JP5962612B2 - Method for producing organosol - Google Patents

Description

  The present invention relates to an organosol and a method for producing the same. More specifically, it is a method for producing an organosol through a method of replacing the dispersion medium of the water-dispersed colloidal solution from water to an organic solvent, in which a good dispersion state is obtained without performing mechanical unit operations such as classification and grinding. The present invention relates to a method for producing an organosol having both transparency and transparency, which can be easily carried out and highly useful, and an organosol obtained thereby.

  The organic solvent-dispersed colloidal solution is characterized in that inorganic oxide fine particles are stably dispersed without agglomerating in an organic solvent, and is also called an organosol. Since such organosols are excellent in compatibility with various organic resins, fields that have been difficult to be widely applied in water-dispersed colloidal solutions, such as organic-inorganic composites, resin modifications, nanofillers, paints, etc. There are many demands.

  Various manufacturing methods are known for organosols, but any method often requires special conditions and special know-how. Such difficulty in production has hindered industrial development in the field, and systematic guidelines for producing simple, general, and useful organosols have been known so far. It wasn't.

  Patent Document 1 (Japanese Patent Laid-Open No. 2012-77267) proposes a method in which a titanium oxide ingot is vaporized by arc plasma in a vacuum and surface-treated in a gas phase after nucleation to form an organic solvent dispersion. Yes. This method is an extreme reaction condition, and it was difficult to carry out with a general reactor.

  Patent Document 2 (Japanese Patent Application Laid-Open No. 2010-143806) exemplifies a method of redispersing silica fine particles that have been wet-surface-treated using a hydrophobic silane coupling agent in an organic solvent. Although this method is simple, the redispersibility of the inorganic fine particles largely depends on the system. That is, it is considered that the success or failure of production is sensitive to the type of solvent and the solvent replacement method. For example, the main point of the proposal is to hydrophobize the microparticles using specific conditions in water, and then add an organic solvent. However, since the hydrophobized microparticles are unstable in water, It is thought that it is difficult to determine the timing of adding. In an industrial process, due to problems such as the rotation rate of manufacturing equipment, it is not always possible to immediately carry out the next process. Therefore, it is desirable that the production intermediate for the next process is stable. However, the examples do not mention the stability of the hydrophobized microparticles in water, and the solvent substitution is a complicated process in which isopropyl alcohol is added little by little while distilling methanol in a rotary evaporator. An operation is requested. Therefore, it cannot be said that this method and its technical idea provide systematic guidelines for producing organosols.

  Patent Document 3 (Japanese Patent Laid-Open No. 2007-246351) and Patent Document 4 (Japanese Patent Laid-Open No. 2009-227500) disclose an example in which the problem regarding stability as described in Patent Document 2 is not significant. Has been. In these proposals, organosols are produced mainly with γ-glycidoxypropyltrimethoxysilane in mind as a surface treatment agent. Since γ-glycidoxypropyltrimethoxysilane has a relatively high solubility in water and is an amphiphilic molecule, it is considered that stable production has been realized. However, the surface treatment agent is not limited to γ-glycidoxypropyltrimethoxysilane, and it is desirable that various surface treatments can be performed. Therefore, it is hard to say that these proposals are highly general.

  Patent Document 5 (Japanese Unexamined Patent Application Publication No. 2009-13033) discloses a method for producing a surface-coated silica organosol. In this proposal, a method of further treating a commercially available silica organosol having a solvent substitution with a silane coupling agent is shown. This production method is in the category of an example of a method for using an organosilica sol, and does not indicate a process for producing an organosol from an aqueous dispersion colloidal solution.

  Patent Document 6 (Japanese Patent No. 3906933) discloses a method of obtaining an organosol by completely removing water of a water-dispersed colloidal solution once produced and redispersing it in an organic solvent. This method requires mechanical unit operations such as grinding and classification in order to redisperse in an organic solvent. Grinding requires not only a lot of energy but also a dispersant, which is not preferable in terms of material efficiency and has industrial disadvantages.

  On the other hand, many excellent production methods are known for aqueous dispersion colloidal solutions. For example, Patent Literature 7 (Japanese Patent No. 2783417), Patent Literature 8 (Japanese Patent No. 3225553), Patent Literature 9 (Japanese Patent No. 4051726), and the like can be mentioned. It is also easy to obtain a commercially available aqueous colloid solution.

  As described above, even in the same colloid solution, the ease of the production method varies greatly depending on whether the dispersion medium is water or an organic solvent, and in particular, a method for producing an organosol in which the dispersion medium is an organic solvent. The field about was left.

JP 2012-77267 A JP 2010-143806 A JP 2007-246351 A JP 2009-227500 A JP 2009-13033 A Japanese Patent No. 3906933 Japanese Patent No. 2783417 Japanese Patent No. 3225553 Japanese Patent No. 4051726

  The present invention has been made in view of the above circumstances, and in a method of producing an organosol starting from an inorganic oxide colloid aqueous dispersion, it can be easily carried out and is highly useful, and mechanical unit operations such as classification and grinding. It is an object of the present invention to provide a method for producing an organosol having both a good dispersion state and transparency without passing through the method, and an organosol obtained by the method.

  The present inventors considered the background art mentioned above and found one problem. That is, when an organosol is produced starting from an inorganic oxide colloid aqueous dispersion, there are mainly a surface treatment step (a) and a solvent replacement step (b), but it is difficult to balance these two steps. Is considered a problem. That is, when the surface treatment efficiently proceeds in the step (a) and the degree of hydrophobicity of the fine particles is improved, the step (b) is easily performed, but the stability of the fine particles in water is lowered. Therefore, the stability at the stage where the step (a) is completed becomes a problem. On the other hand, if the surface treatment in the step (a) is performed to such an extent that the dispersion stability in water can be ensured, the range in which the step (b) can be performed is limited.

  It is a concrete method for solving such conflicting problems at the same time, and has not been submitted so far with a clear technical idea that is highly useful and contributes to the development of the industrial field.

As a result of intensive studies to solve such problems in organosol production, the present inventors have made the following steps (A) to (G), that is,
(A) preparing an inorganic oxide colloid aqueous dispersion,
(B) adding alcohol characterized in that it is not completely compatible with water and forms a two-phase system;
(C) adding an organosilicon compound and / or (partial) hydrolysis condensate thereof,
(D) a step of irradiating microwaves;
(E) adding an organic solvent,
(F) An organosol which undergoes solvent substitution in an aqueous colloidal solution comprising the steps of distilling off water by azeotropic distillation and / or ultrafiltration, and (G) removing water to 1,000 ppm or less as necessary. The fact that the production method is useful has been found and the present invention has been made.

Therefore, the present invention provides the following organosol production method and organosol.
[1]
(A) preparing an inorganic oxide colloid aqueous dispersion,
(B) adding alcohol characterized in that it is not completely compatible with water and forms a two-phase system;
(C) The following general formula (1)
R ¹ _p R ² _q R ³ _r Si (OR ⁴ ) _4-pqr (1)
(In the formula, R ¹ is a hydrogen atom, non-substituted or substituted carbon atoms 1 to 20 monovalent hydrocarbon group, a silicon atom number of 50 or less polydimethylsiloxane group, or an isocyanurate group, R ^2, R ³ and R ⁴ are each an alkyl group having 1 to 6 carbon atoms, p is an integer of 1 to 3, q is 0, 1 or 2, r is 0, 1 or 2, and p + q + r is 1 to 3. (It is an integer.)
A step of adding an organosilicon compound and / or a partially hydrolyzed condensate or hydrolyzed condensate thereof,
(D) a step of irradiating microwaves;
(E) The manufacturing method of the organosol through the solvent substitution of the aqueous colloidal solution which consists of the process of adding an organic solvent, and the process of (F) distilling off water by azeotropic distillation and / or ultrafiltration.
[2]
Furthermore, (G) The manufacturing method of the organosol as described in [1] provided with the process of removing water to 1,000 ppm or less.
[3]
The dispersoid of the inorganic oxide colloid aqueous dispersion prepared in the step (A) is a core-shell fine particle having titanium oxide fine particles as nuclei and a silicon oxide shell outside the nuclei [1] Or the manufacturing method of the organosol as described in [2].
[4]
The dispersoid of the inorganic oxide colloid aqueous dispersion prepared in the step (A) has tetragonal titanium oxide solid solution fine particles in which tin and / or manganese is dissolved as a nucleus, and has a silicon oxide shell outside the nucleus. A core-shell type tetragonal titanium oxide solid solution aqueous dispersion having a volume average 50% cumulative particle diameter of the core fine particles measured by a dynamic light scattering method of 30 nm or less and a volume average 50% cumulative particle of the core-shell type fine particles. The diameter is 50 nm or less, the solid solution amount of the tin component is 10 to 1,000 in terms of the molar ratio with titanium (Ti / Sn), and the solid solution amount of the manganese component is the molar ratio of titanium (Ti / Sn). The method for producing an organosol according to [1] or [2], wherein core-shell type tetragonal titanium oxide solid solution fine particles having a Mn) of 10 to 1,000 are used.
[5]
The dispersoid of the inorganic oxide colloid aqueous dispersion prepared in the step (A) is alumina and / or silica, and the volume average 50% cumulative particle diameter of the dispersoid measured by a dynamic light scattering method is 10 nm. The method for producing an organosol according to [1] or [2], wherein the method is 100 nm or less.
[6]
[1] to [5], wherein the solubility of the alcohol added in the step (B) at 20 ° C. is 1 (1 g alcohol / 100 g water) or more and 30 (30 g alcohol / 100 g water) or less. The manufacturing method of the organosol in any one.
[7]
The alcohol to be added in the step (B) is a linear, branched or cyclic monovalent alcohol which may contain an aromatic group having 4 to 8 carbon atoms, and 3 to 8 carbon atoms. The method for producing an organosol according to any one of [1] to [6], wherein the organosol is one or more selected from the group consisting of monovalent alcohols that are fully or partially substituted with fluorine atoms.
[8]
In the step (D), the integrated microwave irradiation time is 60 seconds or more and 3,600 seconds or less, and the temperature of the system after irradiation is 10 ° C. or more and 150 ° C. or less [1] to [7] ] The manufacturing method of the organosol in any one of.
[9]
The solvent added in the step (E) is one or more selected from the group consisting of hydrocarbon compounds having 5 to 30 carbon atoms, alcohol compounds, ether compounds, ester compounds, ketone compounds, and amide compounds. The method for producing an organosol as described in any one of [1] to [8].
[10]
Any of [2] to [9], wherein the method of removing water to 1,000 ppm or less in the step (G) is physical adsorption using a zeolite having a pore diameter of 3 to 10 mm A method for producing an organosol as described above.
[11]
In the step (G), a method for removing water up to 1,000 ppm or less is an ortho organic acid ester or the following general formula (2)
(R ⁵ O) (R ⁶ O) CR ⁷ R ⁸ (2)
(In the formula, R ⁵ and R ⁶ are each a monovalent hydrocarbon group having 1 to 10 carbon atoms, which may be bonded to each other to form a ring, and R ⁷ and R ⁸ each have 1 carbon atom. 10 or less monovalent hydrocarbon groups which may be bonded to each other to form a ring.
The method for producing an organosol according to any one of [2] to [9], which is a method involving a chemical reaction using a gem-dialkoxyalkane represented by formula (1).

  According to the present invention, an organosol can be easily and reliably produced from an inorganic oxide colloid aqueous dispersion. According to the production method of the present invention, it is possible to produce not only organosilica sol and organoalumina sol but also organotitania sol which has been relatively difficult to produce so far. The coating composition characterized by containing an organotitania sol produced by the method of the present invention can form a coating film excellent in transparency.

It is a measurement result of the particle size distribution of the organosilica sol obtained in Example 1 of the present invention. It is a transmission electron microscope image of the organosilica sol obtained in Example 1 of the present invention. It is a measurement result of the particle diameter distribution of the organo titania sol obtained in Example 4 of this invention. It is a transmission electron microscope image of the organotitania sol obtained in Example 4 of this invention.

Below, the manufacturing method of the organosol of this invention is demonstrated in detail.
The method for producing an organosol of the present invention involves solvent replacement of an aqueous colloidal solution comprising the following steps (A) to (F) and, if necessary, the following step (G).
(A) preparing an inorganic oxide colloid aqueous dispersion,
(B) adding alcohol characterized in that it is not completely compatible with water and forms a two-phase system;
(C) The following general formula (1)
R ¹ _p R ² _q R ³ _r Si (OR ⁴ ) _4-pqr (1)
(In the formula, R ¹ is a hydrogen atom, non-substituted or substituted carbon atoms 1 to 20 monovalent hydrocarbon group, a silicon atom number of 50 or less polydimethylsiloxane group, or an isocyanurate group, R ^2, R ³ and R ⁴ are each an alkyl group having 1 to 6 carbon atoms, p is an integer of 1 to 3, q is 0, 1 or 2, r is 0, 1 or 2, and p + q + r is 1 to 3. (It is an integer.)
A step of adding an organosilicon compound and / or a (partial) hydrolysis condensate thereof,
(D) a step of irradiating microwaves;
(E) adding an organic solvent,
(F) a step of distilling off water by azeotropic distillation and / or ultrafiltration,
(G) The process of removing water to 1,000 ppm or less.

Process (A)
Step (A) in the method for producing an organosol of the present invention is a step of preparing an inorganic oxide colloid aqueous dispersion. The inorganic oxide colloid aqueous dispersion prepared in the step (A) is preferably a dispersion of an inorganic oxide colloid aqueous dispersion such as inorganic oxide particles having a volume average 50% cumulative particle diameter of 1 to 200 nm. Dispersed without agglomerating in the liquid dispersion medium.

Dispersoid of inorganic oxide colloid aqueous dispersion The dispersoid of the inorganic oxide colloid aqueous dispersion used in the present invention is an inorganic oxide such as a metal oxide. Examples of elements constituting the metal oxide include group 13 elements, group 14 elements (excluding carbon), first series transition elements, second series transition elements, third series transition elements, lanthanoids, and the like. Among group 13 elements, oxides derived from aluminum, boron, indium and the like are particularly suitable, and alumina sol is generally known. Among group 14 elements (excluding carbon), oxides derived from silicon, tin and the like are suitable, and silica sol is common. As the first series transition element, an oxide derived from titanium, manganese, zinc or the like is preferable. These oxides are often used as a light-absorbing material having a specific wavelength. As the second series transition element, an oxide derived from yttrium, zirconium or the like is preferable. These oxides are often used as light absorption and fluorescent materials of specific wavelengths. As the third series transition element, an oxide derived from hafnium, tantalum, or the like is preferable. As the lanthanoid, an oxide derived from lanthanum, cerium, praseodymium, neodymium, terbium, dysprodium, ytterbium, or the like is preferable. These oxides are often used as light absorption and fluorescent materials of specific wavelengths.

The dispersoid of the inorganic oxide colloid aqueous dispersion used in the present invention may be one kind or a combination of two or more kinds as long as it is selected from the group of metal oxides. The compound described here has a broad meaning, and any compound may be used as long as it is compounded through simple mixing and chemical bonding. The compound through a chemical bond refers to a form represented by the following general formula (3), for example.
(M ¹ O _x ) _m (M ² O _y ) _n (3)

Here, M ¹ is an element symbol of Al, B, In, Si, Ge, Sn, Ti, Mn, Zn, Y, Zr, Hf, Ta, La, Ce, Pr, Nd, Tb, Dy, Yb. It is one of the types represented. M ² is represented by an element symbol of Al, B, In, Si, Ge, Sn, Ti, Mn, Zn, Y, Zr, Hf, Ta, La, Ce, Pr, Nd, Tb, Dy, and Yb. It is one of these elements and is not the same element as that selected for M ¹ . x and y can be expressed as x = a / 2 if the valence of M ¹ is a, and y = b / 2 if the valence of M ² is b. m and n are real numbers satisfying m + n = 1 and satisfy 0 <m <1 and 0 <n <1. That is, in the structure, M ¹ and M ² have a unit bonded through oxygen. M ¹ and M ² may be scattered in the structure or may be unevenly distributed. What is scattered in the structure of M ¹ and M ² is a structure found in a co-hydrolyzate of a plurality of types of metal alkoxides. What is unevenly distributed in the structure of M ¹ and M ² is a structure found in core-shell particles (particles having metal oxide fine particles as nuclei and having other metal oxide shells outside the nuclei) For example, it is formed by hydrolyzing a plurality of types of metal alkoxides in stages according to the type.

  Examples of the metal oxide used in the present invention include silicon oxide, aluminum oxide, titanium oxide, zinc oxide, cerium oxide, tin oxide, boron oxide, and indium oxide. When these inorganic oxide colloid aqueous dispersions are added to, for example, coating paints, one or more metal oxides are usually used depending on the purpose. It does not prevent the colloidal aqueous dispersion from containing a plurality of types of metal oxides. Examples of the purpose of adding the inorganic oxide colloid aqueous dispersion to the coating paint include imparting mechanical properties, imparting ultraviolet shielding properties, imparting electrical conductivity, and the like. In order to impart mechanical properties, a composite oxide containing one or more of silicon oxide, aluminum oxide, tin oxide, boron oxide and metal elements constituting them is often used. In order to impart UV shielding properties, titanium oxide, zinc oxide, cerium oxide, etc. are often used, and in combination with silicon oxide, aluminum oxide, tin oxide, etc. for imparting mechanical properties. You can also. In order to impart electric conductivity, an indium oxide-tin oxide composite is often used. In any case, these metal oxides can provide various functions, but the chemical engineering aspects of the inorganic oxide colloidal aqueous dispersion are similar. When considering the solvent replacement of the colloidal aqueous dispersion, it is possible to treat the metal oxides listed here alone or in combination of two or more as a group.

Types of Inorganic Oxide Colloidal Aqueous Dispersion Inorganic oxide colloidal aqueous dispersions have various functions depending on the type of dispersoid. Various functionalities include, for example, mechanical properties that can impart scratch resistance and flexibility when added to a coating composition, light refractive index controllability, ultraviolet shielding properties, radiation shielding properties, fluorescence properties, etc. These are the optical characteristics that can be applied, electrical properties that can provide electrical conductivity and dielectric constant, and the like. As described above, the inorganic oxide colloidal aqueous dispersion has various functions as long as there are various types of elements constituting the inorganic oxide colloidal water dispersion. However, the chemical engineering aspects of the inorganic oxide colloidal aqueous dispersion are similar, and therefore, when considering solvent replacement of the inorganic oxide colloidal aqueous dispersion, the metal oxides listed here and the like A single type of inorganic oxide or a combination of two or more types can be handled as a group. A chemical engineering aspect is a physical property discussed in the category of powder engineering or migration phenomenology, such as particle size of a dispersoid, zeta potential, and the like. As long as these physical quantities are used for discussion, the inorganic oxide colloidal aqueous dispersion can be recognized as a parallel set that can be compared with each other even if the types of elements constituting the dispersoid are different. Accordingly, inorganic oxide colloidal water not described in detail in the present specification and examples is not described because all types and / or combinations of inorganic oxide (metal oxide) colloidal aqueous dispersions are not described in detail. The dispersion liquid is not prevented from being included in the scope of the present invention.

The particle size (average cumulative particle size) of the dispersoid of the inorganic oxide colloid aqueous dispersion can be measured by various methods. The particle diameter range in the present invention is discussed as a volume-based 50% cumulative particle diameter (D ₅₀ ) measured by a dynamic light scattering method using laser light. It is also possible to observe. The values obtained by these measuring methods are not dependent on the measuring device, but for example, a device such as Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) can be used as the dynamic light scattering method. . Further, as an electron microscope method, a transmission electron microscope H-9500 (manufactured by Hitachi High-Technologies Corporation) can be exemplified as an apparatus. For example, when an inorganic oxide colloid aqueous dispersion is added to a coating material, transparency in the visible region is important, so the average cumulative particle size of the dispersoid is preferably 1 to 200 nm, and preferably 1 to 100 nm. Is more preferable, it is still more preferable that it is 1-80 nm, and it is especially preferable that it is 1-50 nm. When the average cumulative particle diameter of the dispersoid exceeds 200 nm, the particle diameter becomes larger than the light wavelength in the visible region, and scattering may be significant. On the other hand, when the thickness is less than 1 nm, the total surface area in the dispersoid system may be extremely large, which may make it difficult to handle the inorganic oxide colloid water dispersion.

  The zeta potential (ζ) of inorganic oxide colloidal aqueous dispersion shows the migration phenomenon of dispersoid particles when an electric field is applied to the solid-liquid interface having an electric double layer. Recognized as a value proportional to degrees. The zeta potential can be measured by various methods, and examples of an apparatus for measuring such a value include ELS-3000 (manufactured by Otsuka Electronics Co., Ltd.). For organosols such as the present invention, there are various ranges of dielectric constants of organic solvents. Since the zeta potential is a function that also depends on the dielectric constant, in such a case, the dielectric constant may be measured. As a dielectric constant measuring apparatus, Model-871 (manufactured by Nippon Luft Co., Ltd.) can be exemplified. The zeta potential is often in the range of −200 <ζ <200 in units of mV. The zeta potential indicates that the larger the absolute value, the more stable the dispersion system of the inorganic oxide colloid aqueous dispersion. Therefore, the absolute value (| ζ |) of the zeta potential is preferably 3 mV or more, more preferably 10 mV or more, and further preferably 20 mV or more. If the absolute value of the zeta potential (| ζ |) is less than 3 mV, the dispersion stability of the dispersoid of the inorganic oxide colloid aqueous dispersion may not be sufficient. The upper limit of the absolute value (| ζ |) of the zeta potential is not particularly defined, but usually has a physical limit (about 200 mV).

Dispersion medium of inorganic oxide colloid aqueous dispersion The inorganic oxide colloid aqueous dispersion prepared in the step (A) of the present invention is characterized by using water as a dispersion medium. As water, fresh water such as tap water, industrial water, well water, natural water, rain water, distilled water, ion-exchanged water and the like can be used, and ion-exchanged water is particularly preferable. Ion-exchanged water can be produced using a pure water production device (for example, product name “FW-10” manufactured by Organo Corporation, product name “Direct-QUV3” manufactured by Merck Millipore Corporation), etc.). . Further, the dispersion medium may contain a monohydric alcohol that is arbitrarily miscible with water in the step of producing the inorganic oxide colloid aqueous dispersion as described below. The monohydric alcohol that is optionally miscible with water may be contained as a co-solvent in producing the core-shell fine particles and the origin as a hydrolysis by-product of the metal alkoxide in the sol-gel reaction. The monohydric alcohol arbitrarily miscible with water is preferably contained in an amount of 0% by mass to 30% by mass with respect to water, more preferably 0% by mass to 25% by mass, and 0% by mass. % To 20% by mass is more preferable. If the content of monohydric alcohol arbitrarily miscible with water is more than 30% by mass, it may act as a compatibilizer for alcohol that is not completely compatible with water added in step (B). There may not be.

Concentration of inorganic oxide colloid aqueous dispersion The concentration of the inorganic oxide colloid aqueous dispersion prepared in the step (A) of the present invention is preferably 1% by mass to 35% by mass, more preferably 5% by mass to 30% by mass. % Or less, more preferably 10 mass% or more and 25 mass% or less. When the concentration of the inorganic oxide colloid aqueous dispersion is lower than 1% by mass, the production efficiency may not be good, which is not preferable. When the concentration of the inorganic oxide colloid aqueous dispersion is higher than 35% by mass, gelation may be easily caused depending on conditions such as pH and temperature. The concentration mentioned here should be understood as the ratio of the mass of the dispersoid contained in the entire inorganic oxide colloidal aqueous dispersion (the sum of the mass of the dispersoid and the dispersion medium) expressed as 100 fractions. . The concentration can be determined from a change in mass when a certain amount of the inorganic oxide colloid aqueous dispersion is weighed and the dispersion medium is forcibly dried.

Inorganic oxide colloidal aqueous dispersion containing core-shell fine particles As the inorganic oxide colloidal aqueous dispersion used in the present invention, in particular, a core of one or a combination of two or more of the metal element oxides described above is used. It is preferable to use a colloidal aqueous dispersion containing core-shell fine particles having a shell of one or a combination of two or more of the above-described metal element oxides on the outside of the core. As such a core-shell fine particle-containing colloidal water dispersion, a colloidal water dispersion containing core-shell fine particles having titanium oxide as a nucleus and a silicon oxide shell outside the nucleus, particularly titanium oxide-tin oxide and / or manganese oxide. Examples thereof include a colloidal aqueous dispersion containing a core-shell fine particle having a complex oxide (titanium oxide fine particles in which tin and / or manganese is solid-dissolved) as a nucleus and a silicon oxide shell outside the nucleus. Hereinafter, the core-shell fine particles (core-shell type tetragonal titanium oxide solid solution) colloidal aqueous dispersion used in the present invention will be described in detail.

Core-shell type tetragonal titanium oxide solid solution (fine particles) colloidal water dispersion Core-shell type tetragonal titanium oxide solid solution colloidal water dispersion has a core of tetragonal titanium oxide fine particles in which tin and / or manganese is solid-solved as a nucleus. It is preferable that a core-shell type tetragonal titanium oxide solid solution having a silicon oxide shell outside is dispersed in an aqueous dispersion medium such as water.

  Here, there are usually three types of titanium oxide: rutile type, anatase type, and brookite type. In the present invention, tetragonal rutile type titanium oxide having low photocatalytic activity and excellent ultraviolet absorption ability is replaced with tin and titanium oxide. It is preferable to use it as a solid solvent for manganese.

  The tin component as a solid solute may be derived from a tin salt, and examples thereof include tin chalcogenides such as tin oxide and tin sulfide, and tin oxide is preferable. Tin salts include tin halides such as tin fluoride, tin chloride, tin bromide and tin iodide, tin pseudohalides such as tin cyanide and tin isothiocyanide, or tin nitrate, tin sulfate and tin phosphate. Tin mineral acid salt and the like can be used, but it is preferable to use tin chloride from the viewpoint of stability and availability. Further, tin in the tin salt can be selected from divalent to tetravalent valences, but it is particularly preferable to use tetravalent tin.

  The manganese component as the solid solute may be derived from a manganese salt, and examples thereof include manganese chalcogenides such as manganese oxide and manganese sulfide, and manganese oxide is preferable. Manganese salts include manganese halides such as manganese fluoride, manganese chloride, manganese bromide, and manganese iodide; manganese pseudohalides such as manganese cyanide and manganese isothiocyanide; manganese such as manganese nitrate, manganese sulfate, and manganese phosphate. A mineral acid salt or the like can be used, but it is preferable to use manganese chloride from the viewpoint of stability and availability. Further, manganese in the manganese salt can be selected from divalent to heptovalent valences, but it is particularly preferable to use divalent manganese.

  When tin and manganese are dissolved in tetragonal titanium oxide, the solid solution amount of the tin component is preferably 10 to 1,000, more preferably 20 to 200, in terms of a molar ratio with titanium (Ti / Sn). The solid solution amount of the manganese component is preferably 10 to 1,000, more preferably 20 to 200, in terms of a molar ratio (Ti / Mn) with titanium. When the solid solution amount of the tin component and the manganese component is less than 10 in terms of the molar ratio with titanium (Ti / Sn) and (Ti / Mn), light absorption in the visible region derived from tin and manganese becomes prominent. If it exceeds 1,000, the photocatalytic activity is not sufficiently deactivated, and the crystal system becomes an anatase type having a small visible absorption ability, which is not preferable. In addition, the solid solution amount of the tin component and the solid solution amount of the manganese component in the case where either one of tin and manganese is dissolved in tetragonal titanium oxide are the same as the above values.

  The solid solution mode of the tin component and the manganese component may be a substitution type or an interstitial type. Here, the substitution type is a solid solution mode formed by substituting tin and manganese at the site of titanium (IV) ions of titanium oxide, and the interstitial type is between the crystal lattices of titanium oxide. It is a solid solution mode formed by the presence of tin and manganese. In the interstitial type, an F center that causes coloration is easily formed, and since the symmetry around the metal ion is poor, the Frank-Condon factor of vibronic transition in the metal ion is increased, and visible light is easily absorbed. Therefore, the substitution type is preferable.

  The shell of silicon oxide formed outside the core of tetragonal titanium oxide fine particles with solid solution of tin and / or manganese may contain silicon oxide as the main component and other components such as tin and aluminum. , Any method may be used. For example, the silicon oxide shell can be formed by hydrolytic condensation of tetraalkoxysilane. As tetraalkoxysilane, tetramethoxysilane, tetraethoxysilane, tetra (n-propoxy) silane, tetra (i-propoxy) silane, tetra (n-butoxy) silane and the like, which are usually available, may be used. Tetraethoxysilane is preferably used from the viewpoint of reactivity and safety. As such a thing, commercially available "KBE-04" (made by Shin-Etsu Chemical Co., Ltd.) can be used, for example. The hydrolysis and condensation of tetraalkoxysilane may be performed in water, and a condensation catalyst such as ammonia, aluminum salt, organoaluminum, tin salt, or organotin may be used as appropriate. Ammonia is used as a dispersant for the core fine particles. It is particularly preferable because it also has the above action.

  The ratio of the silicon oxide in the shell to the whole of the core-shell type tetragonal titanium oxide solid solution having the core of tetragonal titanium oxide fine particles in which tin and / or manganese are solid-solved and having a silicon oxide shell outside the nucleus is It is 20-50 mass%, Preferably it is 25-45 mass%, More preferably, it is 30-40 mass%. When the amount is less than 20% by mass, the formation of the shell is insufficient. On the other hand, when the amount exceeds 50% by mass, the aggregation of the particles is promoted and the dispersion becomes opaque.

50% cumulative particle diameter of core-shell type tetragonal titanium oxide solid solution based on volume of tetragonal titanium oxide fine particles with solid solution of tin and / or manganese as cores measured by dynamic light scattering method using laser light (D ₅₀ ) is 30 nm or less, more preferably 20 nm or less, and the volume-based 50% cumulative particle diameter (D ₅₀ ) of the core-shell type tetragonal titanium oxide solid solution is 50 nm or less, more preferably 30 nm or less. . When the D ₅₀ value of the core fine particles and the core-shell solid solution exceeds the upper limit, the dispersion becomes opaque, which is not preferable. Further, the lower limit value of D ₅₀ of the above-mentioned core fine particles is not particularly limited, but usually, the lower limit value of D _{50 of the} core-shell type solid solution is 6 nm or more. An example of an apparatus for measuring such a volume-based 50% cumulative particle diameter (D ₅₀ ) is Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) (hereinafter the same).

  Examples of the aqueous dispersion medium in which the core-shell type tetragonal titanium oxide solid solution is dispersed include water and a mixed solvent of water and a hydrophilic organic solvent mixed at an arbitrary ratio. As water, for example, deionized water (ion exchange water), distilled water, pure water and the like are preferable. As the hydrophilic organic solvent, for example, alcohols such as methanol, ethanol, and isopropanol are preferable. In this case, the mixing ratio of the hydrophilic organic solvent is preferably 0 to 30% by mass in the aqueous dispersion medium. If it exceeds 30% by mass, it may act as a compatibilizing agent for alcohol that is not completely compatible with water in step (B), which may be undesirable. Among these, deionized water and pure water are most preferable from the viewpoints of productivity and cost.

  In the core-shell type tetragonal titanium oxide solid solution colloid aqueous dispersion formed from the core-shell type tetragonal titanium oxide solid solution and the aqueous dispersion medium, the concentration of the core-shell type tetragonal titanium oxide solid solution is 0.1% by mass or more. Less than 10 mass% is preferable, More preferably, it is 0.5-5 mass%, More preferably, it is 1-3 mass%. The aqueous dispersion medium is allowed to contain a basic substance (dispersant) used in the process of producing a core-shell type tetragonal titanium oxide solid solution described later. In particular, since the basic substance has properties as a pH adjusting agent and a dispersing agent, it may be used in an aqueous solution having an appropriate concentration together with the aqueous dispersion medium. However, the core-shell type tetragonal titanium oxide solid solution colloidal aqueous dispersion contains a dispersant (basic substance) other than ammonia, alkali metal hydroxide, phosphate compound, hydrogen phosphate compound, carbonate compound and bicarbonate compound. It is preferable not to contain. This is because it is not necessary to dare to use a polymer dispersing agent that has been conventionally used as a dispersing agent for titanium oxide fine particles by containing the basic substance. This is because it is possible to avoid the inhibition of the scratch resistance of the coating film (cured film) and the adhesion to the base material, which were generated when the titanium oxide fine particle dispersing agent containing sapphire is applied to the coating agent.

  Examples of the basic substance (dispersant) in such a core-shell type tetragonal titanium oxide solid solution aqueous dispersion include ammonia, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, and dihydrogen phosphate. Lithium, monosodium dihydrogen phosphate, monopotassium dihydrogen phosphate, dicesium dihydrogen phosphate, dilithium hydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dicesium hydrogen phosphate, triphosphate Examples include lithium, trisodium phosphate, tripotassium phosphate, tricesium phosphate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, etc. In particular, ammonia and sodium hydroxide are preferred.

  The core-shell type tetragonal titanium oxide solid solution colloidal aqueous dispersion having such a configuration has high transparency, for example, an optical path length filled with a core-shell type tetragonal titanium oxide solid solution colloidal aqueous dispersion having a concentration of 1% by mass. The transmittance of light having a wavelength of 550 nm passing through a 1 mm quartz cell is usually 80% or more, more preferably 85% or more, and still more preferably 90% or more. Such transmittance can be easily obtained by measuring an ultraviolet-visible transmission spectrum.

  In particular, the core shell type tetragonal titanium oxide solid solution colloidal aqueous dispersion manufacturing method in which tin and / or manganese is dissolved as described below is used to obtain mechanical solutions such as pulverization and classification in the manufacturing process when obtaining the solid solution. In spite of not having passed unit operation, since it can be set as the said specific cumulative particle diameter, not only production efficiency is very high but said high transparency can be ensured.

Method for Producing Core-Shell Type Tetragonal Titanium Oxide Solid Solution Colloidal Water Dispersion A method for producing core-shell type tetragonal titanium oxide solid solution aqueous dispersion in which tin and / or manganese having the above-described configuration is dissolved is as follows. ), (B).
・ Process (I)
In this step, first, an aqueous dispersion of tetragonal titanium oxide solid solution fine particles in which a tin component and / or a manganese component are dissolved in tetragonal titanium oxide is prepared. The method for obtaining this water dispersion is not particularly limited, but the titanium compound, tin compound, manganese compound, basic substance and hydrogen peroxide as raw materials are reacted in an aqueous dispersion medium, and then tin and / or manganese are used. A method of obtaining a tetragonal titanium oxide fine particle dispersion in which tin and / or manganese is solid-solved is obtained by hydrothermally treating the peroxotitanic acid solution containing.

  The reaction until obtaining the peroxotitanic acid solution containing tin and / or manganese in the previous stage is performed by adding a basic substance to the raw material titanium compound in the aqueous dispersion medium to form titanium hydroxide, and removing impurity ions contained therein, The raw material titanium compound in the aqueous dispersion medium can also be obtained by adding hydrogen peroxide to form peroxotitanic acid and then adding a tin compound and / or manganese compound to form a peroxotitanic acid solution containing tin and / or manganese. After adding a tin compound and / or a manganese compound to the above, a basic substance is added to form titanium hydroxide containing tin and / or manganese, impurity ions contained are removed, hydrogen peroxide is added, and tin and / or Alternatively, a peroxotitanic acid solution containing manganese may be used.

  Here, as the raw material titanium compound, for example, inorganic acid salts such as titanium hydrochloride, nitrate and sulfate, organic acid salts such as formic acid, citric acid, succinic acid, lactic acid and glycolic acid, alkalis are added to these aqueous solutions. Examples thereof include titanium hydroxide precipitated by hydrolysis by addition, and these may be used alone or in combination of two or more.

  As a tin compound and / or a manganese compound, the above-mentioned tin salt and / or manganese salt are used so that it may become the above-mentioned solid solution amount, respectively. In addition, the aqueous dispersion medium and the basic substance are also used so that the above-mentioned compounds have the aforementioned composition.

  Hydrogen peroxide is used to convert the above raw material titanium compound or titanium hydroxide into peroxotitanium, that is, a titanium oxide-based compound containing a Ti—O—O—Ti bond. used. The amount of hydrogen peroxide added is preferably 1.5 to 5 times the total number of moles of titanium, tin and manganese. Further, the reaction temperature in the reaction of adding hydrogen peroxide to convert the raw material titanium compound or titanium hydroxide to peroxotitanic acid is preferably 5 to 60 ° C., and the reaction time is 30 minutes to 24 hours. It is preferable.

  The peroxotitanic acid solution containing tin and / or manganese thus obtained may contain a basic substance or an acidic substance for pH adjustment or the like. Examples of the basic substance herein include ammonia, and examples of the acidic substance include inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, carbonic acid, phosphoric acid, and hydrogen peroxide, formic acid, citric acid, and oxalic acid. , Organic acids such as lactic acid and glycolic acid. In this case, the pH of the obtained peroxotitanic acid solution containing tin and / or manganese is preferably 1 to 7, particularly 4 to 7 from the viewpoint of handling safety.

  Subsequently, the reaction until obtaining a tetragonal titanium oxide fine particle dispersion in which tin and / or manganese described below are solid-dissolved is carried out using the above-mentioned peroxotitanic acid solution containing tin and / or manganese at a pressure of 0.01 to 4. It is subjected to a hydrothermal reaction under conditions of 5 MPa, preferably 0.15 to 4.5 MPa, a temperature of 80 to 250 ° C., preferably 120 to 250 ° C., and a reaction time of 1 minute to 24 hours. As a result, peroxotitanic acid containing tin and / or manganese is converted into tetragonal titanium oxide fine particles in which tin and / or manganese are dissolved.

  In the present invention, tetraalkoxy titanium oxide fine particle dispersion in which tin and / or manganese thus obtained are solid-dissolved is mixed with monohydric alcohol, ammonia, and tetraalkoxysilane such as tetraethoxysilane.

  As the monohydric alcohol, methanol, ethanol, propanol, isopropyl alcohol, and any mixture thereof are used, and ethanol is particularly preferably used. Such a monohydric alcohol is used in an amount of 100 parts by mass or less, preferably 30 parts by mass or less, with respect to 100 parts by mass of the titanium oxide fine particle dispersion. In particular, by changing the blending amount of monohydric alcohol, in the next step, the thickness of the silicon oxide shell formed outside the nucleus composed of tetragonal titanium oxide fine particles in which tin and / or manganese is dissolved is controlled. It becomes possible. In general, if the amount of monohydric alcohol is increased, the solubility of the silicon reagent such as tetraalkoxysilane in the reaction system is increased while the dispersion of titanium oxide is not adversely affected. Become thicker. That is, the core-shell type tetragonal titanium oxide solid solution aqueous dispersion in which tin and / or manganese obtained in the next step is solid solution is not subjected to mechanical unit operations such as pulverization and classification in the production process. It can be in the range of the specific cumulative particle diameter, and can impart transparency in the visible region. The blending amount of the monohydric alcohol is preferably 30 parts by mass or less, but even if it contains more alcohol than this, it is possible to selectively remove the alcohol in the concentration step. Necessary operations can be added.

  Ammonia is ammonia water, which may be replaced with addition of ammonia water by blowing ammonia gas into a tetragonal titanium oxide fine particle dispersion in which tin and / or manganese are solid-dissolved, and further ammonia in the dispersion. It may be replaced with the addition of aqueous ammonia by adding a reactant capable of generating. The concentration of the ammonia water is not particularly limited, and any commercially available ammonia water may be used. In the process of the present invention, for example, the pH of the tetragonal titanium oxide fine particle dispersion in which tin and / or manganese is solid-solved using 28% by mass of concentrated aqueous ammonia is 9 to 12, more preferably 9.5. It is preferable to add ammonia water to an amount of ˜11.5.

  As the tetraalkoxysilane, those described above can be used, and tetraethoxysilane is preferable. In addition to itself, tetraethoxysilane (partial) hydrolyzate can also be used as tetraethoxysilane. Such a tetraethoxysilane or a (partial) hydrolyzate of tetraethoxysilane may be any commercially available product. For example, trade name “KBE-04” (tetraethoxysilane: manufactured by Shin-Etsu Chemical Co., Ltd.) ), Trade names "silicate 35", "silicate 45" (tetrahydrosilane partial hydrolysis condensate: manufactured by Tama Chemical Industry Co., Ltd.), trade names "ESI40", "ESI48" (tetraethoxysilane partial hydrolysis) Condensate: Colcoat Co., Ltd.) may be used. These tetraethoxysilanes or the like may be used alone or in combination.

  The tetraalkoxysilane is used in an amount of 20 to 50% by mass, preferably 25 to 45% by mass, more preferably 30 to 40% by mass with respect to titanium oxide containing silicon oxide after hydrolysis. When the amount is less than 20% by mass, the formation of the shell is insufficient. When the amount is more than 50% by mass, the aggregation of the particles is promoted and the dispersion may become opaque.

  What is the method of adding tetraalkoxysilane such as monohydric alcohol, ammonia, and tetraethoxysilane to the tetragonal titanium oxide fine particle dispersion in which tin and / or manganese are solid-dissolved? For example, magnetic stirring, mechanical stirring, shaking stirring, etc. can be used.

・ Process (b)
Here, by rapidly heating the mixture obtained in the step (a), tetragonal titanium oxide fine particles in which tin and / or manganese are solid-solved are used as nuclei, and a silicon oxide shell is formed outside the nuclei. Core-shell type tetragonal titanium oxide solid solution fine particles are formed.

  The method for rapidly heating the mixture obtained in step (a) may be any existing method, such as microwave heating, a microreactor capable of achieving high heat exchange efficiency, and an external having a large heat capacity. Heat exchange with a heat source or the like can be used. In particular, a heating method using a microwave is preferable because it allows uniform and rapid heating. In addition, the process of irradiating and heating microwaves may be a batch process or a continuous process.

  In the rapid heating method, it is preferable that the time from reaching room temperature to just below the boiling point of the dispersion medium (usually about 10 to 80 ° C.) is within 10 minutes. This is because when the heating method exceeds 10 minutes, the particles are aggregated, which is not preferable.

  When microwave heating is used for such a rapid heating method, for example, the frequency can be appropriately selected from electromagnetic waves having a frequency of 300 MHz to 3 THz. In Japan, the microwave frequency band that can be normally used is determined by the radio wave law to 2.45 GHz, 5.8 GHz, 24 GHz, etc., but 2.45 GHz is often used for consumer use. Therefore, the magnetron for oscillation at this frequency is advantageous in terms of equipment cost. However, this standard depends on the laws and economic conditions of specific countries and regions, and technically does not limit the frequency. As long as the microwave output has a rating of 100 W to 24 kW, preferably 100 W to 20 kW, any commercially available apparatus may be used. For example, μReactorEx (manufactured by Shikoku Keiki Kogyo Co., Ltd.), Advanced (manufactured by Biotage Co., Ltd.) and the like can be used.

  In order to keep the time required for heating within 10 minutes during microwave heating, the output of the microwave is adjusted, or the reaction liquid volume is adjusted appropriately for batch reactions and the reaction flow rate is adjusted for continuous reactions. Can be done.

  The core-shell type tetragonal titanium oxide solid solution colloidal aqueous dispersion obtained by solidly dissolving tin and / or manganese thus obtained can be suitably used for producing the organosol of the present invention.

As described so far, the inorganic oxide colloidal aqueous dispersion can be produced in-house, but a commercially available one can also be used. For example, the Snowtex (registered trademark) series manufactured by Nissan Chemical Industries, Ltd. or an aqueous alumina sol can be used as the aqueous silica sol.
In this case, the volume-based 50% cumulative particle diameter (D ₅₀ ) measured by a dynamic light scattering method using laser light is preferably 10 nm or more and 100 nm or less, more preferably 12 nm or more and 80 nm or less. When the D ₅₀ value of the dispersoid of the inorganic oxide colloidal aqueous dispersion exceeds the upper limit, it may easily become cloudy, and when it is less than the lower limit, it may easily aggregate.

  The solid content concentration of the inorganic oxide colloid aqueous dispersion is preferably 1% by mass to 30% by mass, more preferably 5% by mass to 25% by mass, and still more preferably 10% by mass to 20% by mass. It is as follows. If it is less than 1% by mass, it may not be preferable from the industrial efficiency in organosol production, and if it exceeds 30% by mass, the inorganic oxide colloidal aqueous dispersion may lose its fluidity and become gelled. There is a case.

  The liquidity of the inorganic oxide colloidal aqueous dispersion is preferably a pH of 2 or more and 12 or less, more preferably a pH of 3 or more and 11 or less, and further preferably 4 or more and 10 or less. If the pH is less than 2 or more than 12, the inorganic oxide colloidal aqueous dispersion may lose its fluidity and gel, which may be undesirable.

Process (B)
Step (B) is a step of adding an alcohol that is not completely compatible with water and forms a two-phase system. Under normal conditions, the alcohol added here is not mixed with the inorganic oxide colloidal aqueous dispersion, and the inorganic oxide dispersoid in the dispersion does not migrate into the alcohol.

  The alcohol added in the step (B) is a linear, branched or cyclic monovalent alcohol which may contain an aromatic group having 4 to 8 carbon atoms, and 3 to 8 carbon atoms. It is preferable that it is 1 type, or 2 or more types selected from the group consisting of monovalent alcohols substituted (partially) with fluorine atoms. Alcohols having 2 or less carbon atoms cannot be used in this step because they are miscible with water under normal conditions. On the other hand, when the number of carbon atoms is larger than 8, it is not preferable because the properties as paraffin are enhanced and application in this step may be difficult. It is more preferably a linear, branched, or cyclic monovalent alcohol that may contain an aromatic group having 4 to 8 carbon atoms. The substitution with a fluorine atom may be either a fully substituted (perfluoroalkyl) type or a partially substituted type. In a long-chain alkyl group, a fully substituted alcohol is expensive, and the number of substitutions can be adjusted according to the cost. If the valence of the alcohol is greater than 2, the water solubility tends to be strong, and the viscosity is increased, making it difficult to handle.

  Specific examples of the alcohol added in the step (B) include 1-butanol, 2-butanol, isobutyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, neopentyl alcohol, cyclopentanol, 1-butanol, Fragrances such as hexanol, 2-hexanol, 3-hexanol, tert-hexyl alcohol, cyclohexanol, etc., straight chain, branched chain, cyclic alcohols, phenol, o-cresol, m-cresol, p-cresol, benzyl alcohol, etc. Cyclic alcohols, heptafluoropropan-1-ol, heptafluoropropan-2-ol, 3,3,4,4,4-pentafluorobutan-1-ol, nonafluorobutan-1-ol, nonafluorobutane- (Partially) substituted with a fluorine atom such as 2-ol Chain, or a cyclic alcohols.

  In the step (B), the solubility of the alcohol to be added in water at 20 ° C. is preferably 1 (alcohol 1 g / water 100 g) or more and 30 (alcohol 30 g / water 100 g) or less, preferably 5 or more and 28 or less. Is more preferably 10 or more and 26 or less. If it is less than 1, the effect of the present invention may not be exhibited, and if it exceeds 30, it may be completely compatible by the action of an alcohol that is arbitrarily mixed with water used in step (A).

  In the step (B), the solubility of the alcohol to be added in water can be measured according to a conventional method. For example, the alcohol is placed in a burette at 20 ° C. and added dropwise to a conical beaker containing 100 g of pure water with good stirring. When the alcohol cannot be dissolved and a two-phase system is formed, the dropping is finished. The amount of weight increase at that time is the solubility of the alcohol in 100 g of water.

  In the step (B), the addition amount of the alcohol to be added is preferably 10 parts by mass or more and 1,000 parts by mass or less with respect to 100 parts by mass of the water component of the inorganic oxide colloid aqueous dispersion used in the step (A). More preferably, they are 15 to 500 mass parts, More preferably, they are 20 to 300 mass parts. If the amount added is less than 10 parts by mass, the extraction efficiency may not be high. When the addition amount is more than 1,000 parts by mass, there are industrial and environmental problems due to the use of a large amount of organic solvent.

Process (C)
Step (C) is a step of adding an organosilicon compound represented by the following general formula (1) and / or (partial) hydrolysis condensate thereof.
R ¹ _p R ² _q R ³ _r Si (OR ⁴ ) _4-pqr (1)
(In the formula, R ¹ is a hydrogen atom, non-substituted or substituted carbon atoms 1 to 20 monovalent hydrocarbon group, a silicon atom number of 50 or less polydimethylsiloxane group, or an isocyanurate group, R ^2, R ³ and R ⁴ are each an alkyl group having 1 to 6 carbon atoms, p is an integer of 1 to 3, q is 0, 1 or 2, r is 0, 1 or 2, and p + q + r is 1 to 3. (It is an integer.)

In the above formula (1), R ¹ is a hydrogen atom, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, particularly 1 to 10 carbon atoms, and 1 to 50 silicon atoms, particularly 5 to 40 carbon atoms. In particular, it is a polydimethylsiloxane group or isocyanurate group of 10 or more and 30 or less, specifically a hydrogen atom; a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or an n-pentyl group. Alkyl groups such as n-hexyl group, n-heptyl group, n-octyl group and n-decyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; alkenyl groups such as vinyl group and allyl group; Aryl group; halogen-substituted hydrocarbon group such as chloromethyl group, γ-chloropropyl group, 3,3,3-trifluoropropyl group, perfluorooctylethyl group; γ-acryloyloxypropyl group, γ-methacryloyloxypropyl group, γ-glycidoxypropyl group, 3,4-epoxycyclohexylethyl group, γ-mercaptopropyl group, γ-aminopropyl group, N- (2-aminoethyl) ) (Meth) acryloyloxy such as aminopropyl group and γ-isocyanatopropyl group, epoxy, mercapto, amino, isocyanate group-substituted hydrocarbon group; polydimethylsiloxane group; isocyanurate group and the like. Moreover, the isocyanurate group which the isocyanate groups of several isocyanate group substituted hydrocarbon groups couple | bonded can also be illustrated. Among these, n-propyl group, vinyl group, γ-acryloyloxypropyl group, γ-methacryloyloxypropyl group, and triisocyanurate are particularly preferable.

R ² , R ³ and R ⁴ are each an alkyl group having 1 to 6 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-pentyl group. N-hexyl group, cyclopentyl group, cyclohexyl group and the like. Among these, R ² and R ³ are preferably a methyl group, and R ⁴ is preferably a methyl group or an ethyl group.

  p is an integer of 1 to 3, preferably 1, q is 0, 1 or 2, preferably 0, r is 0, 1 or 2, preferably 0, and p + q + r is an integer of 1 to 3, preferably 1. is there.

  Specific examples of the organosilicon compound represented by the general formula (1) and its (partial) hydrolysis condensate include hydrogentrimethoxysilane, hydrogentriethoxysilane, methyl when p = 1, q and r = 0. Trimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltriisopropoxysilane, phenyltrimethoxy Silane, vinyltrimethoxysilane, allyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-acryloyloxypropyltrimethoxy Run, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-chloropropyltrimethoxysilane, 3,3,3 -Trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltri Ethoxysilane, N- (2-aminoethyl) aminopropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, tris (3-trimethoxysilane) in which isocyanate groups are bonded to each other Rupropyl) isocyanurate, tris (3-triethoxysilylpropyl) isocyanurate, methyltrimethoxysilane partially hydrolyzed condensate (trade names “KC-89S”, “X-40-9220” manufactured by Shin-Etsu Chemical Co., Ltd.) ), A partial cohydrolysis condensate of methyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane (trade name “X-41-1056” manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

In addition, as an organic silicon compound represented by the general formula (1), p = 1, q, r = 0, and R ¹ is a polydimethylsiloxane group, for example, the following general formula (4) Mention may be made of the compounds represented. In the general formula (4), s is preferably an integer of 1 to 50, more preferably an integer of 5 to 40, and still more preferably an integer of 10 to 30. When s is larger than 50, the properties as a silicone oil become strong, and the solubility of the surface-treated organosol in various resins may be limited. In the general formula (4), a compound having an average structure of s = 30 can be obtained as a trade name “X-24-9822” (manufactured by Shin-Etsu Chemical Co., Ltd.).

  Specific examples of the organosilicon compound represented by the general formula (1) include, when p = 1, q = 1, and r = 0, methyl hydrogen dimethoxy silane, methyl hydrogen diethoxy silane, dimethyl dimethoxy silane, dimethyl Diethoxysilane, methylethyldimethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, methylpropyldimethoxysilane, methylpropyldiethoxysilane, diisopropyldimethoxysilane, phenylmethyldimethoxysilane, vinylmethyldimethoxysilane, γ-glycidoxypropylmethyl Dimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldimethoxy Silane, .gamma.-methacryloyloxy propyl methyl diethoxy silane, .gamma.-mercaptopropyl methyl dimethoxy silane, .gamma.-aminopropyl methyl diethoxy silane, N- (2- aminoethyl) and aminopropyl methyl dimethoxy silane and the like.

  Specific examples of the organic silicon compound represented by the general formula (1) include trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, and n-propyldimethylmethoxysilane when p = 1, q = 1, and r = 1. N-propyldiethylmethoxysilane, n-propyldimethylethoxysilane, isopropyldimethylmethoxysilane, isopropyldiethylmethoxysilane, isopropyldimethylethoxysilane, n-butyldimethylmethoxysilane, n-butyldimethylethoxysilane, n-pentyldimethylmethoxysilane , N-pentyldimethylethoxysilane, n-hexyldimethylmethoxysilane, n-hexyldimethylethoxysilane, n-decyldimethylmethoxysilane, n-decyldimethylethoxysilane, etc. It can be mentioned.

  The amount of silane added in the step (C) is preferably 1% by mass or more and 50% by mass or less, more preferably 3% by mass with respect to the solid content of the inorganic oxide colloid aqueous dispersion in the step (A). % To 40% by mass, more preferably 5% to 30% by mass. When the addition amount is more than 50% by mass, the proportion of the inorganic oxide that is an active ingredient in the organosol is relatively reduced, which is not preferable in terms of industrial efficiency. When the addition amount is less than 1% by mass, it may be difficult to ensure the dispersion stability of the inorganic oxide fine particles in the organic solvent.

  The addition method of the silane in a process (C) can implement dripping in a liquid, liquid dripping, a potion addition, etc., and it is preferable that it is dripping in a liquid.

  The liquid temperature at the time of silane addition in the step (C) is preferably 0 ° C. or higher and 45 ° C. or lower, more preferably 5 ° C. or higher and 40 ° C. or lower, and further preferably 10 ° C. or higher and 35 ° C. or lower. When the liquid temperature is lower than 0 ° C., there is a possibility that the inorganic oxide colloidal aqueous dispersion is deteriorated through a state change due to freezing. When the liquid temperature is higher than 45 ° C., the added organosilicon compound may cause an unexpected hydrolysis condensation reaction.

Process (D)
Step (D) is a step of irradiating microwaves. The microwave irradiation can be appropriately selected from electromagnetic waves having a frequency of 300 MHz to 3 THz. In Japan, the microwave frequency band that can be normally used is determined by the radio wave law to 2.45 GHz, 5.8 GHz, 24 GHz, etc., but 2.45 GHz is often used for consumer use. Therefore, the magnetron for oscillation at this frequency is advantageous in terms of equipment cost. However, this standard depends on the laws and economic conditions of specific countries and regions, and technically does not limit the frequency. As long as the microwave output has a rating of 100 W to 24 kW, preferably 100 W to 20 kW, any commercially available apparatus may be used. For example, μReactorEx (manufactured by Shikoku Keiki Kogyo Co., Ltd.), Advanced (manufactured by Biotage Co., Ltd.) and the like can be used.

  The microwave irradiation time is preferably 60 seconds to 3,600 seconds, more preferably 120 seconds to 1,800 seconds, and still more preferably 180 seconds to 900 seconds. If the time is shorter than 60 seconds, the reaction between the organosilicon compound added in the step (C) and the surface hydroxyl groups of the inorganic oxide fine particles may be insufficient, and if it is longer than 3,600 seconds, it is not preferable in terms of industrial efficiency. The reaction time can be carried out by adjusting other reaction conditions (pH / concentration) so as to fall within these ranges.

  In the step (D), it is preferable to irradiate the microwave while further stirring. For stirring, mechanical stirring, magnetic stirring, shaking stirring, or the like can be used. By stirring, the hydrophobic alcohol and the inorganic oxide aqueous dispersion added in the step (B) are suspended, and the fine particles surface-treated with the organosilicon compound added in the step (C) are efficiently obtained by the microwave. It can migrate to hydrophobic alcohols. The stirring is preferably turbulent stirring.

  The degree of agitation can be estimated by calculating the Reynolds number of the system. The stirring Reynolds number is preferably 3,000 to 1,000,000, more preferably 5,000 to 500,000, and still more preferably 10,000 to 200,000. If it is smaller than 3,000, laminar stirring may occur and efficient suspension may be difficult. If it is larger than 1,000,000, the energy required for stirring becomes unnecessarily large from the viewpoint of industrial efficiency. It is not preferable.

The Reynolds number (Re) can be obtained from the following mathematical formula (1). In Equation (1), ρ represents density (kg / m ³ ), n represents rotation speed (rps), d represents stirrer length (m), and μ represents viscosity (Pa · s).
Re = ρ · n · d ² / μ Equation (1)
In the organosol used in the present invention, ρ is 900 to 2,000 (kg / m ³ ), preferably 1,000 to 1,500 (kg / m ³ ), and μ is 0.001 to 0.05 (Pa S), preferably 0.002 to 0.01 (Pa · s). For example, a magnetic rotor having a stirrer length d of 5 (cm), an organosol having a rotation speed n of 700 (rpm), ρ of 1,000 (kg / m ³ ), and μ of 0.002 (Pa · s) Re is about 15,000. By appropriately selecting n and d, it can be adjusted to be within the desired Re range.

  Moreover, you may implement the stirring efficiency improvement method by using the reactor which installed the baffle plate for stirring.

  Microwave irradiation results in an increase in the temperature of the reaction solution. The temperature range after microwave irradiation is preferably 10 ° C. or higher and 150 ° C. or lower, more preferably 60 ° C. or higher and 100 ° C. or lower, and still more preferably 80 ° C. or higher and 90 ° C. or lower. When the temperature after microwave irradiation is lower than 10 ° C., the reaction may take time. On the other hand, if the temperature after microwave irradiation is higher than 150 ° C., the solvent of the inorganic oxide colloidal aqueous dispersion may boil, making the reaction system difficult to handle.

Process (E)
Step (E) is a step of adding an organic solvent. The organic solvent added in the step (E) is one or more selected from the group consisting of hydrocarbon compounds having 5 to 30 carbon atoms, alcohol compounds, ether compounds, ester compounds, ketone compounds, and amide compounds. is there.

  Specific examples of such organic solvents include pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, icosane, eicosane, docosane, triicosane, tetricosane. Pentycosane, Hexaicosane, Heptaicosane, Octaicosane, Nonaicosane, Triacontane, benzene, toluene, o-xylene, m-xylene, p-xylene, and mixtures containing these such as petroleum ether, kerosene, ligroin, nujol 30 or less hydrocarbon compound; methanol, ethanol, 1-propanol, 2-propanol, cyclopentanol, ethylene glycol, propylene glycol, β Unit price and polyhydric alcohol compounds such as thiadiglycol, butylene glycol, glycerin; diethyl ether, dipropyl ether, cyclopentyl methyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether , Ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, butylene glycol monomethyl ether, butylene glycol monoethyl ether, butylene Ether compounds such as recall monopropyl ether, butylene glycol monobutyl ether; methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, Butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, dimethyl oxalate, diethyl oxalate, dipropyl oxalate, dibutyl oxalate, dimethyl malonate, malonic acid Diethyl, dipropyl malonate, dibutyl malonate, ethylene glycol diformate, ethylene glycol diacetate, ethylene glycol dipropionate, ethylene glycol dibutyrate, propylene glycol Rudiacetate, propylene glycol dipropionate, propylene glycol dibutyrate, ethylene glycol methyl ether acetate, propylene glycol methyl ether acetate, butylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol ethyl ether acetate, butylene glycol monoethyl ether acetate Ester compounds such as acetone, diacetone alcohol, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, methyl normal butyl ketone, dibutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, etc .; dimethylformamide, dimethyl Acetamide, tetraacetyl Ethylene diamide, tetraacetyl hexamethylene tetramide, N, may be mentioned amide compounds such as N- dimethyl hexamethylenediamine diacetate.

  The amount of the organic solvent added in the step (E) is preferably 50 parts by mass or more and 1,000 parts by mass or less with respect to 100 parts by mass of the water component of the inorganic oxide colloid aqueous dispersion used in the step (A). More preferably, it is 100 to 500 mass parts, More preferably, it is 120 to 300 mass parts. If the amount added is less than 50 parts by mass, water may not be sufficiently removed in the next step (F). When the addition amount is more than 1,000 parts by mass, there is an industrial and environmental problem caused by using a large amount of the organic solvent, which is not preferable.

  This step is preferably performed at a temperature of 0 ° C to 45 ° C, more preferably 5 ° C to 40 ° C, and even more preferably 10 ° C to 30 ° C. When the temperature is lower than 0 ° C., the water component derived from the inorganic oxide colloid aqueous dispersion may freeze and be altered. Moreover, when temperature is higher than 45 degreeC, it will become easy to discharge | release VOC (volatile organic compound) to air | atmosphere environment and a working environment, and it is unpreferable on safety | security and work environment health.

  In the step (E), the inorganic oxide fine particles surface-treated by adding the organic solvent can be uniformly dispersed in the organic solvent phase. By adding a solvent in the step (E), the system may form either a homogeneous phase or a two-phase. When two phases are formed, the organic layer can be separated by liquid separation.

Process (F)
Step (F) is a step of removing water by azeotropic distillation and / or ultrafiltration. The removal of water is more preferably carried out by azeotropic distillation.

  The azeotropic distillation in the step (F) is intended to remove water derived from the inorganic oxide colloid aqueous dispersion used in the step (A). The organic solvent azeotroped with water may be derived from one added in either step (B) or step (E). Azeotropic distillation is a phenomenon in which a mixture of water and an organic solvent is distilled off at a rate predicted from a vapor-liquid equilibrium curve when the sum of the vapor pressures of water and an organic solvent is balanced with the system pressure.

  The step (F) is preferably performed at a pressure of 200 mmHg or more and 760 mmHg or less, more preferably performed at a pressure of 300 mmHg or more and 760 mmHg or less, and further preferably performed at a pressure of 400 mmHg or more and 760 mmHg or less. If the pressure is lower than 200 mmHg, the mixture may suddenly boil and be difficult to control, and if the pressure is higher than 760 mmHg, water may be difficult to evaporate.

  The step (F) is preferably performed at a temperature of 50 ° C. or higher and 250 ° C. or lower, more preferably performed at a temperature of 60 ° C. or higher and 200 ° C. or lower, and is preferably performed at a temperature of 80 ° C. or higher and 150 ° C. or lower. Further preferred. When the temperature is lower than 50 ° C., it may take time for distillation, and when the temperature is higher than 250 ° C., the organosol may be altered. The pressure can be appropriately adjusted so that it can be carried out in such a range.

  For the heating required in the step (F), various methods of heating by contact with a heat medium, induction heating, and heating by microwaves can be used.

  In the step (F), ultrafiltration can be carried out instead of or in combination with azeotropic distillation. Ultrafiltration can be performed by passing through pores provided on the surface of an inorganic and / or organic substrate. The inorganic and / or organic base material is not specified as long as it has such pores, but preferably has an average pore diameter of 5 nm to 50 nm, more preferably 5 nm to 30 nm. Is used. If the pore diameter is less than 5 nm, the filtration rate may be slow, and if it exceeds 30 nm, the dispersoid of the organosol may flow out to the filtrate side.

  When carrying out ultrafiltration, it is possible to carry out while adding an organic solvent in consideration of the difference in the permeation coefficient of the filtration membrane depending on the type of solvent.

  The removal of water can be confirmed by measuring the water concentration after the process. As such a confirmation method, coulometric titration using Karl Fischer reaction can be used. Suitable titration apparatuses that can be used for such purposes include “AQV-2100” manufactured by Hiranuma Sangyo Co., Ltd., “KF-200” manufactured by Mitsubishi Chemical Analytech Co., Ltd., and the like.

  The water concentration after the step (F) is preferably 1% by mass or less, more preferably 0.5% by mass or less, and further preferably 0.1% by mass or less. If the water concentration is higher than 1% by mass, it may cause white turbidity when mixed with various resins as an organosol. In addition, although the lower limit of the water concentration after implementation of this step (F) is not particularly defined, it is about 0.1% by mass. The organic solvent itself used in the step (E) may contain water at a certain ratio, and reducing the water concentration by more than 0.1% by mass only by the step (F) It is not preferable in terms of efficiency. When the water concentration does not reach a desired level only by performing the step (F), the next step (G) can be performed.

Process (G)
Step (G) is a step of removing a trace amount of water present in the organosol that could not be removed in the previous step (F). In this step, the water concentration is preferably reduced to 1,000 ppm or less, more preferably 500 ppm or less, still more preferably 100 ppm or less, and most preferably 10 ppm or less. The lower limit of the water concentration in this step is not particularly defined, but is about 10 ppm. Dehydration above 10 ppm is usually not necessary except for special applications.

For the implementation of the step (G), preferably, physical adsorption using a zeolite having a pore diameter of 3 to 10 mm, or an ortho organic acid ester or a gem-dialkoxyalkane represented by the following general formula (2) is used. It can be carried out by a method involving chemical reactions.
(R ⁵ O) (R ⁶ O) CR ⁷ R ⁸ (2)
(In the formula, R ⁵ and R ⁶ are each a monovalent hydrocarbon group having 1 to 10 carbon atoms, which may be bonded to each other to form a ring, and R ⁷ and R ⁸ each have 1 carbon atom. 10 or less monovalent hydrocarbon groups which may be bonded to each other to form a ring.

Examples of substances that can be used as zeolite include K ₄ Na ₄ [Al ₈ Si ₈ O ₃₂ ], Na [AlSi ₂ O ₆ ], Na ₂ [Al ₂ Si ₇ O ₁₈ ], (K, Ba, Sr). ) ₂ Sr ₂ Ca ₂ (Ca, Na) ₄ [Al ₁₈ Si ₁₈ O ₇₂ ], Li [AlSi ₂ O ₆ ] O, Ca ₈ Na ₃ [Al ₁₉ Si ₇₇ O ₁₉₂ ], (Sr, Ba) ₂ [ Al ₄ Si ₁₂ O ₃₂ ], (Sr, Ba) ₂ [Al ₄ Si ₁₂ O ₃₂ ], (Ca _0.5 , Na, K) ₄ [Al ₄ Si ₈ O ₂₄ ], CaMn [Be ₂ Si ₅ O ₁₃ ( OH) ₂ ], (Na, K, Ca _0.5 , Sr _0.5 , Ba _0.5 , Mg _0.5 ) ₆ [Al ₆ Si ₃₀ O ₇₂ ], Ca [Al ₂ Si ₃ O ₁₀ ], (Ca _0.5 , Na, K) _{4-5 [Al 4-5 Si 20-19 O 48} ], Ba [Al 2 Si 3 O 10], (Ca, Na 2) [Al 2 Si 4 O 12], K 2 (Na _{Ca 0.5) 8 [Al 10 Si} 26 O 72], (Na, Ca 0.5, Mg 0.5, K) z [Al z Si 12-z O 24], (K, Na, Mg 0.5, Ca 0.5) 6 [Al ₆ Si ₃₀ O ₇₂ ], NaCa _2.5 [Al ₆ Si ₁₀ O ₃₂ ], Na ₄ [Zn ₂ Si ₇ O ₁₈ ], Ca [Al ₂ Si ₂ O ₈ ], (Na ₂ , Ca, K ₂ ) ₄ [ _{Al 8 Si 16 O 48],} Na 5 [Al 5 Si 11 O 32], (Na, Ca) 6-8 [(Al, Si) 20 O 40], Ca [Al 2 Si 6 O 16], Na 3 Mg ₃ Ca ₅ [Al ₁₉ Si ₁₁₇ O ₂₇₂ ], (Ba _0.5 , Ca _0.5 , K, Na) ₅ [Al ₅ Si ₁₁ O ₃₂ ], (Ca _0.5 , Sr _0.5 , Ba _0.5 , Mg _0.5 , Na, K ₉ [Al ₉ Si ₂₇ O ₇₂ ], Li ₂ Ca ₃ [Be ₃ Si ₃ O ₁₂ ] F ₂ , K ₆ [Al ₄ Si ₆ O ₂₀ ] B (OH) ₄ Cl, Ca ₄ [Al ₈ Si ₁₆ O _{48 ], K 4 Na 12 [Be} 8 Si 28 O 72], (Pb 7 Ca 2) [Al 12 Si 36 (O, OH) 100], (Mg 2.5 K 2 Ca 1.5) [Al 10 Si 26 O 72] K ₅ Ca ₂ [Al ₉ Si ₂₃ O ₆₄ ], Na ₁₆ Ca ₁₆ [Al ₄₈ Si ₇₂ O ₂₄₀ ], K ₉ [Al ₉ Si ₂₃ O ₆₄ ], (Na ₂ , Ca, K ₂ ) ₄ [Al ₈ Si ₄₀ O ₉₆ ], Na ₃ Ca ₄ [Al ₁₁ Si ₈₅ O ₁₉₂ ], Na ₂ [Al ₂ Si ₃ O ₁₀ ], CaKMg [Al ₅ Si ₁₃ O ₃₆ ], (Ca _5.5 Li _3.6 K _1.2 Na _0.2 ) Li ₈ [Be ₂₄ P ₂₄ O ₉₆ ], Ca ₂ [Al ₄ Si ₄ O ₁₅ (OH) ₂ ], (K, Ca _0.5 , Na, Ba _0.5 ) ₁₀ [Al ₁₀ Si ₃₂ O ₈₄ ], K ₉ Na (Ca, Sr) [Al 12 Si 24 O 72], (K, Na, Ca 0.5, Ba 0.5) z [Al z Si 16-z O 32] ·, (Cs, Na) [AlSi 2 O ₆ ], Ca ₂ [Be (OH) ₂ Al ₂ Si ₄ O ₁₃ ], Ca [Al ₂ Si ₃ O ₁₀ ], Ca [Al ₂ Si ₇ O ₁₈ ], (Ca _0.5 , Na, K) ₉ [ Al ₉ Si ₂₇ O ₇₂ ], NaCa [Al ₃ Si ₁₇ O ₄₀ ], Ca ₂ Na [Al ₅ Si ₅ O ₂₀ ], Ca [Al ₂ Si ₆ O ₁₆ ], Ca ₄ (K ₂ , Ca, Sr, Ba) ₃ Cu ₃ (OH) ₈ [Al ₁₂ Si ₁₂ O ₄₈ ], Ca [Al ₂ Si ₄ O ₁₂ ], Ca [Be ₃ (PO ₄ ) ₂ (OH) ₂ ], K _z Ca _{(1.5-0.5 z)} Those having a chemical composition such as [Al ₃ Si ₃ O ₁₂ ] and Ca [Al ₂ Si ₆ O ₁₆ ] can be mentioned.

  As the zeolite used in this step, those having a pore diameter of preferably 3 to 10 mm, more preferably 4 to 8 mm, and still more preferably 4 to 6 mm can be used. If the pore diameter is smaller than 3 mm, water may not be sufficiently adsorbed. If the pore diameter is larger than 10 mm, it may take time to adsorb water.

  Examples of such dehydrating zeolite include molecular sieve 3A, molecular sieve 4A, molecular sieve 5A, molecular sieve 6A, molecular sieve 7A, molecular sieve 8A, molecular sieve 9A, molecular sieve 10A, molecular sieve 4X, molecular sieve 4X, Sieve 5X, molecular sieve 6X, molecular sieve 7X, molecular sieve 8X, molecular sieve 9X, molecular sieve 10X and the like can be used in combination as appropriate. For example, the pore diameter is about 4 mm. As an LTA type zeolite, “catalog number 25958-08” manufactured by Kanto Chemical Co., Inc. can be used.

  The zeolite is preferably 1% by mass or more and 20% by mass or less, more preferably 2% by mass or more and 15% by mass or less, and further preferably 5% by mass or more and 10% by mass or less with respect to the organosol obtained in the step (F). Use. If the amount used is less than 1% by mass, the dehydration effect may not be sufficiently obtained. Even if the amount used is more than 20% by mass, the degree of dehydration is not always improved, so that it is not preferable to use more than this.

In the step (G), as described above, it can also be carried out by a method involving a chemical reaction using an ortho organic acid ester or a gem-dialkoxyalkane represented by the following general formula (2).
(R ⁵ O) (R ⁶ O) CR ⁷ R ⁸ (2)
(In the formula, R ⁵ and R ⁶ are each a monovalent hydrocarbon group having 1 to 10 carbon atoms, which may be bonded to each other to form a ring, and R ⁷ and R ⁸ each have 1 carbon atom. 10 or less monovalent hydrocarbon groups which may be bonded to each other to form a ring.

In the above formula (2), R ^{5 to} R ⁸ are each a monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms. Specifically, methyl group, ethyl group, propyl group, isopropyl group Group, butyl group, isobutyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group and other alkyl groups; cyclopentyl group, cyclohexyl group and other cycloalkyl groups; vinyl group, allyl group and other alkenyl groups; phenyl group An aryl group such as can be exemplified. R ⁵ and R ⁶ , R ⁷ and R ⁸ may combine with each other to form a ring, and in that case, a C 4-8 divalent hydrocarbon group.

  Both ortho-organic acid esters and gem-dialkoxyalkanes have an acetal skeleton in the molecule. Ortho organic acid esters are acetals of organic acid esters, and gem-dialkoxyalkanes are acetals of ketones. Acetal can be used for dehydration because it reacts with water and decomposes into alcohol and a carbonyl compound. The reaction has the same effect as consuming water and adding an organic solvent.

  Specific examples of ortho organic acid esters include methyl orthoformate, ethyl orthoformate, propyl orthoformate, butyl orthoformate, methyl orthoacetate, ethyl orthoacetate, propyl orthoacetate, butyl orthoacetate, methyl orthopropionate, orthopropionic acid. Examples thereof include ethyl, propyl orthopropionate, butyl orthopropionate, methyl orthobutyrate, ethyl orthobutyrate, propyl orthobutyrate, and butyl orthobutyrate.

  Specific examples of gem-dialkoxyalkane include acetone dimethyl acetal, acetone diethyl acetal, acetone dipropyl acetal, acetone dibutyl acetal, acetone ethylene glycol acetal, acetone propylene glycol acetal, methyl ethyl ketone dimethyl acetal, methyl ethyl ketone diethyl acetal, methyl ethyl ketone dipropyl acetal , Methyl ethyl ketone dibutyl acetal, methyl ethyl ketone ethylene glycol acetal, methyl ethyl ketone propylene glycol acetal, methyl isobutyl ketone dimethyl acetal, methyl isobutyl ketone diethyl acetal, methyl isobutyl ketone dipropyl acetal, methyl isobutyl ketone dibutyl acetal, methyl Sobutyl ketone ethylene glycol acetal, methyl isobutyl ketone propylene glycol acetal, cyclopentanone dimethyl acetal, cyclopentanone diethyl acetal, cyclopentanone dipropyl acetal, cyclopentanone dibutyl acetal, cyclopentanone ethylene glycol acetal, cyclopentanone propylene glycol Examples include acetal, cyclohexanone dimethyl acetal, cyclohexanone diethyl acetal, cyclohexanone dipropyl acetal, cyclohexanone dibutyl acetal, cyclohexanone ethylene glycol acetal, and cyclohexanone propylene glycol acetal.

  When there is a preferred type of molecule generated when reacting with water, the selection of these compounds having an acetal skeleton (ortho organic acid ester or gem-dialkoxyalkane represented by the general formula (2)) Can be used in anticipation of it. For example, when water is removed from the organosol and substitution is performed with cyclohexanone and butanol, the object can be achieved by using cyclohexanone dibutyl acetal.

  The compound having an acetal skeleton (ortho organic acid ester or gem-dialkoxyalkane represented by the general formula (2)) is preferably 0.5% by mass or more and 20% by mass with respect to the organosol obtained in the step (F). % Or less, more preferably 2% by mass or more and 15% by mass or less, and further preferably 5% by mass or more and 10% by mass or less. If the amount used is less than 0.5% by mass, the dehydration effect may not be sufficiently obtained. Even if the amount used is more than 20% by mass, the degree of dehydration is not always improved, and when mixed with a resin or the like as an organosol, an unexpected effect such as etching may be brought about. It is practically undesirable to use it.

Organosol The organosol produced according to the present invention preferably contains a dispersoid of 1% by mass to 30% by mass, more preferably 5% by mass to 25% by mass, and even more preferably 10% by mass to 20% by mass. . When the content of the dispersoid is less than 1% by mass, it may be insufficient when mixed with the resin as an effective concentration. When the content of the dispersoid exceeds 30% by mass, the storage stability of the organosol may be insufficient.

  The organosol produced according to the present invention is characterized in that it maintains a good dispersion state even though it has not undergone mechanical unit operations such as grinding and classification after solvent substitution. Observation of such a dispersed state can be examined by carrying out particle size measurement by a dynamic light scattering method using laser light. The inorganic oxide fine particles are dispersed in an organic solvent at a volume average value of 50% cumulative average diameter by dynamic light scattering method, preferably 1 to 200 nm, more preferably 1 to 150 nm, still more preferably 1 to 100 nm. doing. When the 50% cumulative average diameter in volume average by the dynamic light scattering method is larger than 200 nm, the organosol may be easily clouded. When the 50% cumulative average diameter in volume average by the dynamic light scattering method is smaller than 1 nm, it may be difficult to handle as an organosol.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

[Example 1]
Synthesis of organosilica sol (OS-1)
Process (A)
200 g of a commercially available colloidal silica aqueous dispersion (manufactured by Nissan Chemical Industries, Ltd., trade name “Snowtex O”) was placed in a 1,000 mL flask equipped with a magnetic stir bar. The colloidal silica aqueous dispersion “Snowtex O” was confirmed to have a volume average 50% cumulative particle size of 20 nm and a concentration of 20% by mass by dynamic light scattering.
Process (B)
200 g of isobutyl alcohol (manufactured by Delta Kasei Co., Ltd.) was placed in the flask containing the colloidal silica aqueous dispersion in the previous step (A). Colloidal silica and isobutyl alcohol were not completely compatible and formed two phases. The solubility of isobutyl alcohol in water at 20 ° C. was 10 (g / 100 g water).
Process (C)
20 g of 3-acryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-5103”) was put into the flask after the previous steps (A) and (B). It was observed that the silane was mainly dissolved in the organic layer (isobutyl alcohol layer).
Process (D)
The flask which passed through previous process (A)-(C) was put in the cavity of a microwave irradiation apparatus (The product name "microReactorEx" by Shikoku Keiki Kogyo KK). While rotating the magnetic stir bar at 700 rpm, microwaves were irradiated for 5 minutes. The microwave irradiation was controlled by a program built in the apparatus so that the liquid temperature reached 82 ° C. at the maximum. After microwave irradiation, the solution was allowed to stand at room temperature until the liquid temperature reached 40 ° C. At this time, it was observed that the dispersoid component of the aqueous colloidal silica dispersion was transferred to the organic layer (isobutyl alcohol layer).
Process (E)
While stirring with a magnetic stirrer (700 rpm), 300 g of propylene glycol monomethyl ether (PGM, manufactured by Nippon Emulsifier Co., Ltd.) was added to the flask through the previous steps (A) to (D). After the addition of the organic solvent, the reaction solution was uniform and transparent.
Process (F)
The contents of the flask after the previous steps (A) to (E) were transferred to a distillation flask, and the solvent was distilled off by heating under a pressure of 760 mmHg. Distillation occurred when the temperature inside the flask was about 85 ° C. Distillation was continued until the distillate amount reached 500 g. The internal temperature at the end of the distillation was about 120 ° C. The flask contents were cooled to room temperature and analyzed for moisture concentration (Karl Fischer method), and it was 0.15% by mass. The volume average 50% cumulative particle diameter of the synthesized organosilica sol (OS-1) was measured by a dynamic light scattering method. The measurement result was as shown in FIG. In addition, the OS-1 particles were observed (50 k) using a transmission electron microscope (manufactured by Hitachi High-Technologies Corporation, apparatus name “H-9500”). The results are shown in FIG.
Process (G)
When a part (50 g) of the organosilica sol (OS-1) produced in steps (A) to (F) was treated with 5 g of molecular sieve 4A (manufactured by Kanto Chemical Co., Ltd., “25958-08”), the water concentration Decreased to 119 mass ppm. Since aggregation was not observed at this time, it became clear that the molecular sieve treatment is useful for reducing the moisture that could not be removed in the step (F).
Table 1 summarizes the results and steps.

[Example 2]
It replaced with the process (G) of Example 1, and implemented the following process (G ').
Process (G ')
When 50 g of organosilica sol (OS-1) was treated with 2.5 g of ethyl orthoformate (manufactured by Nichibo Chemical Co., Ltd.), the water concentration decreased to 88.3 ppm. Since no aggregation was observed at this time, it became clear that the treatment with ethyl orthoformate was useful for reducing the moisture that could not be removed in step (F).
Table 1 summarizes the results and steps.

[Example 3]
The following step (G ″) was carried out instead of the step (G) in Example 1. In addition, after the PGM was azeotropically distilled up to 400 g in the step (F), the PGM was obtained using an inorganic ceramic ultrafiltration membrane. 100 g of was filtered.
Process (G ")
When 50 g of organosilica sol (OS-1) was treated with 2.5 g of acetone dimethyl acetal (manufactured by Kanto Chemical Co., Inc.), the water concentration decreased to 31.3 ppm. Since aggregation was not observed at this time, it became clear that the acetone dimethyl acetal treatment was useful for reducing the moisture that could not be removed in the step (F).
Table 1 summarizes the results and steps.

[Example 4]
Synthesis of organo titania sol (OT-1)
Process (A)
As an inorganic oxide colloidal water dispersion, a core-shell fine particle having a titanium oxide-tin oxide composite oxide as a core, a silicon oxide shell as a dispersoid, and water as a dispersion medium was prepared. First, a dispersion containing titanium oxide-tin oxide composite oxide fine particles serving as a nucleus was produced, and then tetraethoxysilane was hydrolyzed and condensed to obtain a colloidal aqueous dispersion containing core-shell fine particles.
36 mass% titanium chloride (IV) aqueous solution (Ishihara Sangyo Co., Ltd., product name: TC-36) 66.0 g and tin chloride (IV) pentahydrate (Wako Pure Chemical Industries, Ltd.) After adding 8 g and mixing well, it was diluted with 1,000 g of ion-exchanged water. The solid solution amount of the tin component was 2 mol%. To this metal salt aqueous solution mixture, 300 g of 5% by mass ammonia water (manufactured by Wako Pure Chemical Industries, Ltd.) was gradually added to neutralize and hydrolyze to obtain a titanium hydroxide precipitate containing tin. . The pH of the titanium hydroxide slurry at this time was 8. The resulting precipitate of titanium hydroxide was deionized by repeatedly adding ion-exchanged water and decanting. 100 g of 30% by mass hydrogen peroxide (manufactured by Wako Pure Chemical Industries, Ltd.) is gradually added to the titanium hydroxide precipitate containing tin after the deionization treatment, and then sufficiently stirred for 3 hours at 60 ° C. To react. Thereafter, the concentration was adjusted by adding pure water to obtain a translucent tin-containing peroxotitanic acid solution (solid content concentration 1 mass%). 350 mL of the peroxotitanic acid solution synthesized as described above was charged into an autoclave having a volume of 500 mL (product name: TEM-D500, manufactured by Pressure Glass Co., Ltd.), and this was carried out for 240 minutes at 200 ° C. and 1.5 MPa. Hydrothermally treated. Thereafter, the reaction mixture in the autoclave was discharged into a container held in a water bath at 25 ° C. via a sampling tube, and the reaction was stopped by rapidly cooling to obtain a titanium oxide dispersion (i). . In addition, it was confirmed that the volume average 50% cumulative particle diameter of the titanium oxide-tin oxide composite oxide fine particles in the titanium oxide dispersion liquid (i) was 9 nm by a dynamic light scattering method.
To a separable flask equipped with a magnetic rotor and a thermometer, 1,000 parts by mass of titanium oxide dispersion (i), 100 parts by mass of ethanol, and 2.0 parts by mass of ammonia were added at room temperature (25 ° C.) and magnetically stirred. . The separable flask was immersed in an ice bath and cooled until the content temperature reached 5 ° C. After adding 18 parts by mass of tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBE-04”), the separable flask was set in μReactorEx (manufactured by Shikoku Keiki Kogyo Co., Ltd.). Then, magnetic stirring was performed while irradiating a microwave with a frequency of 2.45 GHz and an output of 1,000 W for 1 minute. Meanwhile, a thermometer was observed to confirm that the content temperature reached 85 ° C. The obtained mixture was filtered with a qualitative filter paper (Advantec 2B) to obtain a diluted colloidal solution. The diluted colloidal solution was concentrated to 10% by mass by ultrafiltration to obtain an inorganic oxide colloidal aqueous dispersion (WT-1). In addition, it confirmed that the volume average 50% cumulative particle diameter by the dynamic light scattering method of the core-shell fine particles in this inorganic oxide colloid water dispersion (WT-1) was 12 nm. WT-1 (200 g) was placed in a 1,000 mL separable flask equipped with a magnetic stir bar.
Process (B)
200 g of isobutyl alcohol (manufactured by Delta Kasei Co., Ltd.) was placed in the flask containing WT-1 in the previous step (A). Colloidal silica and isobutyl alcohol were not completely compatible and formed two phases. The solubility of isobutyl alcohol in water at 20 ° C. was 10 (g / 100 g water).
Process (C)
20 g of 3-acryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-5103”) was put into the flask after the previous steps (A) and (B). It was observed that the silane was mainly dissolved in the organic layer (isobutyl alcohol layer).
Process (D)
The flask which passed through previous process (A)-(C) was put in the cavity of a microwave irradiation apparatus (The product name "microReactorEx" by Shikoku Keiki Kogyo KK). While rotating the magnetic stir bar at 700 rpm, microwaves were irradiated for 5 minutes. The microwave irradiation was controlled by a program built in the apparatus so that the liquid temperature reached 82 ° C. at the maximum. After microwave irradiation, the solution was allowed to stand at room temperature until the liquid temperature reached 40 ° C. At this time, the inorganic oxide colloid aqueous dispersion was in a suspended state.
Process (E)
While stirring with a magnetic stirrer (700 rpm), 300 g of propylene glycol monomethyl ether (manufactured by Nippon Emulsifier Co., Ltd.) was added to the flask through the previous steps (A) to (D). After the addition of the organic solvent, the reaction solution was uniform and transparent.
Process (F)
The contents of the flask after the previous steps (A) to (E) were transferred to a distillation flask, and the solvent was distilled off by heating under a pressure of 760 mmHg. Distillation occurred when the temperature inside the flask was about 85 ° C. Distillation was continued until the distillate amount reached 500 g. The internal temperature at the end of the distillation was about 120 ° C. The flask contents were cooled to room temperature and analyzed for moisture concentration (Karl Fischer method). As a result, the content was 0.20% by mass. The volume average 50% cumulative particle diameter of the synthesized organotitania sol (OT-1) was measured by a dynamic light scattering method. The measurement results were as shown in FIG. Moreover, observation of the particles of OT-1 (50 k) was performed using a transmission electron microscope (manufactured by Hitachi High-Technologies Corporation, apparatus name “H-9500”). The results are shown in FIG.
Process (G)
When a part (50 g) of the organotitania sol (OT-1) produced in steps (A) to (F) was treated with 5 g of molecular sieve 4A (manufactured by Kanto Chemical Co., Ltd., “25958-08”), the water concentration Decreased to 250 ppm by mass. Since aggregation was not observed at this time, it became clear that the molecular sieve treatment is useful for reducing the moisture that could not be removed in the step (F).
Table 1 summarizes the results and steps.

[Example 5]
The same operation as in Example 4 was performed except that, in the step (B) performed in Example 4, 200 g of 1-butanol was used instead of 200 g of isobutyl alcohol. The solubility of 1-butanol in water at 20 ° C. was 7.7 (g / 100 g water).
Table 1 summarizes the results and steps.

[Example 6]
The same operation as in Example 4 was performed except that, in the step (B) performed in Example 4, 200 g of 2-butanol was used instead of 200 g of isobutyl alcohol. The solubility of 2-butanol in water at 20 ° C. was 26 (g / 100 g water).
Table 1 summarizes the results and steps.

[Example 7]
The same operation as in Example 4 was performed except that in Step (B) performed in Example 4, 200 g of cyclopentanol was used instead of 200 g of isobutyl alcohol. The solubility of cyclopentanol in water at 20 ° C. was 1.2 (g / 100 g water).
Table 1 summarizes the results and steps.

[Example 8]
In the step (C) performed in Example 4, 20 g of n-propyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name “KBM-3033”) was used instead of 20 g of 3-acryloyloxypropyltrimethoxysilane. The same operation as in Example 4 was performed except that the above was performed.
Table 1 summarizes the results and steps.

[Example 9]
In the step (C) performed in Example 4, 20 g of vinyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name “KBM-1003”) was used instead of 20 g of 3-acryloyloxypropyltrimethoxysilane. Otherwise, the same operation as in Example 4 was performed.
Table 1 summarizes the results and steps.

[Example 10]
The same operation as in Example 4 was performed except that in Step (E) performed in Example 4, 300 g of diacetone alcohol was used instead of 300 g of propylene glycol monomethyl ether.
Table 2 summarizes the results and steps.

[Example 11]
The same operation as in Example 4 except that in the step (E) performed in Example 4, 300 g of a mixed solvent (propylene glycol monomethyl ether: ligroin = 9: 1) was used instead of 300 g of propylene glycol monomethyl ether. Went.
Table 2 summarizes the results and steps.

[Comparative Example 1]
In the step (B) performed in Example 4, when 200 g of methanol was used instead of 200 g of isobutyl alcohol, agglomeration of dispersoids was observed. The solubility of methanol in water at 20 ° C. was ∞ (arbitrary mixing).
Table 2 summarizes the results and steps.

[Comparative Example 2]
In the step (B) performed in Example 4, when 200 g of ethanol was used instead of 200 g of isobutyl alcohol, aggregation of dispersoids was observed. The solubility of ethanol in water at 20 ° C. was ∞ (arbitrary mixing).
Table 2 summarizes the results and steps.

[Comparative Example 3]
In the step (B) performed in Example 4, when 200 g of 2-propanol was used instead of 200 g of isobutyl alcohol, dispersoid aggregation was observed. The solubility of 2-propanol in water at 20 ° C. was ∞ (arbitrary mixing).
Table 2 summarizes the results and steps.

[Comparative Example 4]
In the step (B) performed in Example 4, when 200 g of 1-decanol was used instead of 200 g of isobutyl alcohol, dispersoid aggregation was observed. The solubility of 1-decanol in water at 20 ° C. was 0.1 (g / 100 g water).
Table 2 summarizes the results and steps.

[Comparative Example 5]
In the process (D) performed in Example 4, it heated so that it might become 82 degreeC with an oil bath instead of microwave heating. The time required for heating was 1 hour. At this time, aggregation of dispersoids was observed.
Table 2 summarizes the results and steps.

[Comparative Example 6]
In the step (G) performed in Example 4, the same amount of sodium sulfate was used as a desiccant in place of 5 g of molecular sieve 4A. At this time, aggregation of dispersoids was observed.
Table 2 summarizes the results and steps.

[Comparative Example 7]
In the step (G) performed in Example 4, the same amount of magnesium sulfate was used as a desiccant in place of 5 g of molecular sieve 4A. At this time, aggregation of dispersoids was observed.
Table 2 summarizes the results and steps.

The meanings of the abbreviations in Tables 1 and 2 are as follows.
Process (A)
STO: Colloidal silica aqueous dispersion, manufactured by Nissan Chemical Industries, Ltd., product name “Snowtex O”
TiO ₂ @SiO ₂ : Example 4 Silica-coated titanium oxide aqueous dispersion step (B) showing the production method in step (A)
IBA: isobutyl alcohol 1-BuOH: 1-butanol 2-BuOH: 2-butanol CypOH: cyclopentanol MeOH: methanol EtOH: ethanol IPA: isopropyl alcohol 1-DecOH: 1-decanol Step (C)
KBM-5103: 3-acryloyloxypropyltrimethoxysilane KBM-3033: n-propyltrimethoxysilane KBM-1003: vinyltrimethoxysilane Step (D)
MW: Microwave heating OB: Oil bath heating process (E)
PGM: Propylene glycol monomethyl ether DAA: Diacetone alcohol LG: Ligroin process (F)
AD: azeotropic distillation (A zeotropic D istillation)
UF: ultrafiltration (U ltra F iltration)
Process (G)
MS4A: Molecular sieve 4A
OFE: ethyl orthoformate DMP: acetone dimethyl acetal (2,2-dimethoxypropane)
Na ₂ SO ₄ : Sodium sulfate MgSO ₄ : Magnesium sulfate Result “◯”: An organosol was obtained without agglomeration, and the volume average 50% cumulative particle size measured by the dynamic light scattering method was 200 nm. What was below “×”: agglomeration occurred, 50% cumulative particle diameter of volume average measured by dynamic light scattering method was larger than 200 nm

Description of Examples and Comparative Examples As inorganic oxide colloidal aqueous dispersions, Examples 1 to 3 are carried out using colloidal silica sol, and Examples 4 to 11 are carried out using water-dispersed titania sol. Thus, it was suggested that the present invention is applicable to various inorganic oxide colloid aqueous dispersions.
In the step (B), when an alcohol having a solubility in water of about 1 to 30 is used, good results are shown. However, alcohol (comparative examples 1 to 3) arbitrarily mixed with water and a low solubility When (Comparative Example 4) was used, good results were not given. The usefulness of using an alcohol having such a specific solubility in the surface treatment process has not been known so far.
In the step (C), it became clear that silanes having various carbon functional groups can be used.
It became clear from Examples 1-11 that the heating of a microwave is important in a process (D). In addition, the heating of the oil bath could not be used suitably (Comparative Example 5). The usefulness of microwaves in the surface treatment process for producing such organosols has not been known so far.
It was found that azeotropic distillation and ultrafiltration can be used in step (F).
In the step (G), molecular sieves and acetal compounds can be suitably used (Examples 1 to 11), whereas aggregation was generated in the anhydrous salts (Comparative Examples 6 and 7). Thus, selection of the dehydrating agent applicable to organosol was not known until now.

FIG. 1 shows the measurement results of the particle size distribution of organosilica sol (OS-1). From FIG. 1, it has been clarified that no aggregation occurs even when the dispersion medium is completely substituted with an organic solvent in the method of the present invention.
FIG. 2 is a transmission electron microscope image of OS-1. FIG. 2 reveals that the silica component of the dispersoid does not change the morphology, and that the method of the present invention is a mild method that does not chemically change the core of the inorganic oxide particles. It was.
FIG. 3 shows the measurement results of the particle size distribution of organotitania sol (OT-1). From FIG. 3, it has been clarified that no aggregation occurs even when the dispersion medium is completely substituted with an organic solvent in the method of the present invention.
FIG. 4 is a transmission electron microscope image of OT-1. FIG. 4 reveals that the dispersoid titania component does not change the morphology, and that the method of the present invention is a mild method that does not chemically change the core of the inorganic oxide particles. It was.
The results in FIGS. 1 to 4 indicate that the two problems of “complete solvent replacement” and “mild and no aggregation” have been solved in a balanced manner. These Examples and Comparative Examples are typical examples for showing the usefulness of the present invention, and do not limit the scope of the present invention.

  The organosol produced according to the present invention can be applied to the field using inorganic oxide fine particles. For example, the application to a coating composition, a light emitting element sealing material, a heat conductive composition, etc. can be considered. In these fields, various mechanical techniques have been used to disperse inorganic oxide fine particles to a high degree. However, using organosols with excellent compatibility with binders contributes to simplification of the composition technique. be able to. In particular, it can be suitably used in fields that require high transparency, high weather resistance, high thermal conductivity, and the like. Further, in the present invention, an organosol can be produced from a readily available or easily synthesized water-dispersed sol, so that the range of material selection at the time of composition can be greatly widened, which is considered to contribute to industrial development in this field. .

Claims (11)

(A) preparing an inorganic oxide colloid aqueous dispersion,
(B) adding alcohol characterized in that it is not completely compatible with water and forms a two-phase system;
(C) The following general formula (1)
R ¹ _p R ² _q R ³ _r Si (OR ⁴ ) _4-pqr (1)
(In the formula, R ¹ is a hydrogen atom, non-substituted or substituted carbon atoms 1 to 20 monovalent hydrocarbon group, a silicon atom number of 50 or less polydimethylsiloxane group, or an isocyanurate group, R ^2, R ³ and R ⁴ are each an alkyl group having 1 to 6 carbon atoms, p is an integer of 1 to 3, q is 0, 1 or 2, r is 0, 1 or 2, and p + q + r is 1 to 3. (It is an integer.)
A step of adding an organosilicon compound and / or a partially hydrolyzed condensate or hydrolyzed condensate thereof,
(D) a step of irradiating microwaves;
(E) The manufacturing method of the organosol through the solvent substitution of the aqueous colloidal solution which consists of the process of adding an organic solvent, and the process of (F) distilling off water by azeotropic distillation and / or ultrafiltration.   Furthermore, the manufacturing method of the organosol of Claim 1 provided with the process of removing (G) water to 1,000 ppm or less.   The dispersoid of the inorganic oxide colloid aqueous dispersion prepared in the step (A) is a core-shell fine particle having titanium oxide fine particles as nuclei and a silicon oxide shell outside the nuclei. Or the manufacturing method of the organosol of 2.   The dispersoid of the inorganic oxide colloid aqueous dispersion prepared in the step (A) has tetragonal titanium oxide solid solution fine particles in which tin and / or manganese is dissolved as a nucleus, and has a silicon oxide shell outside the nucleus. A core-shell type tetragonal titanium oxide solid solution aqueous dispersion having a volume average 50% cumulative particle diameter of the core fine particles measured by a dynamic light scattering method of 30 nm or less and a volume average 50% cumulative particle of the core-shell type fine particles. The diameter is 50 nm or less, the solid solution amount of the tin component is 10 to 1,000 in terms of the molar ratio with titanium (Ti / Sn), and the solid solution amount of the manganese component is the molar ratio of titanium (Ti / Sn). 3. The method for producing an organosol according to claim 1, wherein core-shell type tetragonal titanium oxide solid solution fine particles having a Mn) of 10 to 1,000 are used.   The dispersoid of the inorganic oxide colloid aqueous dispersion prepared in the step (A) is alumina and / or silica, and the volume average 50% cumulative particle diameter of the dispersoid measured by a dynamic light scattering method is 10 nm. The method for producing an organosol according to claim 1 or 2, wherein the thickness is 100 nm or less.   The solubility of the alcohol added in the step (B) at 20 ° C in water is 1 (1 g of alcohol / 100 g of water) or more and 30 (30 g of alcohol / 100 g of water) or less. 2. A method for producing an organosol according to item 1.   The alcohol to be added in the step (B) is a linear, branched or cyclic monovalent alcohol which may contain an aromatic group having 4 to 8 carbon atoms, and 3 to 8 carbon atoms. The method for producing an organosol according to any one of claims 1 to 6, wherein the organosol is one or more selected from the group consisting of monovalent alcohols that are fully or partially substituted with fluorine atoms.   In the step (D), the integrated irradiation time of the microwave is 60 seconds or more and 3,600 seconds or less, and the temperature of the system after irradiation is 10 ° C. or more and 150 ° C. or less. The manufacturing method of the organosol of any one.   The solvent added in the step (E) is one or more selected from the group consisting of hydrocarbon compounds having 5 to 30 carbon atoms, alcohol compounds, ether compounds, ester compounds, ketone compounds, and amide compounds. The method for producing an organosol according to any one of claims 1 to 8, wherein:   The method of removing water to 1,000 ppm or less in the step (G) is physical adsorption using a zeolite having a pore diameter of 3 to 10 mm. The manufacturing method of the organosol as described in a term. In the step (G), a method for removing water up to 1,000 ppm or less is an ortho organic acid ester or the following general formula (2)
(R ⁵ O) (R ⁶ O) CR ⁷ R ⁸ (2)
(In the formula, R ⁵ and R ⁶ are each a monovalent hydrocarbon group having 1 to 10 carbon atoms, which may be bonded to each other to form a ring, and R ⁷ and R ⁸ each have 1 carbon atom. 10 or less monovalent hydrocarbon groups which may be bonded to each other to form a ring.
The method for producing an organosol according to any one of claims 2 to 9, wherein the method involves a chemical reaction using a gem-dialkoxyalkane represented by formula (1).