TWI637031B - Method of preparing coated inorganic particles - Google Patents

Abstract

The present invention provides a method of coating a surface of an inorganic particle with a polyoxygen compound, which is capable of easily producing a more uniform coating, and even using a polyoxygen compound having a Si-H group such as methylhydrogenpolysiloxane or the like. There is also a small amount of Si-H group residue in the coating, which can reduce the amount of hydrogen generated.

The method of the present invention is a method of mixing a liquid and inorganic particle slurry containing a polyoxo compound modified by adding a base with a wet pulverizer or a wet mixer, or mixing a cerium containing an alkali added by a dry pulverizer or a dry mixer. The liquid of the oxygen compound is mixed with the inorganic particle powder, and the surface of the inorganic particle is coated with the polyoxynium compound. As the polyoxymethane compound, dimethyl polyoxyalkylene, methyl hydrogen polyoxyalkylene or the like is used. As the inorganic particles, fine particles of titanium oxide, fine particles of zinc oxide, titanium oxide, and zinc oxide are most suitable.

Description

Method for producing coated inorganic particles

The present invention relates to a method of producing coated inorganic particles.

When the surface of the inorganic particles is coated with an organic compound, the dispersibility, storage stability, and suitability of the inorganic particles can be improved, and the function of the powder, such as adhesion to the skin (adhesion) and touch (using), can be rapidly improved. Sense), gloss, concealing power, tinting strength, transparency, shielding energy of ultraviolet or infrared rays, conductivity, fluorescence, luminescence, catalyst activity, hydrophobicity or hydrophilicity. Therefore, the inorganic particles coated with the organic compound have been widely used in various fields such as cosmetic materials, plastic additives, inks, paints, carbon powders (magnetic powders, external additives), chemical fibers, packaging materials, and electronic materials.

For example, Patent Document 1 discloses a method for producing an organic compound-coated inorganic particle by using a kneading machine to dimeticone (dimethyl polysiloxane) and polydimethyl siloxane/polymethyl. A mixture of a base oxyalkylene copolymer (methylhydrogenpolyoxy-dimethylpolyoxyl copolymer) is mixed in the powder, and the mixture is coated on the surface of the powder. And special Patent Document 2 discloses premixing of inorganic particle powder and surface modifier, followed by treatment with a device having a high-speed shearing action. The surface modifier is preferably used to hydrophobize the surface of the particles of the inorganic particles, specifically, an organic ruthenium compound such as a fluoroalkyl decane, an alkoxy decane, a decane coupling agent or an organic polysiloxane, and Devices having a high-speed shearing action include, for example, a high-speed shearing mill, a blade-type kneading machine, a planetary grinder, and the like.

On the other hand, Patent Document 3 discloses a denatured surface modifier in which a hydrogen atom of a Si-H bond in a molecular chain of a methylhydrogenpolysiloxane is substituted with an alkoxy group. After the surface to be subjected to surface modification is contained as necessary, the denatured surface modifier is added and stirred, followed by drying, whereby a surface-modified powder is obtained. Further, the denatured surface modifying agent is produced by adding methyl hydrogen polyoxyalkylene to a sodium hydroxide solution dissolved in methanol and reacting it.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] JP-A-2007-56082

[Patent Document 2] JP-A-2008-143725

[Patent Document 3] JP-A-2009-138084

According to the methods of Patent Documents 1 and 2, the powder must be strongly pulverized in advance. Moreover, even if the pulverized inorganic particles are still agglomerated powder status. For this reason, even if the polyoxynitride compound is coated, the coating is likely to be uneven. On the other hand, the method of Patent Document 3 uses a denaturing surface modifier which replaces a hydrogen atom of a Si-H bond in a molecular chain of a methylhydropolysiloxane by an alkoxy group in advance, so that the Si-H group is used. Less residue, followed by a decrease in hydrogen production. However, the manufacturing cost or processing cost of the denatured surface treatment agent is required to be reduced.

Therefore, the present inventors have found that in the method of coating the surface of the inorganic particles with the polyoxygenated compound, by using the alkali-modified polyoxo compound, a more uniform coating can be easily produced, and even if methyl hydrogen is used, a polyoxonium compound having a Si-H group such as polyoxymethane or a dimethicone/polymethylaluminoxane copolymer, which may be further coated by alkali modification. The Si-H group has less residue and can reduce the amount of hydrogen gas generated. Further, in addition to the coating of the polyoxyxide compound, the coating of the inorganic compound or the coating of the fatty acid compound can be carried out, and the present invention has been completed.

That is, the present invention is a method for producing coated inorganic particles as follows: (1) A method for producing coated inorganic particles, comprising mixing a liquid containing a base-added polyoxonium compound with inorganic particles (powder or slurry) And a step of coating the surface of the inorganic particles with a polyoxonium compound derived from a polyoxynitride compound to which a base is added, and (2) a method for producing a coated inorganic particle comprising a liquid and an inorganic substance containing a polyoxo compound to which a base is added Compound and inorganic particles (powder or slurry) are mixed, and the mixture is derived from the addition of alkali a step of coating a surface of an inorganic particle with a polyoxonium compound and an inorganic compound, and (3) a method for producing a coated inorganic particle, comprising: a liquid containing a base-added polysiloxane and a fatty acid compound and inorganic particles (powder) a method of coating a surface of an inorganic particle with a polyoxonium compound and a fatty acid compound derived from a polyoxonium compound to which a base is added, and (4) a method for producing a coated inorganic particle, which comprises containing an alkali added The liquid of the polyoxo compound is mixed with the fatty acid compound and the inorganic compound and the inorganic particles (powder or slurry), and the surface of the inorganic particle is coated with the polyoxonium compound derived from the alkali-added polyoxynitride compound and the fatty acid compound and the inorganic compound. Step (5) A method for producing coated inorganic particles, comprising mixing inorganic particles (powder or slurry) with an inorganic compound, and coating the surface of the inorganic particles with an inorganic compound, and then, the inorganic particles (powder or slurry) ) mixed with a liquid containing a base-added polyoxo compound, and added with an inorganic compound a step of coating a surface of an inorganic particle with a polyoxygen compound of a polyoxygen compound, and (6) a method for producing a coated inorganic particle, comprising mixing an inorganic particle (powder or slurry) with an inorganic compound and coating the inorganic compound with an inorganic compound a surface of the particles, followed by mixing the inorganic particles (powder or slurry) with a liquid and a fatty acid compound containing a base-added polyoxo compound, and an inorganic compound and a polyoxonium derived from a base-added polyoxonium compound The step of coating the surface of the inorganic particles with the compound and the fatty acid compound.

According to the method for producing coated inorganic particles of the present invention, By mixing the liquid and the inorganic particles containing the alkali-added polyoxo compound, the polyfluorene oxide compound can easily treat the surface of the inorganic particles, and a more uniform coating can be easily produced. Further, even if a polyoxonium compound having a Si-H group such as methylhydrogenpolysiloxane or polydimethyloxane/polymethylaluminoxane copolymer is used, it can be reduced by alkali modification. The Si-H group remaining on the coating can reduce the amount of hydrogen generated.

Further, the method for producing the coated inorganic particles of the present invention may be coated with an inorganic compound or coated with a fatty acid compound in addition to the coating of the polyoxyxene compound.

Further, in the method of using the inorganic particle slurry of the present invention, after the inorganic particles are wet-formed, the coating of the polyoxyxide compound, the coating of the inorganic compound, or the coating of the fatty acid compound may be carried out without drying. Therefore, it is possible to further reduce the processing cost by reducing the drying energy after wet manufacturing.

The coated inorganic particles produced in this manner are excellent in hydrophobicity (lipophilicity) because of the excellent coating uniformity of the polyoxygenated compound modified by alkali, and when a polyfluorene oxide compound having a Si—H group is used, it is changed by alkali. The decrease in the residual Si-H group is accompanied by a decrease in hydrogen gas generation.

The present invention is a method for producing coated inorganic particles by coating a polyoxyxene compound on at least a part of the surface of the inorganic particles.

Various substances can be used for the inorganic particles. For example, body pigments can be cited as mica, sericite, talc, clay, kaolin, synthetic mica. , calcium carbonate, magnesium carbonate, magnesium citrate, aluminum citrate, calcium phosphate, anhydrous citric acid, aluminum oxide, magnesium oxide, zirconium oxide, aluminum hydroxide, barium sulfate, magnesium aluminate silicate, magnesium metasilicate aluminate , boron nitride, zeolite, hydroxyapatite, ceramic powder, and the like. Further, the white pigment may, for example, be basic lead carbonate, basic lead sulfate, titanium oxide, zinc oxide, cerium oxide, zinc phosphate or aluminum phosphate. The coloring pigments may be listed as iron oxide (Bengala), yellow iron oxide, black iron oxide, cobalt oxide, chromium oxide, chromium hydroxide, dark blue dye, ultramarine blue dye, carbon black, oxygen-deficient titanium oxide (low-order titanium oxide), mango Purple, cuprous oxide, black lead, yellow lead, cadmium yellow, cadmium red, cobalt blue, molybdenum orange, etc. The fluorescent pigment may, for example, be zinc sulfide, zinc antimonate, zinc cadmium sulfate, calcium sulfide, barium sulfide or calcium tungstate. The pearl pigment may, for example, be cerium oxychloride, mica titanium, fish scale foil or the like. Examples of the fine particle powder include fine particle titanium oxide, fine particle zinc oxide, fine particle iron oxide, and fine particle cerium oxide. The metallic luster pigments may be exemplified by aluminum powder, zinc powder, gold powder, silver powder, tin powder, stainless steel powder, diamond powder, copper powder, nickel powder, bronze powder, and the like. The fluorescent pigment may, for example, be zinc sulfide or calcium tungstate. Other powders may be exemplified by tin oxide, ATO (tin oxide doped with antimony), ITO (indium oxide doped with tin), zinc oxide doped with aluminum, and the like.

Among these, fine particle titanium oxide, fine particle zinc oxide, titanium oxide, zinc oxide, etc. are preferable, and fine particle titanium oxide and fine particle zinc oxide are used for an ultraviolet shielding agent, and titanium dioxide and zinc oxide are used for a white pigment or various fillers.

Further, those in which the inorganic particles are composited or coated with an inorganic compound may be used as needed. For example, an oxide or aqueous oxidation of at least one of aluminum, calcium, magnesium, strontium, barium, zirconium, titanium, zinc, iron, cobalt, manganese, nickel, and tin The particles are coated with a fine particle powder such as fine particle titanium oxide, fine particle zinc oxide, fine particle iron oxide or fine particle cerium oxide, and a powder of an inorganic coloring pigment such as iron oxide is coated with anhydrous citric acid, and a powder of a body pigment is coated with a fine particle white pigment.

The inorganic particles may be used in the form of a powder (including a wet state containing a certain degree of moisture), or may be used in the form of a slurry (suspension), but it is preferably used in the form of a slurry.

When it is used in a powder state, it is preferably pulverized in advance by a usual pulverizer, and for example, a dry pulverizer, a crusher, or the like can be used. The dry pulverizer is exemplified by, for example, a ball mill, a bead mill, a colloid mill, a conical mill, a disc mill, an edge mill, a pulverizing mill, a hammer mill, a mortar, Particle Grinder, Vertical Axis Impact (VSI) Grinder, Willy Grinder, Roll Grinder, Jet Mill, Cross Jet Grinder, Air Flow Ultrafine Particle Crusher (Ceren Miller), High Pressure Crushing Roller, Henschel Blending Machine , planetary kneading machine, spiral kneading machine (Nautamixer) and so on. Moreover, the crusher is exemplified as a jaw crusher, a bucket crusher, a Gyratory crushers, a cone crusher, a single roll mill, and a double. Roller, impact mill, etc.

The size of the inorganic particles is preferably adjusted in the range of 0.01 to 10 μm, more preferably in the range of 0.01 to 4.0 μm, by the particle diameter D50.

In the present specification, the particle diameter D50 is a cumulative 50% particle diameter (median diameter), and is measured using a laser diffraction/scattering particle size distribution measuring apparatus (LA-950, manufactured by Horiba, Ltd.).

When it is used in a slurry state, the solvent preferably contains water as a main component, and more preferably water contains about 80% by mass or more. Alcohols such as ethanol, methanol, and isopropyl alcohol may be contained, and sodium hydroxide, potassium hydroxide, calcium hydroxide, hydrochloric acid, sulfuric acid, and the like may be contained as components other than water.

The pH of the inorganic particle slurry can be appropriately set by adding a base or an acid.

A conventional method can be used for preparing the inorganic particle slurry. For example, a kneading machine kneading, a Henschel kneading machine kneading, a roll kneading, an extruder kneading, and the like, a kneading mixer, a paddle kneading machine, a high speed kneading machine, a dissolving machine, a homogenizer, a wet micronizing machine, and a wet spraying can be used. A wet mixing disperser such as a grinder, a colloid mill, a particle mill, a bead mill, a sand mill, a ball mill, a sand grinder, an in-line grinder, or a medium-free high-speed stirring disperser to disperse inorganic particles in a solvent in.

The size of the inorganic particles in the slurry is preferably adjusted in the range of 0.01 to 4.0 μm, more preferably in the range of 0.01 to 0.2 μm, as indicated by the particle diameter D50.

As the inorganic particle slurry, it is preferred to use a slurry in which the inorganic particles are wet-formed, or to wash the slurry separately as needed, and then to re-disperse the slurry without drying. Specifically, it is preferred to use a solution of a fine particle such as titanium oxide, fine particle zinc oxide, fine particle iron oxide or fine particle cerium oxide as a solution of a sulfate, a nitrate, a carbonate or a chloride such as titanium, zinc, iron or bismuth. Hydrolysis or neutralization is carried out to produce a slurry of oxides, hydroxides or hydroxides of the respective metals, and it is preferred to wash the slurry as needed, and then to disperse the slurry in the solvent without drying.

Next, the polyoxonium compound coating treatment of the inorganic particles (powder or slurry) will be described in detail.

Preparing a liquid containing a polyoxosiloxane

The method of the present invention modulates a liquid in which a base is previously added to a polyoxo compound.

When a base is added, the polyoxynitride is modified to be easily coated on the surface of the inorganic particles. For example, when the polyfluorene oxide compound has a Si-H group, the base is a Si-OH group or a Si-OA group (only A represents an alkali metal or an alkaline earth metal), and is reacted with an OH group located on the surface of the inorganic particles to be coated. Polyoxane.

Any base may be used. For example, an alkali metal compound such as sodium hydroxide, sodium carbonate, potassium hydroxide or potassium carbonate, an alkaline earth metal compound such as calcium hydroxide, an ammonium compound such as ammonium hydroxide or ammonium carbonate, or the like can be used. The amount of the base to be added may be such a degree that the polyoxonium compound can be modified, and specifically, it is preferably 0.5 to 20% by mass, more preferably 0.5 to 5% by mass, even more preferably the amount of the polyoxonium compound. 0.5 to 2% by mass. The polyoxymethylene compound may be in a solid state such as a colloid or the like, and may be dissolved in a solvent as needed. As the solvent, an alcohol such as ethanol, methanol or isopropyl alcohol, an organic solvent such as an ether, an aqueous solvent or a mixed solvent thereof can be used, and an organic solvent such as an alcohol which can dissolve a polyoxo compound is more preferable. The liquid containing the alkali-added polyoxo compound may be prepared by diluting the polyoxo compound with a solvent and adding a base under stirring as needed. The temperature of the liquid at the time of preparation can be appropriately set, and for example, a range of about 0 to 100 ° C is appropriate.

The polyoxymethylene compound may also be referred to as a polyoxyalkylene oxide, which is an oligomer or a polymer obtained by hydrolyzing a decane such as dichlorodimethyl decane to dehydrate and condense the produced stanol. Specifically, for example, dimethyl polyoxyl An organic polyoxyalkylene oxide such as an alkane, a dimethoxy polyoxyalkylene or a modified organic polyoxyalkylene, an organic hydrogen polyoxyalkylene such as a methyl hydrogen polyoxyalkylene or the like, and a methylhydroquinone-dimethylene. An oligomer or polymer obtained by dehydrating a decyl alcohol such as a decyl alkane copolymer such as a oxyalkylene copolymer, a polyoxyalkylene polymer or a triorganophosphonium decanoic acid. At least one selected from the above polyoxynitrides may be used. In the method of the present invention, especially in the methods (1) to (6), it is preferred to use a polyfluorene compound having a Si-H group, more preferably a poly Dimethyl decane/polymethyl siloxane copolymer. Further, a polyfluorene oxide compound having a Si—H group and a polyfluorene oxide compound having no Si—H group may be used in combination, and a polyfluorene oxide compound having no Si—H group and polydimethyl hydrazine may be used in combination. Alkane/polymethyl alkane copolymer.

Specifically, the organopolyoxyalkylene is exemplified by, for example, dimethyl polyoxyalkylene (also referred to as polydimethylsiloxane), and its basic chemical structure is represented by the following general formula (I). The n in the general formula (I) is preferably n=1 to 400, and preferably the dynamic viscosity is about 1 to 1000 Torr at 25 ° C.

Further, the organohydrogenpolyoxyalkylene is exemplified by methylhydrogenpolysiloxane or the like, and more preferably the polymerization degree n is an integer of from 3 to 7.

The alkane copolymer is exemplified by, for example, methylhydroquinone-dimethyloxane An alkane copolymer (also known as a polydimethyl siloxane/polymethyl siloxane copolymer) whose basic chemical structure is represented by the following formula (II), and in the present invention, it is preferably a formula (II) Among them, m and n are m=7~14, n=3~8, and m+n=10~22.

(1) A liquid containing a base-added polyoxo compound is mixed with inorganic particles (powder or slurry), and a surface of the inorganic particles is coated with a polyoxygenated compound.

In the method (1), a liquid containing the above-mentioned alkali-added polyoxo compound is mixed with inorganic particles (powder or slurry), and the surface of the inorganic particles is subjected to a polyoxynitride coating treatment.

The mixing may be any method, but a mixer, a mixer, a pulverizer or the like is preferably used. When the inorganic particle powder is used, it is preferably mixed with the polyoxygen compound liquid in a dry pulverizer or a dry mixer, and is exemplified by, for example, a ball mill, a bead mill, a colloid mill, a cone ball mill, a disc mill, and a blade. Crusher, milling grinder, hammer mill, mortar, particle grinder, vertical axis impact (VSI) grinder, Willy grinder, roll grinder, jet mill, cross jet mill, airflow ultrafine particle crushing Machine, high pressure crushing roller, Henschel mixer, planetary mixer, spiral mixer. The operating conditions and the like of the dry pulverizer or the like can be appropriately set. When mixing a polyoxyl compound liquid, it is preferable to use a sprayer, a sprayer, an atomizer, etc., and add a small amount each time. plus. When the inorganic particle slurry is used, it is preferably mixed with the polyoxygen compound liquid in a wet mixer or a wet pulverizer, and examples thereof include a paddle kneader, a high speed kneader, a dissolver, a homogenizer, and a wet micronization. Machine, wet jet mill, colloid mill, particle mill, bead mill, sand mill, ball mill, sand grinder, wire grinder, medium-free high-speed stirring disperser, etc. The operating conditions and the like of the wet pulverizer or the like can be appropriately set. It is preferred to mix the polyoxyxide liquid a small amount from the nozzle each time. The mixing conditions can be appropriately set. For example, the mixing temperature is preferably room temperature, and the mixed environment may be any of an oxidizing atmosphere such as oxygen or the atmosphere, an inert gas atmosphere such as nitrogen or argon, or a reducing gas atmosphere such as hydrogen. In particular, if it is an easily oxidizable inorganic particle, for example, an inorganic particle such as silver or copper, it is preferably an inert gas atmosphere, and if it is an inorganic particle which is hard to be oxidized, for example, inorganic particles such as titanium oxide or zinc oxide, it is carried out in the atmosphere. Economically better. The mixing time can be appropriately set, for example, in the range of about 0.1 to 10 hours. Further, the temperature of the mixed slurry may be appropriately set, for example, in the range of about 0 to 100 ° C. The order of mixing may be in any order to add a liquid containing a base-added polyoxo compound to the inorganic particles (powder or slurry) and to mix them preferably. After mixing the respective liquids, the pH of the slurry may be appropriately adjusted by alkali or acid. The coating amount of the polyoxymethylene compound can be appropriately set, and for example, the inorganic particles are preferably from 1 to 50% by mass, more preferably from 5 to 20% by mass, even more preferably from 5 to 15% by mass.

(2) The liquid containing the alkali-added polyoxo compound is mixed with an inorganic compound and inorganic particles (powder or slurry), and the surface of the inorganic particles is coated with a polyoxo compound and an inorganic compound.

In the method (2), in addition to the polyoxynitride coating treatment on the surface of the inorganic particles, the inorganic compound coating treatment is also performed.

The inorganic compound is exemplified by a metal compound such as aluminum, calcium, magnesium, barium, strontium, zirconium, titanium, zinc, iron, cobalt, manganese, nickel, or tin, or a non-metal compound, and at least one of such inorganic compounds can be used. The inorganic compound is dissolved in a solvent as needed. As the solvent, an aqueous solvent, an organic solvent, a mixed solvent of these or the like can be used, and an aqueous solvent which can dissolve an inorganic compound is preferably used. Further, the inorganic compound may be added to the polyoxonium compound solution in advance.

The inorganic compound and the liquid containing the alkali-added polysulfonium compound are mixed with the inorganic particles (powder or slurry) to coat the surface of the inorganic particles with the coating of the polyoxo compound and the inorganic compound.

The mixing order may be any order, and the inorganic compound may be added to the inorganic particles (powder or slurry), and then the liquid containing the alkali-added polyoxo compound may be added and mixed, and in other orders, the alkali may be added. The liquid of the polyoxygenated compound is added to the inorganic particles (powder or slurry), and then an inorganic compound is added and mixed. Further, a mixture of a base-added polyoxonium compound and an inorganic compound may be added to and mixed with inorganic particles (powder or slurry). The mixing method, the mixing time, the mixing temperature and the like may be the same as the above (1). After mixing the respective liquids, the pH of the slurry may be appropriately adjusted by alkali or acid. The coating of the inorganic compound may be in the form of an inorganic compound or an oxide, a hydroxide, an aqueous oxide or a salt of the inorganic compound. The coating amount of the inorganic compound can be appropriately set, and is, for example, preferably from 1 to 50% by mass, more preferably from 5 to 20% by mass, even more preferably from 5 to 15% by mass, based on the inorganic particles.

(3) A liquid containing a base-added polyoxo compound is mixed with a fatty acid compound and inorganic particles (powder or slurry), and a polyxanium oxide compound and a fatty acid compound are coated on the surface of the inorganic particles.

In the method (3), in addition to the polyoxynitride coating treatment on the surface of the inorganic particles, the fatty acid compound coating treatment is also performed.

The fatty acid compound may, for example, be hexanoic acid, citric acid, lauric acid, myristic acid, isomyristate, palmitic acid, isopalmitic acid, stearic acid, isostearic acid, arachidic acid, undecylenic acid, or oil. Acid, myristoleic acid, elaidic acid, linoleic acid, linolenic acid, arachidonic acid, coconut fatty acid, tallow fatty acid, resin acid (abietic acid), At least one of these fatty acid compounds can be used as the salt, the metal salt or the like. For example, the fatty acid constituting the N-fluorene matrix is preferably a long-chain fatty acid such as caproic acid, capric acid, lauric acid, myristic acid, isomyristate, palmitic acid, isoparic acid, stearic acid, isostearic acid. , arachidic acid, undecylenic acid, oleic acid, myristoleic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, coconut fatty acid, tallow fatty acid, resin acid (tannic acid), and the like. The form of the salt may be a metal salt of Na, K, Ba, Zn, Ca, Mg, Fe, Zr, Co, Al, Zr, Ti, or the like, or an ammonium salt, a monoethanolamine, a diethanolamine, a triethanolamine, a 2-amine. Various alkanolamine salts such as benzyl-2-methyl-propanol, 2-amino-2-methyl-1,3-propanediol, and triisopropanolamine. Further, the cyclodextrin fatty acid ester may be selected from an ester composed of a cyclodextrin and a fatty acid or a derivative thereof. Preferably, it is an ester body or a derivative thereof having at least one molecule of a cyclodextrin having one molecule of a fatty acid having a carbon number of 8 to 24, and is exemplified by, for example, a cyclodextrin. 1 molecule An ester having a structure in which one or a plurality of esters of a hydroxyl group has one or a plurality of fatty acids having a carbon number of 8 to 24 or a hydroxyl group in the ester body and a derivative of another fatty acid. .

The fatty acid compound may be dissolved or emulsified in a solvent as needed. As the solvent, an aqueous solvent, an organic solvent, a mixed solvent of these or the like can be used, and an aqueous solvent is preferably used. Further, a fatty acid compound may be added to the polyoxosiloxane liquid.

The fatty acid compound is mixed with the liquid containing the alkali-added polyoxo compound and the inorganic particles (powder or slurry) to coat the surface of the inorganic particles with the coating of the polyoxygen compound and the fatty acid compound. The order of mixing may be any order, and the fatty acid compound may be added to the inorganic particles (powder or slurry), and then the liquid containing the alkali-added polyoxo compound is added and mixed, and the other order is to add the alkali. The liquid of the polyoxygen compound is added to the inorganic particles (powder or slurry), and then the fatty acid compound is added and mixed. Further, a mixture of a base-added polyoxonium compound and a fatty acid compound may be added to and mixed with inorganic particles (powder or slurry). The conditions of the mixing method, the mixing time, the mixing temperature, and the like may be the same as in the above (1). After mixing the respective solutions, the pH of the slurry may be appropriately adjusted by alkali or acid. The amount of the fatty acid compound to be coated can be appropriately set, and is, for example, preferably from 1 to 20% by mass, more preferably from 1 to 10% by mass, even more preferably from 1 to 5% by mass, based on the inorganic particles.

(4) The liquid containing the alkali-added polyoxo compound is mixed with the fatty acid compound and the inorganic compound and the inorganic particles (powder or slurry), and the polysiloxane compound and the fatty acid compound and the inorganic compound are coated on the surface of the inorganic particles.

In the method (4), in addition to the polyoxynitride coating treatment on the surface of the inorganic particles, the coating treatment of the fatty acid compound and the inorganic compound is also performed. This method can be carried out in accordance with the above (1), (2), (3).

(5) mixing inorganic particles (powder or slurry) with an inorganic compound, and coating the surface of the inorganic particles with an inorganic compound, followed by mixing with the inorganic particles (powder or slurry) and a liquid containing a base-added polyoxo compound. The inorganic compound and the polyoxyxide compound are coated on the surface of the inorganic particles.

In the method (5), after the inorganic compound is coated on the surface of the inorganic particles, the polyoxynitride coating treatment is performed. This method or the like can be carried out in accordance with the above (1), (2).

First, inorganic particles (powder or slurry) are mixed with an inorganic compound, and if necessary, hydrolyzed or neutralized, and the inorganic particles are coated on the surface of the inorganic particles to treat the inorganic compound (first stage). Subsequently, the inorganic compound-coated inorganic particles (powder or slurry) are separated and washed as needed, and then dispersed into a slurry, and then a liquid containing a base-added polyoxo compound is mixed to perform a polyoxynitride coating treatment ( Phase 2).

In the first step, the inorganic particle slurry is used, and in the second step, the inorganic particle powder or the like is used. The inorganic particles used in the first stage and the second stage may be in the same state as the powder or the slurry, or may be in different states.

The inorganic particles may be coated with an inorganic compound on the entire surface of the particles, and may be coated with a polyoxyxide compound via an inorganic compound, or may be coated with an inorganic compound on one surface of the particle, and may be coated with an inorganic compound. Part of the oxygen compound.

(6) mixing inorganic particles (powder or slurry) with an inorganic compound, and coating the inorganic compound on the surface of the inorganic particles, followed by the inorganic particles (powder or slurry) and the liquid containing the alkali-added polyoxo compound The fatty acid compound is mixed, and the inorganic compound and the polyoxyxide compound and the fatty acid compound are coated on the surface of the inorganic particles.

In the method (6), after the inorganic compound is coated on the surface of the inorganic particles, the polyoxo compound and the fatty acid compound are coated. This method or the like can be carried out in accordance with the above (1) to (4).

First, inorganic particles (powder or slurry) are mixed with an inorganic compound, and if necessary, hydrolyzed or neutralized, and inorganic compound coating treatment is performed on the surface of the inorganic particles (first stage). Subsequently, the inorganic compound-coated inorganic particles (powder or slurry) are separated and washed as needed, and then dispersed into a slurry, and then mixed with a liquid containing a base-added polyoxo compound and a fatty acid compound to carry out polyoxyl The compound is coated with a fatty acid compound (stage 2).

The inorganic particle slurry is used in the first step, and the inorganic particle powder or the like is used in the second step. The inorganic particles used in the first stage and the second stage may be in the same state as the powder or the slurry, or may be in different states.

The inorganic particles may be coated with an inorganic compound as a whole of the surface of the particles, and may be coated with a polyfluorene oxide compound via an inorganic compound, or may be a part of the surface of the particle coated with the inorganic compound, and may be coated with a polyoxonium compound without intervening the inorganic compound. Part of it.

In addition to the polyoxonium compound or the fatty acid compound described in the methods (1) to (6), the alkoxydecane or alkyl hydrazine may be further coated. An organic hydrazine compound such as an alkane or a trimethyl decyl decanoic acid, or an organic compound such as a polyolefin, a hydrogenated lecithin or an N-mercaptoamino acid. The alkoxydecane is exemplified by methyltrimethoxydecane, ethyltriethoxydecane, octyltriethoxydecane, and the like. The alkyl decane is exemplified by methyl decane, ethyl decane, octyl decane, and the like. Further, trimethylphosphonium decanoic acid is obtained by dissolving sodium obtained by substituting sodium trimethyl sulfonyl in water glass in a solvent. Further, as the polyolefin, polyethylene, polypropylene or the like can be used. For example, a low molecular weight polyethylene having a molecular weight of 500 to 20,000 and a melting point of 40 ° C or higher, or an oxidized polyethylene obtained by oxidizing polypropylene, maleated polyethylene can be used. Commercial products such as oxidized polypropylene. Further, the hydrogenated lecithin is obtained by hydrogenating natural lecithin or synthetic lecithin extracted from egg yolk, soybean, corn, vegetable, etc., and the iodine value is preferably 30 or less, more preferably 15 or less hydrogenated lecithin. It is a glyceride having a phosphate group. As for the salt form, it is preferably a water-insoluble hydrogenated lecithin metal salt of Al, Mg, Ca, Zn, Zr, Ti or the like. Further, the N-decylamino acid is an amine group and/or an imine group of an amino acid. The types of amino acids may be exemplified by glycine, alanine, β-alanine, valine, leucine, isoleucine, phenylalanine, valine, threonine, serine, Arginine, histidine, lysine, aspartic acid, glutamic acid, tyrosine, methionine, cystine, cysteine, and the like.

The dry powder or the wet powder obtained by the coating treatment in the above (1) to (6) may be pulverized into a dry pulverized powder by using a dry pulverizer or a dry mixer as needed. As the dry pulverizer or the like, the above-described pulverizer or mixer can be used, and it is preferably an air flow pulverizer. The air flow pulverizer sprays argon gas or nitrogen gas from the nozzle at a high speed, and accelerates the powder particles by the air flow. As the machine which is pulverized by mutual collision, a jet mill, a cross jet mill, an air flow type ultrafine pulverizer or the like can be used. Further, it is preferably pulverized by a mixer such as a Henschel mixer or an ultra-kneader, a ball mill or a sand mill. The pulverization conditions can be appropriately set. For example, the pulverization temperature is preferably room temperature, and the mixed environment is preferably an oxidizing atmosphere such as oxygen or the atmosphere, an inert gas atmosphere such as nitrogen or argon, or a reducing gas atmosphere such as hydrogen. In particular, if it is an easily oxidizable inorganic particle, for example, an inorganic particle such as silver or copper, it is preferably an inert gas atmosphere, and if it is an inorganic particle which is hard to be oxidized, for example, inorganic particles such as titanium oxide or zinc oxide, it is carried out in the atmosphere. It is better in terms of cost.

The dry powder or the wet powder which has been subjected to the coating treatment in the above (1) to (6) or the above-mentioned dry pulverized powder may be dried or fired as needed. Further, the inorganic particle slurry which has been subjected to the coating treatment in the above (1) to (6) may be separated and washed as necessary, and then dried or fired. The drying temperature is in the range of about 50 to 200 ° C, and the firing temperature is preferably in the range of about 200 to 500 ° C. The drying and firing environment can be carried out in an oxygen atmosphere such as the atmosphere or oxygen, or an inert gas atmosphere such as nitrogen. . The coated inorganic particles which are dried or fired may be pulverized by a dry pulverizer or a dry mixer depending on the intended use. As the dry pulverizer or the like, the above-described pulverizer or mixer can be used, and a jet mill such as a jet mill, a cross jet mill, or an air flow type ultrafine pulverizer is preferable. Further, it is preferably pulverized by a mixer such as a mixer such as a Henschel mixer or an ultra-kneader, a ball mill or a sand mill. The pulverization conditions can be appropriately set. For example, the pulverization temperature is preferably room temperature, and the mixed environment is preferably an oxidizing environment such as oxygen or atmosphere, nitrogen, argon, or the like. Any of a reducing gas environment such as an inert gas atmosphere or hydrogen. In particular, if it is an easily oxidizable inorganic particle, for example, an inorganic particle such as silver or copper, it is preferably an inert gas atmosphere, and if it is an inorganic particle which is hard to be oxidized, for example, inorganic particles such as titanium oxide or zinc oxide, it is carried out in the atmosphere. It is better in terms of cost.

Next, the coated inorganic particles of the present invention may be prepared as a dispersion dispersed in a dispersion medium as needed. The concentration of the coated inorganic particles can be appropriately adjusted, but it is preferably a higher concentration. Specifically, it is preferably from 10 to 75% by mass, more preferably from 10 to 65% by mass, even more preferably from 30 to 60% by mass. The dispersion medium is not particularly limited, and various suitable ones can be used, and a lipophilic dispersion medium can be suitably used.

Specifically, it is exemplified by a monohydric alcohol solvent such as ethanol, propanol, isopropanol, butanol, pentanol, hexanol, heptanol, octanol, octyl alcohol, decyl alcohol, decyl alcohol, phenol, benzyl alcohol or the like. Petroleum hydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane, isohexane, isooctane, gasoline, mineral oil, benzene, toluene, xylene, cyclohexane, ethylbenzene, pentane Aromatic hydrocarbon-based solvents such as benzene, plant-based hydrocarbon solvents such as dipentene and turpentine, nitrohydrocarbon solvents such as nitroalkane and nitrobenzene, acetone, methyl ethyl ketone, a ketone solvent such as methyl isobutyl ketone, ethyl butyl ketone or diisobutyl ketone; a halogenated hydrocarbon solvent such as dichloromethane, chloroform, carbon tetrachloride, perchloroethylene or monochlorobenzene; , ether, isopropyl ether, dibutyl ether, hexyl ether, propylene oxide, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether and other ether solvents, methyl methyl ester, ethyl formate, Butyl formate, methyl acetate, ethyl acetate, butyl acetate, amyl acetate, ethyl propionate, butyl propionate, propionic acid Ester ester solvents such as butyl ester, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, butyl lactate, and amyl lactate, safflower oil, soybean oil, evening primrose oil, grape seed oil, rose hip (rose hip) oil, kukui nuts, almond oil, sesame oil, wheat germ oil, maize oil, cottonseed oil, avocado oil, olive oil, camellia oil, apricot oil, castor oil, peanut oil, hazelnut oil (hazelnut oil), macadamia nut oil, white mango seed oil, cocoa butter, shea butter, wood wax, coconut oil, palm oil, palm kernel oil, tallow, horse fat, oyster sauce, cream , oils such as egg butter and sea turtle oil, hydrocarbon oils such as liquid alkanes, liquid isoparaffins, squalane, squalene, petrolatum, alkanes, ceresin wax, microcrystalline wax, etc., lauric acid , fatty acids such as myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, undecylenic acid, hydroxystearic acid, sheep fatty acid, myristyl alcohol, cetyl alcohol, whale Wax stearyl alcohol, stearyl alcohol, aryl alkanol, behenyl alcohol, oleyl alcohol, oil palm alcohol, shark liver alcohol (batyl a Lcohol), cholesterol, phytosterol, sheep alcohol, isostearyl alcohol and other higher alcohols, isopropyl isostearate, ethyl oleate, isopropyl myristate, isopropyl palmitate, cetyl octanoate Ester, diisostearyl malate, tricaprylin, isooctyl isodecanoate, isodecyl isononanoate, isotridecyl isononanoate, octyl dodecyl pivalate, pivalic acid Esteryl tridecyl ester, myristyl pivalate, propylene glycol diisophthalate, triethyl 2-ethylhexanoate, trimethylolpropane triethylolpropane, etc., beeswax , Candelilla wax, cetyl wax, cotton wax, carnauba wax, bayberry wax, rice bran wax, insects wax, orange roughy oil, brown medium Waxes, wax, wax, shellac, lanolin, jojoba oil, etc. , methyl polyoxyalkylene, methyl phenyl polyoxyalkylene, decamethylcyclotetraoxane, alkyl modified polyoxyl, alcohol modified polyoxyl, amine modified polyoxyl, epoxy denatured poly Oxygen, olefin denatured polyoxygen, carboxyl modified polyoxyl, carbitol denatured polyoxyl, phenol denatured polyoxyl, methacrylic denatured polyoxygen, sulfhydryl modified polyoxyl, phosphoric acid denatured polyoxygen, fluorine Polyfluorenes, polycondensed polyfluorenes, polyether-denatured polyfluorenes, perfluoropolyethers, perfluoropolyethers, hydrofluoroethers, perfluoromethylcyclopentanes, perfluorodimethylcyclohexanes , perfluorodimethylcyclobutane, methoxy nonafluorobutane, ethoxy nonafluorobutane, dodecafluoropentane, tetradecafluorohexane, perfluorodecane, perfluorooctane, 4- a fluorine-based oil agent such as tris-trifluoromethylperfluoromorpholine or 4-pentafluoroethylperfluoromorpholine, as a UV absorber, an aminobenzoic acid, a p-aminobenzoic acid monoglyceride, N, N-dimethyl-p-aminobenzoic acid ethyl ester, N,N-diethoxy-p-aminobenzoic acid ethyl ester, N,N-dipropoxy-p-aminobenzoic acid ethyl ester, etc. High menthyl-N-acetamidobenzoic acid Aminobenzoic acid such as ester, amyl salicylate, menthyl salicylate, permentyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, etc., Octyl cinnamate, ethyl 4-isopropyl cinnamate, methyl 2,5-diisopropyl cinnamate, ethyl 2,4-diisopropyl cinnamate, propyl p-methoxycinnamate, Isopropyl p-methoxycinnamate, isoamyl p-methoxycinnamate, octyl p-methoxycinnamate, 2-ethoxyethyl p-methoxycinnamate, p-methoxy Cinnamonic acid such as cyclohexyl cinnamate, 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxydi Benzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 4-hydroxy-3-carboxybenzophenone, etc. Class, 3-benzylidene-d, l-camphor, urinary journal Urocanic acid, ethyl urate, 2-phenyl-5-methylbenzoxazole, dibenzalazine, difenylidene methane, 4-tert-butyl-4'- Oxydiphenylmethane methane, polyfluorene-denatured ultraviolet absorber, fluorine-denatured ultraviolet absorber, and the like. One or two or more of these may be used as the lipophilic solvent of the present invention.

Further, a pigment dispersant, an oil agent, a surfactant, a UV absorber, a preservative, an antioxidant, a film former, a moisturizer, a tackifier, a dye, a pigment, a perfume, and the like can be appropriately formulated in the dispersion of the present invention.

For example, an alkyl ether sulfate ester such as POE lauryl triethanolamine or the like, an alkylbenzenesulfonate such as sodium dodecylbenzenesulfonate, a higher alkylsulfate salt such as sodium lauryl sulfate or potassium lauryl sulfate. , higher fatty acid decyl sulfonate such as N-mercapto sarcosine, N-myristyl-N-methyl taurate, and higher fatty acid ester sulphate of hardened coconut fatty acid glycerol sulfate , higher fatty acid ester sulfonate, higher fatty acid alkanolamine sulfate salt, fatty acid soap, sulfosuccinate, secondary alcohol sulfate, POE alkyl ether carboxylic acid, POE alkyl allyl ether carboxylate Anionic surfactant such as acid salt, α-olefin sulfonate, sodium lauryl monoethanol decyl succinate, N-palmitanyl aspartate diethanolamine, casein sodium, etc., chlorinated stearyl An alkyltrimethylammonium salt such as methylammonium or an alkyl quaternary ammonium salt such as distearyldimethylammonium chloride or dialkyldimethylammonium chloride; or an alkylpyridinium salt , alkylamine salt, alkyl dimethyl benzyl ammonium salt, alkyl isoquinolinium salt, dialkyl morpholinium salt, POE alkylamine, polyamine fat Derivatives, amyl alcohol fatty acid derivatives, benzalkonium chloride, benzyl ammonium chloride, ethane (benzethonium Cationic surfactant such as chloride), imidazoline-based amphoteric surfactant such as 2-cocoyl-2-imidazolium hydroxide-1-carboxyethoxy 2 sodium salt, alkylbetaine, guanamine A betaine amphoteric surfactant such as betaine or lauryl dimethylaminoacetic acid betaine, a glycerin fatty acid ester such as glycerol sesquiole or glyceryl monostearate, and hexaglyceryl polyricinoleate. Polyglycerin fatty acid esters such as diglyceryl monostearate and decaglyceryl decatilate; sorbitan fatty acid esters such as sorbitan monooleate and sorbitan sesquioleate; A propylene glycol fatty acid ester such as propylene glycol monostearate, a POE sorbitan fatty acid ester such as POE sorbitan monooleate, or a POE glycerin fatty acid ester such as POE glyceryl triisostearate, POE POE fatty acid esters such as monooleate, POE distearate, POE alkyl ether such as POE lauryl ether and POE stearyl ether, POE. POP hydrogenated sheep oil and other POE. a non-ionic surfactant such as a POP alkyl ether, a hardened castor oil derivative, a glycerin alkyl ether, an alkanolamine, a sucrose fatty acid ester, a dextrin fatty acid ester, a starch fatty acid ester, or a hydroxystearic acid. Other phospholipids such as lecithin, glycolipids such as trehalose lipids, fluorine-based surfactants such as perfluoroalkyl phosphates, perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, etc., acrylic acid A natural or synthetic clay mineral such as an alkyl methacrylate copolymer, bentonite, montmorillonite or kaolin, an organic modified clay mineral such as an organic amine cation-denatured bentonite, or an aerosol.

The method of kneading or mixing and dispersing the coated inorganic particles in the dispersion medium is not particularly limited as long as a conventional method is employed. A kneading mixer such as kneading machine kneading, Henschel kneading, roll kneading, and extruder kneading can be used, a paddle kneading machine, a high speed kneading machine, a dissolving machine, a homogenizing machine, Wet type micro-machine, wet jet mill, colloid mill, particle mill, bead mill, sand mill, ball mill, sand grinder, in-line grinder, medium-free high-speed stirring disperser, etc. A dispersion disperser and a wet pulverizer were used to produce a dispersion.

Further, as the cosmetic material to which the inorganic particles of the present invention are formulated, the dispersion may be used as a liquid cosmetic. It can be exemplified by, for example, foundation, liquid foundation, oily foundation, vermicelli, honey powder, powder cake, lipstick, lipstick, blush, eye shadow, eyebrow pencil, eyeliner, mascara, water-based nail polish, oily nail polish, emulsified nail polish, Cosmetics for nail polish, nail primer, protective oil, etc., moisturizing cream, cold cream, whitening cream, lotion, lotion, beauty lotion, carmine lotion, liquid face wash, face wash, Skin care products such as face cream, face powder, makeup remover, body gloss, hair gloss, hair cream, shampoo, conditioner, hair dye, hair varnish For hair cosmetics, for other purposes, sunscreen or sun cream or lotion, soap, body wash, perfume, etc.

The amount of the inorganic particles to be coated may be appropriately adjusted depending on the form of the cosmetic material, and is, for example, preferably from 1 to 20% by mass, more preferably from 1 to 15% by mass, even more preferably from 1 to 10% by mass, based on the liquid cosmetic. A general blender can be used for the cosmetic, for example, a pigment dispersant, an oil agent, a surfactant, a UV absorber, a preservative, an antioxidant, a film former, a moisturizer, a tackifier, a dye, a pigment, and a fragrance can be appropriately formulated. Wait.

The coated inorganic particles of the present invention can also be preferably used in applications other than dispersions and cosmetics, and in plastic additives, inks, and coatings. It is widely used in various fields such as materials, carbon powder (magnetic powder, external additives), chemical fibers, packaging materials, and electronic materials.

[Examples]

The embodiments of the invention are shown below, but the invention is not limited thereto.

Example 1

The titanium tetrachloride aqueous solution is hydrolyzed to obtain fine particle titanium oxide. The aqueous titanium oxide slurry was filtered, washed and redispersed to prepare an aqueous slurry of titanium oxide.

The slurry contains 90% by mass of water, and the size of the inorganic particles in the slurry is in the range of 0.3 to 1.5 μm as indicated by the particle diameter D50.

An aqueous solution of sodium aluminate was added to the aqueous slurry of titanium oxide to adjust the pH to 6.5, and the titanium oxide was subjected to a coating treatment of 23 mass% of aluminum hydroxide.

On the other hand, 0.05 ml/g of a 20% aqueous sodium hydroxide solution is added to the solution obtained by previously diluting the polydimethylsiloxane/polymethyloxane copolymer in 4 times the mass of ethanol. The polydimethylsiloxane/polymethyloxane copolymer was partially hydrolyzed by stirring for 15 minutes. The sodium hydroxide added to the polydimethyl siloxane/polymethyl siloxane copolymer was 1% by mass. This was taken as a polyoxosiloxane liquid to which a base was added.

The alkali-added polyoxosiloxane liquid (15% by mass based on TiO ₂ -converted titanium oxide) was added to the aluminum hydroxide-coated titanium oxide aqueous slurry, and the mixture was stirred and mixed at 70 ° C for 2 hours in a homogenizer. The resulting slurry was filtered and washed to obtain a filter cake of fine particle titanium oxide coated with aluminum hydroxide and polyoxynitride. Then, the filter cake was dried by heating in a dryer at 150 ° C for 4 hours, and then finely pulverized by a jet mill (jet mill) to obtain coated inorganic particles of the present invention (sample A).

Example 2

In the first embodiment, the addition of a base-added polyoxosiloxane liquid to 10% by mass of titanium oxide and the addition of sodium stearate of 5% by mass to titanium oxide are added in an amount of 15% by mass based on the addition of titanium oxide. The coated inorganic particles of the present invention (sample B) were obtained in the same manner as in Example 1 except that a filter cake of fine titanium oxide coated with aluminum hydroxide and polyoxyxamate and stearic acid was obtained. ).

Example 3

In Example 1, except that the solution obtained by diluting the polydimethyl methoxy oxane/polymethyl siloxane copolymer in 4 times the amount of ethanol in advance was added 1 ml/g of a 20% aqueous sodium hydroxide solution instead of adding The coated inorganic particles of the present invention (sample C) were obtained in the same manner as in Example 1 except that 0.05 ml/g of a polyoxyl compound liquid was added as a base. The sodium hydroxide added to the polydimethyl siloxane/polymethyl siloxane copolymer was 20% by mass.

Example 4

In Example 1, except that polydimethyl methoxy oxane/polymethyl group was previously The oxirane copolymer was diluted in a solution of 4 times the amount of ethanol, and 0.05 ml/g of a 2% aqueous sodium hydroxide solution was added and stirred for 1 minute instead of adding 0.05 ml/g of a 20% aqueous sodium hydroxide solution and stirring 15 The coated inorganic particles of the present invention (Sample D) were obtained in the same manner as in Example 1 except that a polyoxosiloxane liquid to which a base was added was added in a minute. The sodium hydroxide added to the polydimethyl siloxane/polymethyl siloxane copolymer was 0.1% by mass.

Example 5

The aluminum hydroxide-coated titanium oxide aqueous slurry of Example 1 was dried, and a specific amount was preliminarily pulverized by a jet mill (jet mill) to be fed into a Henschel kneading machine, and sprayed by a sprayer. For the aluminum hydroxide-coated titanium oxide, the mass of the titanium oxide was 6% by mass of the alkali-added polyoxosiloxane liquid of Example 1, and stirred. After mixing, it was again pulverized by a jet mill (jet mill). The pulverized powder was heat-treated at 140 ° C for 30 minutes in a dryer to obtain coated inorganic particles (sample E).

Example 6

In the same manner as in Example 5, except that the aluminum hydroxide-coated titanium oxide aqueous slurry was dried by a hammer mill and pulverized by a jet mill, the coated inorganic particles were obtained. F).

Example 7

In Example 5, except that a droplet is added instead of the spray spray, In the same manner as in Example 5, coated inorganic particles (sample G) were obtained.

Example 8

In Example 5, the same treatment as in Example 5 was carried out except that the powder was sprayed again by a hammer mill, and the coated inorganic particles (sample H) were obtained.

Example 9

To the aqueous slurry of the aluminum hydroxide-coated titanium oxide of Example 1, the alkali-added polyoxyxide liquid of Example 1 (6 mass% with respect to titanium oxide) was added, and the mixture was stirred at room temperature for 30 minutes, and then beads were used. The grinder is wet pulverized to a specific particle size. The resulting slurry was washed by filtration to obtain a filter cake of fine particle titanium oxide coated with aluminum hydroxide and polyoxynitride. Subsequently, the filter cake was dried by heating in a dryer at 90 ° C for 4 hours, and further heat-treated at 140 ° C for 30 minutes, and finely pulverized by a jet mill (jet mill) to obtain coated inorganic particles (Sample I).

Comparative example 1

In Example 1, except that the polydimethyl siloxane/polymethyl siloxane copolymer was diluted with 4 times the amount of ethanol added to the titanium oxide to obtain a polysiloxane liquid (without adding sodium hydroxide) instead of adding The coated inorganic particles (sample J) were obtained in the same manner as in Example 1 except that the alkali-containing polyoxosiloxane liquid was added in an amount of 15% by mass.

Comparative example 2

In Example 1, the aluminum hydroxide treated microparticles titanium oxide was filtered. Wash. After drying, it was pulverized using a hammer mill. 7.5% by mass of polydimethyl methoxy oxane/polymethyl decane copolymer was added to the powder, stirred and mixed using a Henschel mixer, and heat treated at 150 ° C for 20 minutes, followed by a jet mill. (Jet Grinding Machine) Fine pulverization was carried out to obtain coated inorganic particles (sample K).

Evaluation method

(Evaluation of hydrogen production)

4 g of each of the samples obtained in Examples 1 to 9 and Comparative Examples 1 and 2 and 40 ml of ethanol were placed in a 50 ml Erlenmeyer flask and stirred. Hydrogen was generated by dropwise addition of 5 ml of a 10% aqueous sodium hydroxide solution in a closed system, and the amount of gas generated was measured by cylinder trapping.

*Hydrogen generation amount (ml/g) = (all gas generation amount (ml) when adding 10% sodium hydroxide - gas production amount (ml) when adding ethanol) / sample mass (g)

(hydrophobicity evaluation)

The evaluation was carried out by the following water/methanol method.

(1) Each sample was floated in an aqueous solution having various changes in the range of from 0/100 to 100/0 in a mass ratio of methanol to water, and gently shaken and then allowed to stand.

(2) The sample has a maximum amount of methanol which can maintain hydrophobicity with respect to the aqueous solution as the degree of hydrophobicization.

The evaluation results are shown in Table 1. Examples 1-9 are used for gathering Since sodium hydroxide was added to the dimethyl siloxane/polymethyl siloxane copolymer, the amount of hydrogen gas generation was suppressed more than that of Comparative Example 2. On the other hand, since the degree of hydrophobicization became higher than that of Comparative Example 1, it was found that the polyoxynitride compound can be more uniformly coated.

[Industrial availability]

According to the present invention, it is possible to produce coated inorganic particles excellent in oil-dispersion stability and hydrophobic stability for a long period of time at a low cost by a simple method. The coated inorganic particles are widely used in various fields such as cosmetics, plastic additives, inks, paints, carbon powders (magnetic powders, external additives), chemical fibers, packaging materials, and battery materials.

Claims (16)

A method for producing coated inorganic particles, comprising: adding a base to a polyfluorene oxide at a ratio of 0.5 to 20% by mass of a polyfluorene oxide to reform a polyoxyl oxide base, and then modifying the alkali-containing substance The liquid of the polyoxygenated compound is mixed with the inorganic particles, and the step of coating the surface of the inorganic particles with the alkali-modified polyoxyl compound. A method for producing coated inorganic particles, comprising: adding a base to a polyfluorene oxide at a ratio of 0.5 to 20% by mass of a polyfluorene oxide to reform a polyoxyl oxide base, and then modifying the alkali-containing substance The liquid of the polyoxygenated compound is mixed with the inorganic compound and the inorganic particles, and the surface of the inorganic particles is coated with the alkali-modified polysiloxane and the inorganic compound. A method for producing coated inorganic particles, comprising: adding a base to a polyfluorene oxide at a ratio of 0.5 to 20% by mass of a polyfluorene oxide to reform a polyoxyl oxide base, and then modifying the alkali-containing substance The liquid of the polyoxygenated compound is mixed with the fatty acid compound and the inorganic particles, and the alkali-modified polysiloxane compound and the fatty acid compound are coated on the surface of the inorganic particles. A method for producing coated inorganic particles, comprising: adding a base to a polyfluorene oxide at a ratio of 0.5 to 20% by mass of a polyfluorene oxide to reform a polyoxyl oxide base, and then modifying the alkali-containing substance The liquid of the polyoxygenated compound is mixed with the fatty acid compound, the inorganic compound and the inorganic particles, and the surface of the inorganic particle is coated with the alkali-modified polysiloxane compound, the fatty acid compound and the inorganic compound. A method for producing coated inorganic particles, comprising: mixing inorganic particles with an inorganic compound, and coating the surface of the inorganic particles with an inorganic compound, and then, the inorganic particles are 0.5 to 20% by mass with respect to the polysiloxane Adding a base to the polyoxonium compound at a ratio to modify the polyoxynitride base, and mixing the liquid containing the alkali-modified polyoxo compound, and coating the inorganic compound with the alkali-modified polyoxyl compound Particle surface. A method for producing coated inorganic particles, comprising: mixing inorganic particles with an inorganic compound, and coating the surface of the inorganic particles with an inorganic compound, and then, the inorganic particles are 0.5 to 20% by mass with respect to the polysiloxane Adding a base to the polyoxonium compound at a ratio to modify the polyoxynitride base, and mixing the liquid and the fatty acid compound containing the alkali-modified polyoxo compound, and the inorganic compound and the alkali-modified polycondensate The oxygen compound and the fatty acid compound coat the surface of the inorganic particles. The method for producing coated inorganic particles according to any one of claims 1 to 6, wherein the inorganic particles are used as a slurry. The method for producing coated inorganic particles according to claim 7, wherein the inorganic particle slurry and the liquid containing the alkali-added polyoxo compound are mixed by a wet pulverizer or a wet mixer. The method for producing coated inorganic particles according to claim 7, wherein the inorganic particles in the slurry have a particle diameter D50 of from 0.01 to 4.0 μm. The method for producing coated inorganic particles according to any one of claims 1 to 6, wherein the inorganic particles are used as the powder. A method for producing coated inorganic particles according to claim 10, The inorganic particle powder and the liquid containing the alkali-added polyoxo compound are mixed by a dry pulverizer or a dry mixer. The method for producing coated inorganic particles according to claim 10, wherein the particle diameter D50 of the inorganic particle powder is in the range of 0.01 to 10 μm. The method for producing coated inorganic particles according to any one of claims 1 to 6, wherein the surface of the inorganic particles is coated with a polyfluorene oxide compound derived from a polyoxosiloxane to which an alkali is added, and then pulverized by a jet mill. The method for producing coated inorganic particles according to claim 13, which is pulverized by a jet mill and then dried. The method for producing coated inorganic particles according to any one of claims 1 to 6, wherein the polyfluorene oxide compound is a compound having a Si-H group. The method for producing coated inorganic particles according to claim 15, wherein the compound having a Si-H group is a dimethicone/polymethyloxane copolymer.