JP2011083753A - Amphiphilic particle and producing method of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an amphiphilic particle which has an excellent surface activation (emulsification capacity, dispersion stability and the like). <P>SOLUTION: The amphiphilic particle, which is a secondary agglomerate particle includes hydrophilic fine particle consisting of a silica and/or an alumina and a hydrophobic fine particle, and in which the surface of the secondary agglomerate particle is divided into a hydrophilic surface and a hydrophobic surface, is used. The producing method of the amphiphilic particle includes: a hydrophobic process to obtain a hydrophobic particle (p2) by conducting a surface treatment of the secondary agglomerate (p1) of a hydrophilic fine particle having a primary particle diameter of 1 to 80 nm by using a lipophilic compound or a hydrophobic fine particle; a dispersion process to obtain a dispersion liquid of a hydrophobic particle (p2) by dispersing a hydrophobic particle (p2) into an organic solvent (s1) having a dielectric constant of 5 to 50; and a crushing process to obtain an amphiphilic particle by crushing so that the volume average particle diameter of the hydrophobic particle (p2) in the dispersion liquid becomes 0.1 to 10 μm. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to amphiphilic particles and a method for producing the same.

  Conventionally, raw material particle particles having a crystal structure and not soluble in any of water, hydrophilic solvent and lipophilic solvent and having a hydrophilic surface are treated with hydrophobic organic compounds (raw material particles generated by grinding of raw material particles). Surface active particles having a hydrophilic surface and a hydrophobic surface, obtained by grinding in the presence of a substance that binds to the surface and thereby stabilizes the nascent surface energetically; and having a crystalline structure and water The raw material particle particles, which are not dissolved in any of the hydrophilic solvent and the lipophilic solvent and have a hydrophobic surface, are combined with the hydrophilic organic compound, water or oxygen (the new surface of the raw material particles generated by grinding of the raw material particles). Thus, there is known a surface active particle having a hydrophilic surface and a hydrophobic surface obtained by grinding in the presence of a substance that stabilizes the new surface in terms of energy (Patent Document 1).

JP 2003-64110 A

However, with conventional surfactant particles, it is difficult to control the proportion of the nascent surface and to control the position thereof. For example, if grinding is performed strongly in order to obtain high surface activity, the nascent surface increases as the nascent surface increases. The surface is scattered throughout the particle, and as a result, the hydrophilic portion and the hydrophobic portion are uniformly distributed over the entire particle surface, and particles having high surface activity cannot be obtained.
On the other hand, if the grinding is carried out weakly in order to make the reactant (hydrophobic organic compound or hydrophilic organic compound) unevenly distributed on the particle surface, there will be fewer nascent surfaces, and as a result, the newly generated hydrophilic portion or hydrophobic Only the particles having a low surface activity can be obtained due to remarkably fewer active parts.
As described above, conventional surface active particles have a problem that they cannot exhibit high surface activity (emulsification ability, dispersion stability, etc.). That is, an object of the present invention is to provide amphiphilic particles having excellent surface activity (emulsification ability, dispersion stability, etc.).

  The amphiphilic particles of the present invention are characterized by secondary agglomerated particles composed of hydrophilic fine particles composed of silica and / or alumina and hydrophobic fine particles, wherein the surface of the secondary agglomerated particles is a hydrophilic surface. And the hydrophobic surface.

A feature of the method for producing amphiphilic particles of the present invention is a method for producing the above-mentioned amphiphilic particles, wherein the secondary aggregate (p1) of hydrophilic fine particles having a primary particle diameter of 1 to 80 nm is used as a parent. A hydrophobizing step of obtaining hydrophobized particles (p2) by surface treatment with an oily compound or hydrophobic fine particles;
A dispersion step of dispersing the hydrophobic particles (p2) in an organic solvent (s1) having a relative dielectric constant of 5 to 50 to obtain a dispersion of the hydrophobic particles (p2); and the hydrophobic particles (p2) in the dispersion The gist of the present invention is to include a crushing step of crushing the volume average particle diameter to 0.1 to 10 μm to obtain amphiphilic particles.

  The amphiphilic particles of the present invention are remarkably superior in surface activity (emulsification ability, dispersion stability, etc.) as compared with conventional amphiphilic particles. Therefore, when the amphiphilic particles of the present invention are used, stable emulsion particles and suspension particles can be prepared without using an organic low molecular weight surfactant.

  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.

  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.

  The fine particles composed of silica and / or alumina include fine particles composed of silica, alumina and 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 a hydrolyzate of aluminum alkoxide and alumina obtained by calcining aluminum hydroxide.

  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 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.

<Silica gel method>
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, sabonite, etc.), vermiculite, mica (mica), chlorite, hydrotalcite, layered polysilicate (kanemite, macatite) Fine particles composed of ialite, magadiite, and Kenyaite} and fine particles obtained by hydrophilizing hydrophobic fine particles (hydrophobic fine particles obtained by surface modification with hydrophilic compounds (hydrophilic fine particles, hydrophilic resins, etc.), hydrophobic with an oxidizing agent Fine particles obtained by oxidizing the surface of the conductive 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.
<Method i> 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.
<Method ii> An aqueous solution (an 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 hydrophilize the surface. Wet coating method.
<Method iii> A method of hydrophilizing the surface by physically depositing a metal oxide film on the surface of the hydrophobic fine particles using metal oxide fine particles such as silica and alumina.
<Method iv> 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. If it is in this range, the hydrophilicity is uniformly treated and the amount of unadsorbed hydrophilic compounds is reduced, so that the surface activity is further improved.

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 surface activity 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 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 surface activity.

  Examples of the lipophilic compound used for hydrophobizing hydrophilic fine particles include halosilane, alkoxysilane, fatty acid having 4 to 24 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 24 carbon atoms include butanoic acid, hexanoic acid, lauric acid, stearic acid, oleic acid, and behenic 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 polydimethylsiloxane, alkyl group-modified polydimethylsiloxane (modified alkyl group having 2 to 6 carbon atoms), hydroxyl group-modified polydimethylsiloxane, amino group-modified polydimethylsiloxane, polyether-modified polydimethylsiloxane, and hydrogen poly. Examples thereof include dimethylsiloxane.

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

As the polyether-modified polydimethylsiloxane, those 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 and hydrophobic groups in a molecule, and its value is “property and application of surfactant” (author Takao Karime, publisher Koyukibo, Inc., September 1980). (Issued on Jan. 1), page 89 to page 90, and “calculation method of HLB by emulsification test”. For example, polyether-modified polydimethylsiloxane can be calculated by the following test method.

<Measurement method of HLB by emulsification test of polyether-modified polydimethylsiloxane>
The polyether-modified polydimethylsiloxane X whose HLB is unknown and the emulsifier A whose HLB is known are mixed at different ratios, and the oil whose HLB is known is emulsified. The HLB of the polyether-modified polydimethylsiloxane 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 the emulsifier A based on the total weight of the polyether-modified polydimethylsiloxane X and the emulsifier A, and W _X is the polyether-modified polydimethylsiloxane X based on the total weight of the polyether-modified polydimethylsiloxane X and the emulsifier A. HLB _A is the HLB of the emulsifier A, and HLB _X is the HLB of the polyether-modified polydimethylsiloxane X.

As the hydroxyl group-modified polysiloxane, amino group-modified polysiloxane, and hydrogen polydimethylsiloxane, 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 viewpoint of surface activity, more preferably silicone compounds, and particularly preferably dimethylsiloxane having a kinematic viscosity of 10 to 3000 (mm ² / s, 25 ° C.). And an alkyl group-modified polydimethylsiloxane obtained by modifying the dimethylsiloxane, most preferably dimethylsiloxane having a kinematic viscosity of 20 to 100 (mm ² / s, 25 ° C.).

  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 performed by a known method, for example, by the methods described in <Method 1-1> and <Method 1-2> below.

<Method 1-1>
While the hydrophilic fine particles and the lipophilic compound or hydrophobic fine particles dispersed in a solvent (paraffin oil, mineral oil, organic solvent, etc. having a kinematic viscosity of 5 to 30 mm ² / s (40 ° C.)) are stirred with a stirrer, A method in which a compound or hydrophobic fine particle is adsorbed or reacted on the surface of a hydrophilic fine particle to make it hydrophobic (wet method).

<Method 1-2>
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, from the viewpoint of surface activity (from the viewpoint that crushing of the secondary aggregate (p1) is facilitated and the surface activity of the amphiphilic particles is good), <Method 1-2> A dry method is preferred.

  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.

  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. Within this range, the hydrophobicity is uniformly treated and the amount of unadsorbed hydrophobic fine particles is reduced, so that the surface activity 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, it is considered that they are more easily crushed than crystalline fine particles, and are easily divided into a hydrophilic surface and a hydrophobic surface, and the surface activity of the amphiphilic particles is further improved. Whether the fine particles are amorphous fine particles can be confirmed by performing powder diffraction X-ray diffraction analysis according to JIS K 0131 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. Bisection means that the hydrophilic surface and the hydrophobic surface are localized in one secondary aggregate as if the positive electrode and the negative electrode were localized in one magnet (one Different from those scattered in secondary aggregates). 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 of the present invention is preferably 0.1 to 10, more preferably 0.1 to 5, particularly preferably from the viewpoint of surface activity (emulsification ability and dispersion stability). Preferably it is 0.2-1 and most preferably 0.2-0.5.

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

  The amphiphilic particles of the present invention are hydrophilic having a primary particle diameter of 1 to 80 (preferably 5 to 30, more preferably 10 to 25) nm from the viewpoint of surface activity (emulsification ability and dispersion stability). Amphiphilic particles obtained by hydrophobizing the secondary aggregate (p1) composed of fine particles and then crushing are preferable.

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

  As a method for hydrophobizing the secondary aggregate, a method similar to the above-described fine particles obtained by hydrophobizing the hydrophilic fine particles (fine particles obtained by surface modification of hydrophilic fine particles with lipophilic compounds or hydrophobic fine particles) can be applied.

  The secondary aggregate (p1) is used in distinction from the term secondary aggregate particles, and the volume average particle diameter (μm) is preferably 1 to 100, more preferably 1.5 to 40, and particularly preferably 2 to 2. 30. Within this range, the secondary aggregate (p1) can be easily crushed and the surface activity is further improved.

  In addition, the volume average particle diameter of the secondary aggregate (p1) is based on JIS Z8825-1: 2001 in which the dispersion obtained by dispersing the secondary aggregate (p1) in ion-exchanged water so as to have a concentration of 1% by weight. Using a laser diffraction particle size analyzer {for example, Microtrac series manufactured by Leeds & Northrup, Partica LA series manufactured by HORIBA, Ltd.}, 1000 parts by weight of deionized water having an electric conductivity (25 ° C.) of 0.1 mS / m or less, A measurement dispersion was prepared by adding a measurement sample to a measurement sample concentration of 0.1% by weight, and measured at a measurement temperature of 25 ± 5 ° C. Then, the refractive index of water was 1.333. Literature values ("A GUIDE FOR ENTERING MICROTRAC" RUN INFORMATION "(F3) DATA", Leed) & Northrup Co. created) using a determined as a 50% cumulative volume-average particle diameter.

  As the method for producing the amphiphilic particles of the present invention, the following (Production Method 1) to (Production Method 4) can be applied.

<Manufacturing method 1>
A method in which the secondary aggregate (p1) made of hydrophilic fine particles is hydrophobized and then crushed.
As a method for hydrophobizing the secondary aggregate, a method similar to the above-described fine particles obtained by hydrophobizing the hydrophilic fine particles (fine particles obtained by surface modification of hydrophilic fine particles with lipophilic compounds or hydrophobic fine particles) can be applied.

<Manufacturing method 2>
A method in which a secondary aggregate composed of hydrophobic fine particles is hydrophilized and then crushed.
The secondary aggregate is hydrophilized by fine particles obtained by hydrophilizing the above hydrophobic fine particles (fine particles obtained by modifying the surface of hydrophobic fine particles with hydrophilic compounds (hydrophilic fine particles, hydrophilic resins, etc.), hydrophobic with an oxidizing agent. The same method as that for the fine particles obtained by oxidizing the surface of the conductive fine particles) 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.

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

In <Production Method 1>, hydrophobization to obtain hydrophobized particles (p2) by surface-treating secondary aggregates (p1) of hydrophilic fine particles having a primary particle size of 1 to 80 nm with lipophilic compounds or hydrophobic fine particles Process;
A dispersion step of dispersing the hydrophobic particles (p2) in an organic solvent (s1) having a relative dielectric constant of 5 to 50 to obtain a dispersion of the hydrophobic particles (p2); and the hydrophobic particles (p2) in the dispersion Are crushed so as to have an average particle diameter of 0.1 to 10 μm (preferably 0.1 to 5 μm, more preferably 0.2 to 1 μm, particularly preferably 0.2 to 0.5 μm), It is preferable to include a crushing step for obtaining particles.

  The following <dispersion method 1> to <dispersion method 3> can be applied to the step of dispersing the hydrophobized particles (p2).

<Dispersion method 1>
A method in which hydrophobic particles (p2) and an organic solvent (s1) having a relative dielectric constant of 5 to 50 are simultaneously placed in a dispersion container and uniformly dispersed.
<Dispersion method 2>
A method of uniformly dispersing by adding an organic solvent (s1) having a relative dielectric constant of 5 to 50 to a dispersion container in which hydrophobic particles (p2) are previously contained.
<Dispersion method 3>
A method in which hydrophobic particles (p2) are added and dispersed uniformly in a dispersion container containing an organic solvent (s1) having a relative dielectric constant of 5 to 50 in advance.

  Among these, <dispersion method 1> and <dispersion method 3> are preferable, and <dispersion method 3> is more preferable from the viewpoint that poor dispersion hardly occurs and the surface activity tends to be good.

In the dispersion process of the hydrophobized particles (p2), a known disperser (feather stirrer, high-speed rotary homomixer, high-pressure homogenizer, dissolver, ball mill, kneader, sand mill, triple roll, ultrasonic disperser, planetary mixer A disperser (such as a planetary mixer) or a three-axis planetary mixer) can be used.
Among these dispersers, a feather stirrer, a high-speed rotation homomixer, a high-pressure homogenizer, and a dissolver are preferable from the viewpoint of good dispersibility and good surface activity, and more preferably a high-speed rotation homomixer and a high-pressure homogenizer. And a dissolver, particularly preferably a high-speed rotary homomixer.

  As the organic solvent (s1) having a relative dielectric constant of 5 to 50 {the numerical values in parentheses below represent the relative dielectric constant}, nonpolar solvents {such as ethyl acetate (6) and methylene chloride (9)}, Protic polar solvents {acetic acid (6.2), 1-butanol (18), 2-propanol (18), 1-propanol (20), ethanol (24), methanol (33), etc.}} and aprotic polar solvents {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 because the reaggregation of the dispersed particles in the pulverization step is small and the surface activity is good. Preferably a protic solvent having a relative dielectric constant of 5-50, 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).

  The proportion (% by weight) of the dispersed hydrophobic particles (p2) is preferably 1 to 30, more preferably 3 to 25 based on the total weight of the hydrophobic particles (p2) and the organic solvent (s1). Preferably it is 5-20. Within this range, the viscosity of the dispersion is low and the dispersion is further facilitated, and crushing in the crushing process, which is the next process, proceeds well, and the surface activity 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. Within this range, the surface activity is further improved.

In the crushing process, a known crusher or the like can be used, and a wet medium type crusher {bead mill, sand grinder, colloid mill, attritor (manufactured by Nippon Coke Industries, "Attritor" is a registered trademark of Nippon Coke Industries, Ltd. ), DISPERMAT (VMA-GETAMANN GMBH), etc.}, wet jet mill {Nanomizer (manufactured by Yoshida Kikai Co., Ltd., “Nanomizer” is a registered trademark of SG Engineering Co., Ltd.), Starburst Co., Ltd. Sugino Machine, “Starburst” is a registered trademark of Sugino Machine Co., Ltd.), Gorin homogenizer (manufactured by APV), etc.}.
Among these, the wet medium type pulverizer is preferable in that reaggregation of the amphiphilic particles hardly occurs and the surface activity is further improved.

  In the method for producing amphiphilic particles of the present invention, 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, use a method of filtering and classifying the amphiphilic particle dispersion through a wire mesh, a method of allowing the amphiphilic particle dispersion to stand and settling large particles, and a difference in sedimentation speed due to the difference in particle diameter. The sedimentation rate method etc.

<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 amphiphilic particles of the present invention, a solvent removal step and a dispersion medium concentration step may be provided after the pulverization step. The solvent removal step and the dispersion medium concentration step can be performed by a known method such as a method of 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 amphiphilic particles of the present invention, 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 following <Usage Form 1> to <Usage Form 3> can be applied to the form of use of the amphiphilic particles of the present invention.
<Usage form 1>
A form in which the dispersion containing the amphiphilic particles obtained in the crushing step is used as it is without removing the dispersion medium.
<Usage form 2>
A form using amphiphilic particles obtained by removing the dispersion medium from the dispersion containing the amphiphilic particles obtained in the crushing step and drying.
<Usage form 3>
A form in which a dispersion containing amphiphilic particles obtained in the crushing step is concentrated to a predetermined concentration before use.

  In <Use Form 2>, the amphiphilic particles obtained by removing the dispersion medium and drying can be crushed and / or classified. The crushing performed here is to return the tertiary aggregate obtained by reaggregating the amphiphilic particles to the secondary aggregated particles, and crushing the hydrophobic particles (hydrophobized secondary aggregates). Different. The crushing can be performed by a known method. Using a jaw crusher, a hammer mill, a roller mill, an impact pulverizer, a jet pulverizer, or the like, the rotation speed and pressure of the pulverizer are appropriately adjusted so that the crushing does not occur. It is done with adjustment.

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

The volume average particle diameter of the hydrophilic fine particles (p101 to p115) used in Examples and Comparative Examples 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”.

The M value of the hydrophobized particles (p201 to p215, hp1 and hp2) obtained in Examples and Comparative Examples was measured by the following method.
<Measurement of M value>
0.2 g of the secondary aggregate obtained in Examples and Comparative Examples was added to 50 mL of ion-exchanged water in a beaker having a capacity of 250 mL. 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 total amount of secondary aggregates was suspended in ion exchange water. The drop amount (g) of methanol at the time when the total amount of the 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

<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., 3 L capacity, the same applies hereinafter) and while stirring at low speed (750 rpm), the lipophilic compound (a1) {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 hydrophobized particles (p201). The M value of the hydrophobized particles (p201) was 35.

  3 parts of hydrophobized particles (p201) and 97 parts of methanol (manufactured by Kanto Chemical Co., Inc., reagent grade 1, the same shall apply hereinafter) equipped with impeller blades (manufactured by High Flex Disperser HG-92G Taitec Co., Ltd.) The mixture was stirred at 4,000 rpm at 25 ± 3 ° C. for 15 minutes to obtain a dispersion (b1).

  Dispersion (b1) 300 ml of wet medium type grinder {DISPERMAT SL-C-12 (manufactured by VMA-GETAMANN GMPH, the same applies below) filled with 100 ml of zirconia beads having a particle size of 0.7 mm at a rotor speed of 4000 rpm. The dispersion (c1) of amphiphilic particles (j1) was obtained by crushing for 60 minutes.

  Subsequently, the dispersion liquid (c1) 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 (j1) of this invention.

<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 being (750 rpm), 5 parts of lipophilic compound (a2) {polydimethylsiloxane having a kinematic viscosity of 20 mm ² / s at 25 ° C. (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 hydrophobized particles (p202). The M value of the hydrophobized particles (p202) was 50.

  Next, “3 parts of“ hydrophobized particles (p201) ”were changed to“ 5 parts of hydrophobized particles (p202) ”,“ 97 parts of methanol ”was changed to“ ethanol (manufactured by Kanto Chemical Co., Ltd., reagent grade 1, etc.). The mixture was stirred in the same manner as in Example 1 except that it was changed to “95 parts” to obtain a dispersion (b2).

  Next, “dispersion (b1)” was changed to “dispersion (b2)”, “zirconia beads having a particle size of 0.7 mm” was changed to “zirconia beads having a particle size of 1 mm”, and “60 minutes”. Except for changing to “40 minutes”, the mixture was crushed in the same manner as in Example 1 and dried to obtain a dispersion (c2) of amphiphilic particles (j2) and the amphiphilic particles (j2) of the present invention. Obtained.

<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). )} ”And“ lipophilic compound (a2) 50 parts ”as“ lipophilic compound (a3) {polydimethylsiloxane having a kinematic viscosity of 10 mm ² / s at 25 ° C. (manufactured by Shin-Etsu Chemical Co., Ltd., product) Hydrophobized particles (p203) were obtained in the same manner as in Example 2 except that the name was changed to “KF-96-50cs)} 75 parts”. The M value of the hydrophobized particles (p203) was 85.

  Subsequently, the same as Example 1 except that “3 parts of hydrophobized particles (p201)” were changed to “25 parts of hydrophobized particles (p203)” and “97 parts of methanol” were changed to “75 parts of methanol”. To obtain a dispersion (b3).

  Subsequently, the dispersion (c3) of amphiphilic particles (j3) was dried after crushing in the same manner as in Example 1 except that “dispersion (b1)” was changed to “dispersion (b3)”. And the amphiphilic particles (j3) of the present invention were obtained.

<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 (a2) 50 parts" to "lipophilic compound (a4) {polydimethylsiloxane having a kinematic viscosity of 50 mm ² / s at 25 ° C (trade name: KF, manufactured by Shin-Etsu Chemical Co., Ltd.) Hydrophobized particles (p204) were obtained in the same manner as in Example 2, except that the change was changed to "-96-50cs)} 10 parts". The M value of the hydrophobized particles (p204) was 65.

  Next, “3 parts of hydrophobized particles (p201)” were changed to “10 parts of hydrophobized particles (p204)”, and “97 parts of methanol” was changed to “2-propanol (Kanto Chemical Co., Ltd., reagent grade, the same applies hereinafter). A dispersion (b4) was obtained by stirring in the same manner as in Example 1 except that the amount was changed to “90 parts”.

  Next, Example 1 was changed except that “dispersion (b1)” was changed to “dispersion (b4)” and “zirconia beads having a particle diameter of 0.7 mm” were changed to “zirconia beads having a particle diameter of 1 mm”. After crushing similarly, it dried and obtained the dispersion liquid (c4) of the amphiphilic particle (j4) and the amphiphilic particle (j4) of the present invention.

<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 (a5) {modified amide 1 part of wax (by Big Chemie Japan Co., Ltd., trade name CERAFLOUR960, volume average particle size 4 μm)} is placed in 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, and after heat treatment at 100 ° C. for 1 hour, the mixture was cooled to room temperature over 2 hours under high-speed stirring, and the hydrophobized particles (p205) were removed. Obtained. The M value of the hydrophobized particles (p205) was 35.

  Next, “3 parts of hydrophobized particles (p201)” were changed to “1 part of hydrophobized particles (p205)”, and “97 parts of methanol” was changed to “99 parts of ethyl acetate (Kanto Chemical Co., Ltd., reagent grade 1)”. A dispersion (b5) was obtained by stirring in the same manner as in Example 1 except that the change was made.

  Next, “dispersion (b1)” was changed to “dispersion (b5)”, “zirconia beads having a particle diameter of 0.7 mm” was changed to “glass beads having a particle diameter of 3 mm”, and “60 minutes”. Except that it was changed to “20 minutes”, it was crushed in the same manner as in Example 1 and then dried to give a dispersion (c5) of amphiphilic particles (j5) and the amphiphilic particles (j5) of the present invention. Obtained.

<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 the hydrophobized particles (p206) were obtained in the same manner as in Example 2 except that“ 5 parts of lipophilic compound (a2) ”was changed to“ 2 parts of lipophilic compound (a2) ”. Obtained. The M value of the hydrophobized particles (p206) was 45.

  Subsequently, stirring was performed in the same manner as in Example 1 except that “3 parts of hydrophobized particles (p201)” was changed to “3 parts of hydrophobized particles (p206)” to obtain a dispersion (b6).

  Then, after changing the “dispersion (b1)” to “dispersion (b6)” and changing “60 minutes” to “40 minutes”, crushing treatment was performed in the same manner as in Example 1, and then drying, A methanol dispersion (c6) of the amphiphilic particles (j6) and the amphiphilic particles (j6) of the present invention were obtained.

<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 (a6) {polydimethylsiloxane having a kinematic viscosity of 100 mm ² / s at 25 ° C. (trade name: KF-96-100cs, manufactured by Shin-Etsu Chemical Co., Ltd.)} in methanol 50 Next, the Henschel mixer was spun 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 heat-dried at 100 ° C. for 2 hours. The hydrophobized particles (p207) were obtained, and the M value of the hydrophobized particles (p203) was 70. .

  Subsequently, Example 1 except that “3 parts of hydrophobized particles (p201)” was changed to “15 parts of hydrophobized particles (p207)” and “97 parts of methanol” was changed to “85 parts of 2-propanol”. And a dispersion (b7) was obtained.

  Subsequently, Example 1 was changed except that “dispersion (b1)” was changed to “dispersion (b7)” and “zirconia beads having a particle diameter of 0.7 mm” was changed to “zirconia beads having a particle diameter of 1 mm”. After crushing similarly, it was dried to obtain a dispersion (c7) of amphiphilic particles (j7) and the amphiphilic particles (j7) of the present invention.

<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)} Hydrophobized particles (p208) were obtained in the same manner as in Example 7, except that “30 parts of lipophilic compound (a6)” was changed to “50 parts of lipophilic compound (a6)”. . The M value of the hydrophobized particles (p208) was 85.

  Subsequently, the same as Example 1 except that “3 parts of hydrophobized particles (p201)” were changed to “20 parts of hydrophobized particles (p208)” and “97 parts of methanol” were changed to “80 parts of ethanol”. To obtain a dispersion (b8).

  Next, "dispersion (b1)" was changed to "dispersion (b8)", "zirconia beads with a particle size of 0.7 mm" was changed to "zirconia beads with a particle size of 1 mm", and "60 minutes" Except that it was changed to “20 minutes”, it was crushed in the same manner as in Example 1 and then dried to obtain a dispersion (c8) of amphiphilic particles (j8) and the amphiphilic particles (j8) of the present invention. Got.

<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 (a6) 30 parts” to “lipophilic compound (a7) polydimethylsiloxane having a kinematic viscosity of 3000 mm ² / s at 25 ° C. (trade name KF-96- manufactured by Shin-Etsu Chemical Co., Ltd.) Except for the change to “3000 cs)} 2 parts”, hydrophobized particles (p209) were obtained in the same manner as in Example 7. The M value of the hydrophobized particles (p209) was 80.

  Next, “3 parts of hydrophobized particles (p201)” were changed to “25 parts of hydrophobized particles (p208)”, and “97 parts of methanol” was changed to “tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd., reagent grade 1, etc.). The mixture was stirred in the same manner as in Example 1 except that it was changed to “75 parts” to obtain a dispersion (b9).

  Next, “dispersion (b1)” was changed to “dispersion (b9)”, “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 Example 1 and dried to obtain a dispersion (c9) of amphiphilic particles (j9) and the amphiphilic particles (j9) of the present invention. Obtained.

<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 (a5) 1 part ”is changed to“ hydrophobic fine particles (a8) {modified polyethylene wax (trade name CERAFLOUR 961, volume average particle diameter 5 μm) manufactured by BYK Japan KK ”} 70 Hydrophobized particles (p210) were obtained in the same manner as in Example 5 except that the “parts” were changed. The M value of the hydrophobized particles (p210) was 85.

  Subsequently, the same as Example 1 except that “3 parts of hydrophobized particles (p201)” were changed to “30 parts of hydrophobized particles (p210)” and “97 parts of methanol” were changed to “70 parts of tetrahydrofuran”. To obtain a dispersion (b10).

  Next, “dispersion (b1)” was changed to “dispersion (b10)”, “zirconia beads having a particle diameter of 0.7 mm” was changed to “glass beads having a particle diameter of 3 mm”, and “60 minutes”. Except for changing to “20 minutes”, after crushing in the same manner as in Example 1, it was dried to obtain a dispersion (c10) of amphiphilic particles (j10) and the amphiphilic particles (j10) of the present invention. Obtained.

<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 in the same manner as in Example 5, except that the“ hydrophobic fine particles (a5) 1 part ”was changed to“ hydrophobic fine particles (a8) 10 parts ”. Obtained. The M value of the hydrophobized particles (p211) was 65.

  Subsequently, the same as Example 1 except that “3 parts of hydrophobized particles (p201)” were changed to “20 parts of hydrophobized particles (p211)” and “97 parts of methanol” were changed to “80 parts of ethanol”. To obtain a dispersion (b11).

  Next, “dispersion (b1)” was changed to “dispersion (b11)”, “zirconia beads having a particle diameter of 1 mm” was changed to “glass beads having a particle diameter of 1 mm”, and “60 minutes” was changed to “20”. Except for changing to “minute”, after crushing in the same manner as in Example 1, it was dried to obtain a dispersion (c11) of amphiphilic particles (j11) and the amphiphilic particles (j11) of the present invention. .

<Example 12>
Hydrophobized particles (p212) were obtained in the same manner as in Example 5, except that “1 part of hydrophobic particles (a5)” was changed to “65 parts of hydrophobic particles (a5)”. The M value of the hydrophobized particles (p212) was 75.

  Subsequently, the same as Example 1 except that “3 parts of hydrophobized particles (p201)” were changed to “25 parts of hydrophobized particles (p212)” and “97 parts of methanol” were changed to “75 parts of tetrahydrofuran”. To obtain a dispersion liquid (b12).

  Next, “dispersion (b1)” was changed to “dispersion (b12)”, “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 Example 1 and then dried to obtain a dispersion (c12) of amphiphilic particles (j12) and the amphiphilic particles (j12) of the present invention. .

<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 hydrophobized particles (p213) were obtained in the same manner as in Example 2, except that" 5 parts of lipophilic compound (a2) "was changed to" 80 parts of lipophilic compound (a3) ". It was. The M value of the hydrophobized particles (p213) was 70.

  Subsequently, the same as Example 1 except that “3 parts of hydrophobized particles (p201)” were changed to “25 parts of hydrophobized particles (p213)” and “97 parts of methanol” were changed to “75 parts of methanol”. To obtain a dispersion (b13).

  Next, the dispersion (c13) of amphiphilic particles (j13) was dried after crushing in the same manner as in Example 1 except that “dispersion (b1)” was changed to “dispersion (b13)”. And the amphiphilic particles (j13) of the present invention were obtained.

<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 )} ”, And in the same manner as in Example 2, except that the“ lipophilic compound (a2) 5 parts ”was changed to“ lipophilic compound (a3) 2 parts ”. Obtained. The M value of the hydrophobized particles (p214) was 30.

  Next, Example 1 except that “3 parts of hydrophobized particles (p201)” was changed to “10 parts of hydrophobized particles (p214)” and “97 parts of methanol” was changed to “90 parts of 2-propanol”. And a dispersion (b14) was obtained.

  Next, the dispersion liquid (c14) of amphiphilic particles (j14) was dried after crushing in the same manner as in Example 1 except that the “dispersion liquid (b1)” was changed to “dispersion liquid (b14)”. And the amphiphilic particles (j14) of the present invention were obtained.

<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 a low speed (750 rpm), the lipophilic compound (a9) {alkoxy-modified polydimethylsiloxane having a kinematic viscosity of 80 mm ² / s at 25 ° C (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 hydrophobized particles (p215). The M value of the hydrophobized particles (p215) was 30.

  Subsequently, stirring was performed in the same manner as in Example 1 except that “3 parts of hydrophobized particles (p201)” was changed to “3 parts of hydrophobized particles (p215)” to obtain a dispersion (b15).

  Next, the dispersion (c15) of amphiphilic particles (j15) was dried after crushing in the same manner as in Example 1 except that “dispersion (b1)” was changed to “dispersion (b15)”. And the amphiphilic particles (j15) of the present invention were obtained.

<Comparative Example 1>
100 parts of the hydrophilic fine particles (p111) were put in a Henschel mixer with a heater, and 5 parts of the lipophilic compound (a2) 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).

<Comparative Example 2>
Hydrophilic fine particles (p115) {quartz particles (manufactured by Tatsumori Co., Ltd., trade name: Crystallite A-1, average particle size 12 μm)} and lipophilic compound (a10) {1-hexadecyl alcohol (Kanto Chemical Co., Inc.) Manufactured, reagent grade 1)} A solution obtained by dissolving 0.1 part in 500 parts of n-hexane is placed in a polyethylene pot containing four alumina balls (10 mmφ) as a grinding medium and rotated for 6 hours in a ball mill. Quartz particles were ground to obtain an n-hexane dispersion (hc1) of particles (hp2). Subsequently, the dispersion liquid (hc1) was dried in the same manner as in Example 1 to obtain comparative particles (hp2).

  For the amphiphilic particles (j1 to j15) obtained in Examples 1 to 15 and the particles (hp1 and hp2) obtained in Comparative Examples 1 and 2, the volume average particle size is measured by laser diffraction / scattering particle size distribution. Table 1 shows the results of measurement using an apparatus (Partica LA-950, manufactured by Horiba, Ltd.). For the amphiphilic particles (j1 to j15, hp2), the volume average particle diameter of the amphiphilic particles or particles contained in the dispersion (c1 to c15, hc1) is measured, and for the particles (hp1), the particles The volume average particle diameter of particles contained in a dispersion obtained by dispersing 1 part in 99 parts of 2-propanol using an ultrasonic disperser was measured.

1% of the amphiphilic particles (j1 to j15) obtained in Examples 1 to 15 were obtained by dispersing 1 part 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.

1% dispersion obtained by dispersing 1 part of particles (hp1, hp2) obtained in Comparative Examples 1 and 2 in 99 parts of 2-propanol using an ultrasonic disperser for 1 minute at an output of 70%. the 02G, 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, 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.

  The surface activity of the amphiphilic particles (j1 to j15) obtained in Examples 1 to 15 and the particles (jp1 and jp2) obtained in Comparative Examples 1 and 2 were evaluated by the following emulsification tests. These results are shown in Table 2.

<Emulsification test>
8 parts of a measurement sample (amphiphilic particles or particles) was placed in isoparaffin (Nippon Oil Corporation, trade name: Pearl Ream EX), and dispersed for 1 minute at an output of 70% using an ultrasonic disperser. The obtained dispersion (40 cm ³⁾ and ion-exchanged water (40 cm ³⁾ were put into a glass container having an inner diameter of 41 mm and a capacity of 170 ml, and emulsified by shaking for 30 minutes with a paint shaker. The emulsion was allowed to stand in a room at 25 ± 3 ° C. for 24 hours, the separated state of the water layer and the oil layer was visually observed, and the thickness of the separated layer was measured. The thinner the separated layer, the better the emulsifiability and the higher the surface activity. Further, when separation of the aqueous layer is observed, it means that the emulsification is insufficient and the surface activity is insufficient.

  The emulsion using the amphiphilic particles (j1 to j15) of the present invention is superior in emulsifiability and has high surface activity compared to the emulsion using the particles (jp1, jp2) of the comparative examples. Was confirmed.

  Since the amphiphilic particles of the present invention are excellent in surface activity, they are suitable as particle stabilizers such as emulsion polymerization and suspension polymerization. The amphiphilic particles of the present invention can be dispersed in a hydrophilic solvent or a hydrophobic solvent, and particles incompatible with the solvent can be dispersed and emulsified therein. Hydrophilic solvents include water, lower alcohols, ketones and ethers, and hydrophobic solvents include hydrocarbons, silicones, and paraffins. Dispersions and emulsions to which the amphiphilic particles of the present invention are applied can be used in paints, cosmetics, pharmaceuticals, and the like.

Claims (7)

Secondary agglomerated particles composed of hydrophilic fine particles composed of silica and / or alumina and hydrophobic fine particles,
An amphiphilic particle, wherein the surface of the secondary agglomerated particle is divided into a hydrophilic surface and a hydrophobic surface. The amphiphilic particles according to claim 1, wherein the volume average particle diameter is 0.1 to 10 μm. The amphiphilic particles according to claim 1 or 2, which are obtained by hydrophobizing a secondary aggregate (p1) composed of hydrophilic fine particles having a primary particle diameter of 1 to 80 nm and then crushing. The amphiphilic particles according to claim 3, wherein the secondary aggregate (p1) has a volume average particle diameter of 1 to 100 µm. A method for producing the amphiphilic particles according to any one of claims 1 to 4,
Hydrophobizing step of obtaining hydrophobized particles (p2) by subjecting secondary aggregates (p1) of hydrophilic microparticles having a primary particle size of 1 to 80 nm to surface treatment with lipophilic compounds or hydrophobic microparticles;
A dispersion step of dispersing the hydrophobic particles (p2) in an organic solvent (s1) having a relative dielectric constant of 5 to 50 to obtain a dispersion of the hydrophobic particles (p2); and the hydrophobic particles (p2) in the dispersion A method for producing amphiphilic particles, comprising a crushing step of crushing the volume average particle diameter of the particles to 0.1 to 10 μm to obtain amphiphilic particles. The production method according to claim 5, wherein the lipophilic compound is a silicone compound. The production method according to claim 5, wherein the hydrophobic fine particles are hydrophobic organic fine particles.