and a dissolver are more preferable, and a high-speed rotating homomixer is particularly preferable. According to these dispersers, since the dispersibility of the amphiphilic particles (a) is further improved, the surface activity of the amphiphilic particles (a) is further improved, and the defoaming composition has a sustained defoaming property. It becomes good.

  The antifoaming composition of the present invention is preferably an emulsion-dispersed type containing amphiphilic particles (a), an oil component (b) and water (c). As the emulsification dispersion type, the following emulsification dispersion types (type 1) to (type 4) are included.

(Type 1) A water-in-oil (w / o) type in which water (c) is emulsified and dispersed in the oil component (b).
(Type 2) An oil-in-water (o / w) type in which the oil component (b) is emulsified and dispersed in water (c).
(Type 3) A w / o / w type in which a water-in-oil (w / o) type emulsified dispersion composition is emulsified and dispersed in water (c).
(Type 4) An o / w / o type in which an oil-in-water (o / w) type emulsified dispersion composition is emulsified and dispersed in the oil component (c).

  The antifoaming composition of the present invention is appropriately selected from the above-mentioned (type 1) to (type 4) according to the use, but from the viewpoint of initial antifoaming property and sustained antifoaming property, etc. (type 1) {Water-in-oil (W / O) type}, (Type 2) {Oil-in-water (o / w) type} and (Type 3) {w / o / w type} are more preferable, and (Type 2) { Oil-in-water (o / w) type}.

  The defoamer composition which is an emulsification dispersion type of the present invention can be produced by a known method except that the amphiphilic particles (a), the oil component (b) and the water (c) are used. ) To (Production Method 3).

(Manufacturing method 1)
A method comprising an emulsification dispersion step in which the amphiphilic particles (a), the oil component (b) and the water (c) are mixed at a time and emulsified and dispersed.

(Manufacturing method 2)
A dispersion step of dispersing the amphiphilic particles (a) in the oil component (b) to obtain the amphiphilic particles oil dispersion (do); and water (c) and the amphiphilic particles oil dispersion (do). A method comprising an emulsifying and dispersing step of mixing and emulsifying and dispersing.

(Manufacturing method 3)
A step of dispersing the amphiphilic particles (a) in water (c) to obtain an amphiphilic particle aqueous dispersion (dw); and mixing the oil component (b) and the amphiphilic particle aqueous dispersion (dw) And a method including an emulsification dispersion step of emulsifying and dispersing.

  Among these production methods, (Production Method 3) is preferred from the viewpoint of sustained defoaming properties. This is considered to be because, when (Production Method 3) is applied, the surface activity of the amphiphilic particles (a) is further improved, and the stability of the emulsified dispersed particles is further improved.

  The amphiphilic particle oil dispersion (do) used in (Production Method 2) is (1) the amphiphilic particle oil dispersion of <Use Form 3> and (2) the parents of <Use Form 1>. A dispersion obtained by mixing and dispersing the powder of the medium particles (a) in the oil component (b) can be used. Among these, from the viewpoint of sustained defoaming property and the like, (1) the amphiphilic particle oil-based dispersion of <Use Form 3> is preferable.

  From the viewpoint of emulsion dispersion stability, the amphiphilic particle oil dispersion of <Use Form 3> is further mixed and dispersed to replace the amphiphilic particle oil dispersion from the viewpoint of emulsion dispersion stability and the like. A body (do) is preferred.

  The aqueous dispersion (dw) of amphiphilic particles used in (Production Method 3) is (3) the aqueous dispersion of amphiphilic particles of <Use Form 2> and (4) the amphiphile of <Use Form 1>. A dispersion in which the powder of the conductive particles (a) is mixed and dispersed in water (c) can be used. Among these, from the viewpoint of continuous defoaming property and the like, (1) the amphiphilic particle aqueous dispersion of <Use Form 2> is preferable.

  In the above <Use Form 2>, the amphiphilic particle aqueous dispersion is obtained by replacing the organic solvent with water (c) from the viewpoint of emulsification dispersion stability and the like, followed by further mixing and dispersing. (Dw) is preferable.

  For mixing and dispersing the amphiphilic particle aqueous dispersion of <Use Form 2> and the amphiphilic particle oil dispersion of <Use Form 3>, the above-mentioned known dispersers can be used.

  The amphiphilic particle aqueous dispersion (dw) or the amphiphilic oil dispersion (do) can be used after defoaming, and a known defoaming method such as vacuum defoaming or centrifugal defoaming can be applied.

  The content (% by weight) of the amphiphilic particles (a) contained in the amphiphilic particle aqueous dispersion (dw) or the amphiphilic oily dispersion (do) is that of the oily component (b) or water (c). Based on weight, 1-30 are preferable, More preferably, it is 3-25, Most preferably, it is 5-20. Within this range, the continuous antifoaming property of the antifoaming composition is further improved.

  In (Production Method 2), the emulsified dispersion of the amphiphilic particle aqueous dispersion (dw) and the oil component (b) is carried out by gradually adding the oil component (b) to the amphiphilic particle aqueous dispersion (dw). Alternatively, it may be carried out after the total amount of the amphiphilic particle aqueous dispersion (dw) and the oily component (b) is put in the emulsification dispersion apparatus described later. The rate of addition when the emulsification dispersion step is carried out while gradually adding the oily component (b) to the amphiphilic particle aqueous dispersion (dw) is appropriately determined according to the volume average particle diameter of the target emulsified dispersion particles. Selected.

  In (Production Method 3), the emulsified dispersion of the amphiphilic particle oil dispersion (do) and water (c) may be performed while gradually adding water (c) to the amphiphilic particle oil dispersion. Then, the total amount of the amphiphilic particle oil dispersion and water (c) may be added to the emulsification dispersion apparatus described later. The rate of addition when the emulsification dispersion step is carried out while gradually adding water (c) to the amphiphilic particle oil dispersion is appropriately selected according to the volume average particle diameter of the intended emulsification dispersion particles.

  As the emulsifying / dispersing device used in the emulsifying / dispersing step, the above-mentioned known dispersers and crushing / dispersing devices can be used. A Lee mixer and a vibratory stirrer, particularly preferably a high-speed rotating homomixer, a wing stirrer and a vibratory stirrer. When these dispersers are used, the volume average particle diameter of the emulsified dispersed particles can be within the above-mentioned preferable range, and the initial defoaming property and the sustained defoaming property are improved. Moreover, these dispersers and crushers can also be used in combination of two or more.

Such an emulsification dispersion operation can be appropriately selected according to the form of the target emulsification dispersion composition, and may be performed in one step or in two or more steps.
As a specific method of emulsification and dispersion performed in two steps, there may be mentioned a method of emulsifying one step of emulsification with a wing stirrer and subsequently emulsifying the mixture through a high-pressure rotary homomixer or the like. By emulsifying and dispersing in two or more steps in combination of two or more types of emulsifying devices, the volume average particle size of the emulsified dispersed particles can be reduced, and the particle size distribution can be narrowed.

  The operating conditions of the stirring mixer and / or the emulsifying disperser can be appropriately selected according to the volume average particle diameter of the target emulsified dispersion. Specifically, under the operating conditions where a stronger shearing force is applied, the volume average particle size of the emulsified dispersed particles can be reduced, and the residence time of the emulsified dispersed composition in the stirring mixer and / or the emulsified disperser can be reduced. When the length is increased, the particle size distribution of the emulsified dispersed particles can be narrowed.

  The temperature of the emulsification dispersion is not particularly limited as long as the oil component (b) and water (c) become liquid, but is preferably 10 to 100 ° C., more preferably from the viewpoint of the stability of the emulsified dispersion particles. Is 20 to 80 ° C, particularly preferably 25 to 70 ° C.

  When the antifoam composition of the present invention is w / o / w type, emulsification of the water-in-oil (w / o) type antifoam composition prepared by the above method and water (c). It can be produced by a method of further dispersing. On the other hand, in the case of the o / w / o type, it is produced by a method of further emulsifying and dispersing the oil-in-water (o / w) type antifoam composition prepared by the above method and the oil component (c). be able to.

  The antifoaming composition of the present invention may be added to the liquid to be added in advance or after foaming. As a method of adding after foaming of the liquid to be added, it can be added by a batch addition method, a continuous addition method, an intermittent addition method, or a method in which a foam measuring device and an antifoaming agent adding device are linked. You may add in one place with respect to a to-be-added liquid, and may be divided and added in several places. Further, upon addition, it may be diluted with a suitable diluent solvent or water.

  The antifoaming composition of the present invention is a known antifoaming agent {for example, a polyether antifoaming agent, a silicone antifoaming agent (Japanese Patent Publication No. 51-35556, Japanese Patent Laid-Open No. 52-2887, Japanese Patent Publication No. 52-19836). No. 55-23084, JP-A-6-142410 and JP-A-6-142411, etc.), mineral oil defoaming agents (JP-B 49-109276, JP-A 52-22356, JP-A-5-142356) 54-32187, JP-A-55-70308, JP-A-56-136610, etc.) and wax emulsion antifoaming agents (JP-A-47-114336, JP-A-60-156516, JP-A-5-156516) 62-171715, JP-A-64-68595, JP-A-1-210005 and JP-A-4-349904, etc.)} and the like.

  The addition amount (% by weight) of the antifoaming composition of the present invention is appropriately set according to the foaming state, temperature, viscosity, etc. of the liquid to be added, but based on the weight of the liquid to be added, 0.0001 to 10, more preferably 0.0005 to 8, particularly preferably 0.001 to 5, and most preferably 0.005 to 3. The addition temperature is preferably about 0 to 100 ° C, more preferably 10 to 60 ° C, particularly preferably 20 to 50 ° C.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. Unless otherwise specified, parts means parts by weight.

(Creation of amphiphilic particles)
The volume average particle diameter of the hydrophilic fine particles (p101 to p114) used in Production Examples 1 to 15 and Comparative Production Example 1 was measured by the following method.
<Volume average particle diameter of hydrophilic fine particles (particle diameter of secondary aggregate)>
Ion exchange water {electric conductivity (25 ° C.) 0.1 mS / m, so on, so that the concentration of hydrophilic fine particles is 1% by weight, and so on. } Was dispersed for 1 minute at an output of 60% using an ultrasonic disperser (manufactured by Hiel-Scher GmbH, ULTRASONIC PROCESSOR MODEL UP400S, the same applies hereinafter). Next, the volume average particle size in the dispersion was measured with a laser diffraction / scattering particle size distribution measuring device (manufactured by Horiba, Ltd., Partica LA-950).

  The volume average particle diameter of the hydrophobic fine particles was measured in the same manner as described above except that “ion exchange water” was changed to “2-propanol”.

M values of the hydrophobized aggregates (p201 to p215, hp1; secondary aggregates) obtained in Production Examples 1 to 15 and Comparative Production Example 1 were measured by the following method.
<Measurement of M value>
0.2 g of the hydrophobized aggregate (secondary aggregate) was added to 50 mL of ion exchange water in a 250 mL beaker. Subsequently, while constantly stirring the solution in the beaker with a magnetic stirrer, methanol (Kanto Chemical Co., Ltd., reagent grade, the same applies hereinafter) was gradually added dropwise from the burette to the beaker along the wall. The dropwise addition of methanol was continued until the entire amount of the hydrophobized aggregate (secondary aggregate) was suspended in ion-exchanged water. The drop amount (g) of methanol at the time when the entire amount of the hydrophobized aggregate (secondary aggregate) was suspended was recorded, and the M value was calculated from the following formula.

M value = (Methanol dropping amount) ÷ {(Methanol dropping amount) +50} × 100

<Production Example 1>
Hydrophilic fine particles (p101) {precipitation silica Nipsil CX-200 (primary particle size 4 nm, secondary aggregate particle size 1.7 μm, specific surface area 750 m ² / g by BET method)} (Mitsui Miike Seisakusho Co., Ltd., volume 3 L, the same applies hereinafter) and while stirring at low speed (750 rpm), the lipophilic compound (m1) {decyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-3103C)} A solution in which 1 part was dissolved in 50 parts of methanol (manufactured by Kanto Chemical Co., Inc., reagent grade 1, the same applies hereinafter) was sprayed. Next, the Henschel mixer was rotated at high speed (2000 rpm) for 15 minutes at room temperature (about 25 ° C., the same applies hereinafter), and mixed uniformly. Next, the Henschel mixer was heated with a heater and heat-dried at 80 ° C. for 3 hours to obtain a hydrophobized aggregate (p201). The M value of the hydrophobized aggregate (p201) was 35.

  Homogenizer (High Flex Disperser HG-92G Tytec) equipped with 3 parts of hydrophobized aggregate (p201) and 97 parts of methanol (manufactured by Kanto Chemical Co., Inc., reagent grade 1, the same applies hereinafter) with a 40 mm diameter sawtooth disc impeller. The dispersion liquid (e1) was obtained by stirring at 4000 rpm at 25 ± 3 ° C. for 15 minutes.

  In a wet medium type pulverizer {DISPERMAT SL-C-12 (manufactured by VMA-GETAMANN GMPH Co., Ltd., the same shall apply hereinafter) filled with 300 ml of dispersion (e1) with 100 ml of zirconia beads having a particle size of 0.7 mm at a rotor rotational speed of 4000 rpm. The dispersion (f1) containing the amphiphilic particles (a1) was obtained by crushing for 60 minutes.

  Subsequently, the dispersion liquid (f1) was dried under reduced pressure (70 to 80 ° C., a rotary evaporator) until the change in weight before and after the reduced pressure drying was 0.1% by weight or less. Subsequently, it dried for 90 minutes with a 130 degreeC normal air dryer, and obtained the amphiphilic particle (a1).

<Production Example 2>
100 parts of hydrophilic fine particles (p102) {precipitation silica Nipsil VN3 (primary particle diameter 15 nm, secondary aggregate particle diameter 18 μm, specific surface area 200 m ² / g by BET method)} are placed in a Henschel mixer with a heater and stirred at low speed While spraying (750 rpm), 5 parts of lipophilic compound (m2) {dimethylpolysiloxane having a kinematic viscosity (25 ° C.) of 20 mm ² / s (trade name: KF-96-20cs, manufactured by Shin-Etsu Chemical Co., Ltd.)} was sprayed. . Next, the Henschel mixer was rotated at a high speed (2000 rpm) for 15 minutes at a room temperature of 20 to 25 ° C. and mixed uniformly. Next, the Henschel mixer was heated with a heater, and heat treatment was performed at 230 ° C. for 3 hours to obtain a hydrophobized aggregate (p202). The M value of the hydrophobized aggregate (p202) was 50.

  Subsequently, “hydrophobic aggregate (p201) 3 parts” was changed to “hydrophobized aggregate (p202) 5 parts”, “methanol 97 parts” was changed to “ethanol (manufactured by Kanto Chemical Co., Ltd., reagent grade 1, below) Similarly.) The mixture was stirred in the same manner as in Production Example 1 except that it was changed to “95 parts” to obtain a dispersion (e2).

  Next, “dispersion (e1)” was changed to “dispersion (e2)”, “zirconia beads having a particle diameter of 0.7 mm” was changed to “zirconia beads having a particle diameter of 1 mm”, and “60 minutes”. Except for changing to “40 minutes”, the mixture was crushed in the same manner as in Production Example 1 and then dried to obtain a dispersion liquid (f2) containing amphiphilic particles (a2) and amphiphilic particles (a2). .

<Production Example 3>
“Hydrophilic fine particles (p102)” is changed to “hydrophilic fine particles (p103) {precipitation silica Nipsil AZ-204 (primary particle diameter 10 nm, secondary aggregate particle diameter 1.3 μm, specific surface area 300 m ² / g by BET method). )} ”,“ Lipophilic compound (m2) 50 parts ”is changed to“ lipophilic compound (m3) {dimethylpolysiloxane having a kinematic viscosity (25 ° C.) of 10 mm ² / s (Shin-Etsu Chemical Co., Ltd., Hydrophobized aggregate (p203) was obtained in the same manner as in Production Example 2 except that the product name was changed to “trade name KF-96-10cs)} 75 parts”. The M value of the hydrophobized aggregate (p203) was 85.

  Subsequently, Production Example 1 except that “3 parts of hydrophobized aggregate (p201)” was changed to “25 parts of hydrophobized aggregate (p203)” and “97 parts of methanol” was changed to “75 parts of methanol”. And a dispersion (e3) was obtained.

  Next, the dispersion liquid (f3) containing amphiphilic particles (a3) was crushed in the same manner as in Production Example 1 except that “dispersion liquid (e1)” was changed to “dispersion liquid (e3)”. ) And amphiphilic particles (a3).

<Production Example 4>
“Hydrophilic fine particles (p102)” are referred to as “hydrophilic fine particles (p104) {precipitation silica Nipsil AY-200 (primary particle diameter 10 nm, secondary aggregate particle diameter 2 μm, specific surface area 300 m ² / g by BET method)} “Lipophilic compound (m2) 50 parts” is changed to “lipophilic compound (m4) {dimethylpolysiloxane having a kinematic viscosity (25 ° C.) of 50 mm ² / s (manufactured by Shin-Etsu Chemical Co., Ltd., trade name) Hydrophobized aggregate (p204) was obtained in the same manner as in Production Example 2, except that it was changed to “KF-96-50cs)} 10 parts”. The M value of the hydrophobized aggregate (p204) was 65.

  Subsequently, “3 parts of hydrophobized aggregate (p201)” was changed to “10 parts of hydrophobized aggregate (p204)”, and “97 parts of methanol” was changed to “2-propanol (Kanto Chemical Co., Ltd., reagent grade, The same as in Production Example 1 except that the same was changed to “90 parts” to obtain a dispersion (e4).

  Next, with the exception of changing “dispersion (e1)” to “dispersion (e4)” and changing “zirconia beads having a particle diameter of 0.7 mm” to “zirconia beads having a particle diameter of 1 mm”, production example 1 After crushing similarly, it was dried to obtain a dispersion liquid (f4) containing amphiphilic particles (a4) and amphiphilic particles (a4).

<Production Example 5>
Hydrophilic fine particles (p105) {precipitation silica Nipsil KQ (primary particle size 14 nm, secondary aggregate particle size 100 μm, specific surface area 220 m ² / g by BET method)} and hydrophobic fine particles (m5) {modified amide 1 part of a wax (made by Big Chemie Japan Co., Ltd., trade name CERAFLOUR960, volume average particle size 4 μm)} is put into a Henschel mixer with a heater, and then the Henschel mixer is rotated at high speed (2000 rpm) at room temperature for 60 minutes to mix uniformly. did. Next, the Henschel mixer was heated with a heater while continuing high-speed rotation, heat-treated at 100 ° C. for 1 hour, then cooled to room temperature over 2 hours under high-speed stirring, and then the hydrophobized aggregate (p205) Got. The M value of the hydrophobized aggregate (p205) was 35.

  Next, “3 parts of hydrophobized aggregate (p201)” was changed to “1 part of hydrophobized aggregate (p205)”, and “97 parts of methanol” was changed to “ethyl acetate (Kanto Chemical Co., Ltd., reagent grade 1) 99”. A dispersion (e5) was obtained by stirring in the same manner as in Production Example 1 except that the part was changed to “part”.

  Next, “dispersion (e1)” was changed to “dispersion (e5)”, “zirconia beads with a particle size of 0.7 mm” was changed to “glass beads with a particle size of 3 mm”, and “60 minutes” Except for changing to “20 minutes”, the mixture was crushed in the same manner as in Production Example 1, and then dried to obtain a dispersion liquid (c5) containing amphiphilic particles (a5) and amphiphilic particles (a5). .

<Production Example 6>
“Hydrophilic fine particles (p102)” are changed to “hydrophilic fine particles (p106) {precipitation silica Nipsil E-220 (primary particle diameter 25 nm, secondary aggregate particle diameter 1.6 μm, specific surface area 120 m ² / g by BET method). )} ”, And hydrophobized aggregate (p206) in the same manner as in Production Example 2, except that“ 5 parts of lipophilic compound (m2) ”is changed to“ 2 parts of lipophilic compound (m2) ”. Got. The M value of the hydrophobized aggregate (p206) was 45.

  Subsequently, a dispersion (e6) was obtained by stirring in the same manner as in Production Example 1 except that “3 parts of the hydrophobized aggregate (p201)” was changed to “3 parts of the hydrophobized aggregate (p206)”.

  Then, after changing “dispersion (e1)” to “dispersion (e6)” and changing “60 minutes” to “40 minutes”, crushing treatment was performed in the same manner as in Production Example 1, and then dried. A dispersion liquid (f6) containing amphiphilic particles (a6) and amphiphilic particles (a6) were obtained.

<Production Example 7>
100 parts of “hydrophilic fine particles (p107) {precipitation silica Nipsil NA (primary particle diameter 25 nm, secondary aggregate particle diameter 9 μm, specific surface area 110 m ² / g by BET method)} are put into a Henschel mixer with a heater, and low speed While stirring (750 rpm), 30 parts of lipophilic compound (m6) {dimethylpolysiloxane having a kinematic viscosity (25 ° C) of 100 mm ² / s (trade name: KF-96-100cs) manufactured by Shin-Etsu Chemical Co., Ltd.} The solution dissolved in 50 parts was sprayed, and then the Henschel mixer was rotated at a high speed (2000 rpm) at room temperature for 15 minutes and mixed uniformly, then the Henschel mixer was heated with a heater, and heated and dried at 100 ° C. for 2 hours. To obtain a hydrophobized aggregate (p207) having an M value of 70. There was.

  Next, manufacturing was performed except that “3 parts of hydrophobized aggregate (p201)” was changed to “15 parts of hydrophobized aggregate (p207)” and “97 parts of methanol” was changed to “85 parts of 2-propanol”. Stirring was carried out in the same manner as in Example 1 to obtain a dispersion (e7).

  Next, with the exception of changing “dispersion (e1)” to “dispersion (e7)” and changing “zirconia beads having a particle size of 0.7 mm” to “zirconia beads having a particle size of 1 mm”, After crushing similarly, it was dried to obtain a dispersion (f7) containing amphiphilic particles (a7) and amphiphilic particles (a7).

<Production Example 8>
“Hydrophilic fine particles (p102)” are referred to as “hydrophilic fine particles (p108) {precipitation silica Nipsil E-170 (primary particle diameter 28 nm, secondary aggregate particle diameter 3 μm, specific surface area 110 m ² / g by BET method)} The hydrophobized aggregate (p208) was obtained in the same manner as in Production Example 7, except that “30 parts of lipophilic compound (m6)” was changed to “50 parts of lipophilic compound (m6)”. It was. The M value of the hydrophobized aggregate (p208) was 85.

  Subsequently, Production Example 1 except that “3 parts of hydrophobized aggregate (p201)” was changed to “20 parts of hydrophobized aggregate (p208)” and “97 parts of methanol” was changed to “80 parts of ethanol”. And a dispersion (e8) was obtained.

  Next, “dispersion (e1)” was changed to “dispersion (e8)”, “zirconia beads having a particle diameter of 0.7 mm” was changed to “zirconia beads having a particle diameter of 1 mm”, and “60 minutes”. Except for changing to “20 minutes”, the mixture was crushed in the same manner as in Production Example 1 and then dried to obtain a dispersion liquid (f8) containing amphiphilic particles (a8) and amphiphilic particles (a8). It was.

<Production Example 9>
“Hydrophilic fine particles (a102)” are changed to “hydrophilic fine particles (a109) {precipitation silica Nipsil ER (primary particle size 30 nm, secondary aggregate particle size 11 μm, specific surface area 100 m ² / g by BET method)}” Changed, “lipophilic compound (m6) 30 parts” to “lipophilic compound (m7) {dimethylpolysiloxane having a kinematic viscosity (25 ° C.) of 3000 mm ² / s (trade name: KF-, manufactured by Shin-Etsu Chemical Co., Ltd.) 96-3000cs)} 2 parts ”, except that the hydrophobized aggregate (p209) was obtained in the same manner as in Production Example 7. The M value of the hydrophobized aggregate (p209) was 80.

  Subsequently, “hydrophobized aggregate (p201) 3 parts” was changed to “hydrophobized aggregate (p209) 25 parts”, “methanol 97 parts” was changed to “tetrahydrofuran (Kanto Chemical Co., Ltd., reagent grade 1, below) The same as in Preparation Example 1 except that the amount was changed to “75 parts”. A dispersion (e9) was obtained.

  Next, “dispersion (e1)” was changed to “dispersion (e9)”, “zirconia beads having a particle diameter of 0.7 mm” was changed to “zirconia beads having a particle diameter of 1 mm”, and “60 minutes”. Except for changing to “20 minutes”, the mixture was crushed in the same manner as in Production Example 1 and then dried to obtain a dispersion liquid (f9) containing amphiphilic particles (a9) and amphiphilic particles (a9). .

<Production Example 10>
“Hydrophilic fine particles (p105)” is changed to “hydrophilic fine particles (p110) {precipitation silica Nipsil E-743 (primary particle size 60 nm, secondary aggregate particle size 1.5 μm, BET specific surface area 50 m ² / g). )} ”,“ Hydrophobic fine particles (m5) 1 part ”is changed to“ hydrophobic fine particles (m8) {modified polyethylene wax (manufactured by Big Chemie Japan Co., Ltd., trade name CERAFLOUR 961, volume average particle diameter 5 μm)} 70 A hydrophobized aggregate (p210) was obtained in the same manner as in Production Example 5 except that the part was changed to “part”. The M value of the hydrophobized aggregate (p210) was 85.

  Subsequently, Production Example 1 except that “3 parts of hydrophobized aggregate (p201)” was changed to “30 parts of hydrophobized aggregate (p210)” and “97 parts of methanol” was changed to “70 parts of tetrahydrofuran”. And a dispersion (e10) was obtained.

  Next, “dispersion (e1)” was changed to “dispersion (e10)”, “zirconia beads with a particle size of 0.7 mm” was changed to “glass beads with a particle size of 3 mm”, and “60 minutes”. Except for changing to “20 minutes”, the mixture was crushed in the same manner as in Production Example 1 and then dried to obtain a dispersion liquid (f10) containing amphiphilic particles (a10) and amphiphilic particles (a10). .

<Production Example 11>
“Hydrophilic fine particles (p105)” is changed to “hydrophilic fine particles (p111) {precipitation method silica Nipsil E-75 (primary particle size 75 nm, secondary aggregate particle size 2.3 μm, specific surface area 40 m ² / g by BET method). )} ”, And the hydrophobized aggregate (p211) in the same manner as in Production Example 5 except that“ 1 part of hydrophobic fine particles (m5) ”is changed to“ 10 parts of hydrophobic fine particles (m8) ”. Got. The M value of the hydrophobized aggregate (p211) was 65.

  Subsequently, Production Example 1 except that “3 parts of hydrophobized aggregate (p201)” was changed to “20 parts of hydrophobized aggregate (p211)” and “97 parts of methanol” was changed to “80 parts of ethanol”. And a dispersion (e11) was obtained.

  Next, “dispersion (e1)” was changed to “dispersion (e11)”, “zirconia beads having a particle size of 1 mm” was changed to “glass beads having a particle size of 1 mm”, and “60 minutes” was changed to “20”. Except for changing to “minute”, after crushing in the same manner as in Production Example 1, it was dried to obtain a dispersion liquid (f11) containing amphiphilic particles (a11) and amphiphilic particles (a11).

<Production Example 12>
A hydrophobized aggregate (p212) was obtained in the same manner as in Production Example 5, except that “1 part of hydrophobic particles (m5)” was changed to “65 parts of hydrophobic particles (m5)”. The M value of the hydrophobized aggregate (p212) was 75.

  Subsequently, Production Example 1 except that “3 parts hydrophobized aggregate (p201)” was changed to “25 parts hydrophobized aggregate (p212)” and “97 parts methanol” was changed to “75 parts tetrahydrofuran”. The mixture was stirred in the same manner as above to obtain a dispersion (e12).

  Next, “dispersion (e1)” was changed to “dispersion (e12)”, “zirconia beads having a particle diameter of 1 mm” was changed to “glass beads having a particle diameter of 3 mm”, and “60 minutes” was changed to “20”. Except for changing to “minutes”, the mixture was crushed in the same manner as in Production Example 1 and then dried to obtain a dispersion liquid (f12) containing amphiphilic particles (a12) and amphiphilic particles (a12).

<Production Example 13>
“Hydrophilic fine particles (p102)” is changed to “hydrophilic fine particles (p112) {Pyrolytic silica aerosil 50 (primary particle size 30 nm, secondary aggregate particle size 0.52 μm, specific surface area 50 m ² / g by BET method). } ", And the hydrophobized aggregate (p213) was prepared in the same manner as in Production Example 2, except that" 5 parts of lipophilic compound (m2) "was changed to" 80 parts of lipophilic compound (m3) ". Obtained. The M value of the hydrophobized aggregate (p213) was 70.

  Subsequently, Production Example 1 except that “3 parts of hydrophobized aggregate (p201)” was changed to “25 parts of hydrophobized aggregate (p213)” and “97 parts of methanol” was changed to “75 parts of methanol”. And a dispersion (e13) was obtained.

  Next, the dispersion (f13) containing amphiphilic particles (a13) was crushed in the same manner as in Production Example 1 except that “dispersion (e1)” was changed to “dispersion (e13)”. ) And amphiphilic particles (a13).

<Production Example 14>
“Hydrophilic fine particles (p102)” is changed to “hydrophilic fine particles (p113) {Silica gel Nipgel CX-200 (primary particle diameter 5 nm, secondary aggregate particle diameter 2.1 μm, specific surface area by BET method 750 m ² / g Hydrophobized aggregate (p214) in the same manner as in Production Example 2, except that “5 parts of lipophilic compound (m2)” is changed to “2 parts of lipophilic compound (m3)”. Got. The M value of the hydrophobized aggregate (p214) was 30.

  Next, manufacturing was performed except that “3 parts of hydrophobized aggregate (p201)” was changed to “10 parts of hydrophobized aggregate (p214)” and “97 parts of methanol” was changed to “90 parts of 2-propanol”. Stirring was carried out in the same manner as in Example 1 to obtain a dispersion (e14).

  Next, the dispersion liquid (f14) containing amphiphilic particles (a14) was crushed in the same manner as in Production Example 1, except that “dispersion liquid (e1)” was changed to “dispersion liquid (e14)”. ) And amphiphilic particles (a14).

<Production Example 15>
100 parts of “hydrophilic fine particles (p114) {combustion method alumina Aeroxide AluC (primary particle size 13 nm, secondary aggregate particle size 0.18 μm, specific surface area 100 m ² / g by BET method)}” in a Henschel mixer with heater While stirring at low speed (750 rpm), the lipophilic compound (m9) {alkoxy-modified dimethylpolysiloxane having a viscosity at 25 ° C of 80 mm ² / s (trade name X-40-9225, manufactured by Shin-Etsu Chemical Co., Ltd.)} A solution of 2 parts in 50 parts of methanol was sprayed. Next, the Henschel mixer was rotated at a high speed (2000 rpm) at room temperature for 15 minutes and mixed uniformly. Next, the Henschel mixer was heated with a heater and heat-dried at 100 ° C. for 2 hours to obtain a hydrophobized aggregate (p215). The M value of the hydrophobized aggregate (p215) was 30.

  Subsequently, a dispersion liquid (e15) was obtained by stirring in the same manner as in Production Example 1 except that “3 parts of the hydrophobized aggregate (p201)” was changed to “3 parts of the hydrophobized aggregate (p215)”.

  Next, the dispersion liquid (e15) was crushed in the same manner as in Example Production 1 except that the dispersion liquid (e1) was changed to the “dispersion liquid (e15)”, and then dried to obtain a dispersion liquid containing amphiphilic particles (a15) ( f15) and amphiphilic particles (a15) were obtained.

<Comparative Production Example 1>
100 parts of hydrophilic fine particles (p111) were put into a Henschel mixer with a heater, and 5 parts of lipophilic compound (m2) were sprayed while stirring at low speed (750 rpm). Next, the Henschel mixer was rotated at a high speed (2000 rpm) for 15 minutes at a room temperature of 20 to 25 ° C. and mixed uniformly. Next, the Henschel mixer was heated with a heater and heat-treated at 230 ° C. for 3 hours to obtain comparative particles (hp1). The M value of the comparative particles (hp1) was 50.

   For the amphiphilic particles (a1 to a15) obtained in Production Examples 1 to 15 and the comparative particles (hp1) obtained in Comparative Production Example 1, the volume average particle size is measured by a laser diffraction / scattering particle size distribution measuring device. Table 1 shows the results measured with (Horiba Ltd., Partica LA-950). For the amphiphilic particles (a1 to a15), the volume average particle diameter of the amphiphilic particles contained in the dispersions (f1 to f15) is measured, and for the particles (hp1), 1 part of the particles is 2-propanol. The volume average particle diameter of the particles contained in the dispersion dispersed in 99 parts using an ultrasonic disperser was measured.

1% by weight obtained by dispersing 1 part of amphiphilic particles (a1 to a15) obtained in Production Examples 1 to 15 in 99 parts of 2-propanol using an ultrasonic disperser for 1 minute at an output of 70%. the dispersion 0.02 g, was allowed to stand for entering the addition to the test tube for 60 minutes with ion-exchanged water 5 cm ³ and n- hexane 5 cm ^3, amphoteric medium of the present invention the interface between the ion-exchanged water and n- hexane An aggregate layer of particles was formed, and the upper and lower layers were clean layers that did not contain amphiphilic particles. From this, it is considered that the particle surface is divided into a hydrophilic surface and a hydrophobic surface.

Comparative particles (hp1) obtained in Comparative Production Example 1, comparative particles (hp2) used in Comparative Production Example 3 to be described later {Fine-burning silica hydrophobized fine particles Aerosil R974 (secondary aggregate particle size) 1.2 μm, specific surface area by BET method 170 m ² / g, M value 40, manufactured by Nippon Aerosil Co., Ltd.)} and comparative particles used in Comparative Production Example 4 (hp3) {fine particles obtained by hydrophobizing precipitated silica Nipsil SS-50F (secondary aggregate particle size 1.1 μm, BET specific surface area 180 m ² / g, M value 60, manufactured by Tosoh Silica Corporation)} 1 part of 2-propanol 99 parts by ultrasonic disperser 1 wt% dispersion 0.02g obtained by dispersing 1 minute at an output of 70% with, in addition to the test tube containing the ion-exchanged water 5 cm ³ and n- hexane 5 cm ³ 60 minutes Were location, the particles dispersed in n- hexane layer, the entire n- hexane layer became cloudy. From this, it is considered that the particle surface is not divided into a hydrophilic surface and a hydrophobic surface.

(Preparation of amphiphilic particle oil dispersion (do))
<Production Example 16>
In an eggplant flask attached to a rotary evaporator, 100 parts of a dispersion (f1) containing the amphiphilic particles (a1) obtained in Production Example 1 and an oily component (b1) {kinematic viscosity (40 ° C.) is 21 mm ² / S mineral oil (Cosmo Oil Lubricants Co., Ltd., trade name Cosmo SC22)} is put in 97 parts, heated at normal pressure (approximately 101 kPa), reached 90 ° C., and maintained at that temperature, 12 kPa The organic solvent (methanol) was distilled off while gradually reducing the pressure to a pressure of. The distillation operation was stopped 30 minutes after the evaporation of the organic solvent (methanol) ceased. At this time, the weight of the organic solvent (methanol) distilled off was 97 parts, and the weight of the liquid remaining in the reaction vessel was 100 parts. Thereafter, the liquid remaining in the reaction vessel was dispersed for 1 minute at an output of 70% using an ultrasonic disperser (manufactured by Hielscher Ultrasonics, Ultrasonic Processor UP400S, the same applies hereinafter), and an amphiphilic particle oil dispersion ( do1) was obtained.

<Production Example 17>
"100 parts of dispersion (f1) containing amphiphilic particles (a1) obtained in Production Example 1" is "100 parts of dispersion (f2) containing amphiphilic particles (a2) obtained in Production Example 2" ”97 parts of“ oil component (b1) ”and“ oil component (b2) {dimethylpolysiloxane having a kinematic viscosity (25 ° C.) of 500 mm ² / s (trade name: KF96-500cs, manufactured by Shin-Etsu Chemical Co., Ltd.)} In the same manner as in Production Example 16, except that 97 parts of “oil component (b1)” is changed to “75 parts” of “oil component (b1)”, an amphiphilic particle oil dispersion (do2) is obtained. It was.

<Production Example 18>
"100 parts of dispersion (f1) containing amphiphilic particles (a1) obtained in Production Example 1" is referred to as "100 parts of dispersion (f3) containing amphiphilic particles (a3) obtained in Production Example 3" An amphiphilic particle oil dispersion (do3) was obtained in the same manner as in Production Example 16 except that the composition was changed to "".

(Preparation of amphiphilic particle aqueous dispersion (dw))
<Production Example 19>
100 parts of the dispersion (f4) containing the amphiphilic particles (a4) obtained in Production Example 4 and 90 parts of ion-exchanged water are placed in a pressure-reducible reaction vessel equipped with a heating and stirring device, and normal pressure (approximately The mixture was heated to 101 kPa and reached 80 ° C., and the organic solvent (2-propanol) was distilled off while gradually reducing the pressure to 70 kPa while maintaining the temperature. The distillation operation was stopped 60 minutes after the organic solvent (2-propanol) was removed. At this time, the weight of the organic solvent (2-propanol) distilled off was 90 parts, and the weight of the liquid remaining in the reaction vessel was 100 parts. Thereafter, the liquid remaining in the reaction vessel was dispersed for 1 minute at an output of 70% using an ultrasonic disperser to obtain an amphiphilic particle aqueous dispersion (dw4).

<Production Examples 20-23>
“Dispersion (f4) containing amphiphilic particles (a4) obtained in Production Example 4” is used in the “dispersion containing amphiphilic particles” described in Table 2, and the amount of ion-exchanged water used is “90 parts. The aqueous amphiphilic particle dispersions (dw5) to (dw8) were obtained in the same manner as in Production Example 19, except that the amount of ion-exchanged water described in Table 2 was changed.

<Production Example 24>
25 parts of amphiphilic particles (a9) obtained in Production Example 9 and 75 parts of ion-exchanged water were dispersed at an output of 70% for 3 minutes using an ultrasonic disperser, and an amphiphilic particle aqueous dispersion ( dw9) was obtained.

<Production Examples 25-27>
“Amphiphilic particles (a9) obtained in Production Example 9” are listed in “Amphiphilic particles” listed in Table 3, and the amount of amphiphilic particles used “25 parts” is listed in Table 3. In the same manner as in Production Example 24 except that the amount of ion-exchanged water “75 parts” was changed to the amount of ion-exchanged water listed in Table 3 in “Amount of active particles used” The bodies (dw10) to (dw12) were obtained.

(Preparation of comparative particle oil dispersion)
<Comparative Production Example 2>
10 parts of the comparative particles (hp1) obtained in Comparative Production Example 1 and 90 parts of the oil component (b1) were dispersed for 3 minutes at an output of 70% using an ultrasonic disperser to produce a comparative particle oil dispersion. (Hdo1) was obtained.

<Comparative Production Example 3>
10 parts of hydrophobic fine particles (hp2) and 90 parts of oily component (b2) were dispersed for 3 minutes at an output of 70% using an ultrasonic disperser to obtain a comparative particle oily dispersion (hdo2).

(Preparation of aqueous particle dispersion for comparison)
<Comparative Production Example 4>
10 parts of hydrophobic fine particles (hp3) and 90 parts of ion-exchanged water were dispersed for 3 minutes at an output of 70% using an ultrasonic disperser to obtain a comparative particle water dispersion (hdw3).

<Example 1>
The amphiphilic particle oil dispersion (do1) obtained in Production Example 16 was used as the antifoam composition (df1) of the present invention.

<Comparative Example 1>
The comparative particle oil dispersion (hdo1) obtained in Comparative Production Example 2 was used as a comparative antifoam composition (hdf1) as it was.

<Examples 2 to 15 and Comparative Examples 2 to 3>
Each component described in Table 4 and Table 5 is put into a glass container having an inner diameter of 41 mm and a capacity of 170 ml in a lump, and a paint shaker (manufactured by Red Device Equipment, trade name: 1400 classic shaker) is used at 25 ± 3 ° C. Shake for a minute to emulsify and disperse the defoamer composition of the present invention (df2 to df15; emulsified and dispersed antifoam composition) and comparative antifoam compositions (hdf2 and hdf3; emulsified and dispersed defoamer). A foam composition) was prepared.

<Comparative example 4>
22.50 parts of stearyl alcohol (manufactured by SASOL, trade name Nacol 18-98) in a glass container having an inner diameter of 41 mm and a capacity of 170 ml was heated and melted to 75 ± 3 ° C. Next, 7.50 parts of calcium carbonate (product name: Brilliant-1500, manufactured by Shiroishi Kogyo Co., Ltd.) was added, and 10 minutes at 4000 rpm using a homogenizer equipped with a 40 mm diameter sawtooth disc impeller while maintaining 75 ± 5 ° C. Stir for minutes to mix. Next, 69.94 parts of warm water adjusted to 75 ± 3 ° C. was gradually dropped using a dropper while stirring at 3000 rpm while maintaining 75 ± 3 ° C. to prepare an emulsified dispersion. Next, 0.06 part of wera gum (trade name K1A96, manufactured by Sanki Co., Ltd.) is added to the emulsified dispersion and cooled to obtain a comparative antifoam composition (hdf4; o / w type antifoam composition). It was.

  In addition, the numerical value corresponding to each component in Table 4 and Table 5 represents parts by weight, and the oil component (b3) is an oil compound obtained as follows.

<Creation of oil component (b3)>
Mineral oil with kinematic viscosity (40 ° C.) 5 mm2 / s {Product name: Cosmo Pure Spin E, manufactured by Cosmo Oil Lubricants Co., Ltd.} After 70 parts were put into a container capable of heating, stirring and cooling, the temperature was raised to 50 ° C. while stirring, and heating and stirring were continued at this temperature for another 3 hours. Further, the mixture was stirred for 15 minutes at 4000 rpm with an Excel Auto Homogenizer ED-7 (manufactured by Nippon Seiki Seisakusyo Co., Ltd.) equipped with impeller blades, and a dispersion test {JISK 5600-2-5: 1999 (corresponding to ISO 1524: 1983) }, It was confirmed that there were no grains of 5 microns or more, and an oily component (b3) was obtained.

  The types of the antifoam composition (df2 to df15) obtained in Examples 2 to 15 and the comparative antifoam composition (hdf2 and 3) obtained in Comparative Examples 2 to 3 were determined as follows. And listed in Tables 4 and 5.

<Determination of emulsified dispersion type of antifoam composition>
One drop (approximately 0.05 g) of the antifoam composition was dropped into approximately 1 ml of ion-exchanged water using a dropper. An oil-in-water (O / W) type in which an antifoam composition is easily diffused and mixed in ion-exchanged water is used as an oil-in-water (O / W) type, or remains separated from ion-exchanged water or an antifoam composition remains in droplets What remained was made into the water-in-oil (W / O) type. In addition, the antifoamer composition for comparison (hdf2, 3) obtained in Comparative Examples 2 to 3 was a gel-like product and had poor emulsification, and the type was unknown.

  About the antifoamer composition obtained in Examples 1-15 and Comparative Examples 1-3, defoaming property (initial defoaming property and continuous defoaming property) was evaluated as follows, and the result is shown in Table 6. Described. In the table, the contents (% by weight) of the amphiphilic particles (a), the oil component (b) and the water (c) contained in the antifoam composition of the present invention are described.

<Initial defoaming property>
200 mL of a foamable liquid prepared by diluting 100 parts of a commercially available latex emulsion (JSR0696, manufactured by JSR Corporation) with 100 parts of ion-exchanged water was placed in a glass measuring cylinder having an inner diameter of 50 mm and a height of 350 mm, and a measurement sample (antifoaming) Agent composition) 0.1 g was added, and according to the foaming test of JIS K2518: 2003, a diffuser stone was inserted to the bottom of the liquid and air was aerated at 1000 mL / min, and the foam surface from the bottom after 30 seconds. The height (mm, liquid level height) was read. A similar test (blank test) was performed on the foamable liquid not containing the antifoam composition, and the initial antifoaming property was calculated using the following formula. The larger this value, the smaller the amount of foam generated and the better the initial defoaming property.

Initial defoaming property (%) = {(Liquid surface height in blank test) − (Liquid surface height in test after addition of antifoam composition)} ÷ (Liquid surface height in blank test)

<Sustained defoaming property>
The foaming liquid containing the antifoaming composition whose initial defoaming property was measured and the foaming liquid used for the blank test were put in a sealed container, respectively, and stored at 50 ° C. for 1 week. The value calculated by the following formula was evaluated as the continuous defoaming property.

Sustained defoaming property (%) = {(Liquid surface height in blank test) − (Liquid surface height in foaming liquid containing antifoam composition)} ÷ (Liquid surface height in blank test)

  It has confirmed that the antifoamer composition (df1-df15) of this invention was remarkably excellent in a lasting defoaming property compared with the antifoamer composition for a comparison (hdf1-hdf4). Moreover, the antifoamer composition (df2-df15) containing water (c) was remarkably excellent also in the initial defoaming property.

  The antifoaming composition of the present invention can be applied to an additive liquid containing water, etc., and is a pulp and paper industry, food industry, textile industry, paint industry, ink industry, adhesive industry, petroleum industry, latex production process and wastewater treatment. It can be used as an antifoaming agent for processes.

Claims (5)

An antifoam composition comprising amphiphilic particles (a) and an oil component (b),
The amphiphilic particles (a) are composed of secondary agglomerated particles composed of hydrophilic fine particles composed of silica and / or alumina and hydrophobic fine particles, and the surface of the secondary agglomerated particles is hydrophobic with the hydrophilic surface. An antifoam composition characterized by being divided into two parts. Based on the weight of the amphiphilic particles (a) and the oil component (b), the content of the amphiphilic particles (a) is 0.1 to 15% by weight, and the content of the oil component (b) is 85 to 99. The antifoaming composition according to claim 1, wherein the composition is 9% by weight. Furthermore, the antifoamer composition of Claim 1 or 2 containing water (c). The antifoaming composition according to claim 3, wherein the content of water (c) is 5 to 400% by weight based on the weight of the amphiphilic particles (a) and the oily component (b). The antifoaming composition according to claim 3 or 4, which is of an emulsifying dispersion type.