JP6428588B2 - Surface-treated inorganic oxide particles, dispersion containing the particles, and method for producing the same - Google Patents

Description

  The present invention relates to surface-treated inorganic oxide particles, a dispersion containing the particles, and a method for producing the same. More specifically, inorganic oxide particles coated with hydrogen polysiloxane via a siloxane bond, which are well dispersed and non-polar with a non-polar solvent without mechanical unit operations such as classification and grinding. The present invention relates to a method for providing a dispersion liquid containing particles having properties, and also relates to a production method that can be easily carried out and has high utility.

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

  In particular, sols composed of nanoparticles whose particle size is controlled on the order of nanometers have little light scattering in the visible light region, and are dispersed in resin to provide a high refractive index and high durability for resin materials used in displays. And functionalities such as ultraviolet absorption characteristics can be imparted.

  In order to prepare the organosol, it is important to impart high dispersibility to the organic solvent to the inorganic oxide particles. In order to achieve such improvement in dispersibility, surface treatment using a silane coupling agent or a polymeric dispersant having a polar group in the side chain is often performed. Patent Document 1 (Japanese Patent No. 3906933) discloses a technique of completely removing water from a water-dispersed colloidal solution once produced and redispersing it in an organic solvent to obtain an organosol. However, the above proposal is characterized by using a polar organic solvent having a dipole moment of 1.9 [Debye] or more as a dispersion medium, and it is expected that the dispersibility in a nonpolar organic solvent is poor. In addition, 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.

  As a method for producing an organosol that does not use mechanical unit operations such as pulverization and classification, Patent Document 2 (Patent No. 5337393) discloses that an aqueous dispersion of titanium oxide particles coated with silicon hydrated oxide is organic An organosol is obtained by distilling off water in the state where a solvent and a polymeric dispersant having an amino group coexist. Moreover, in patent document 3 (Unexamined-Japanese-Patent No. 2010-143806), the organosilica sol which has a nano-order particle size is obtained by using the silane coupling agent hydrolyzed beforehand. However, although the particles obtained by the above-mentioned method are specified for dispersion in a polar organic solvent such as an alcohol or a polyether, no mention is made about dispersion in a nonpolar organic solvent.

  As a result of the study by the present inventors, in Patent Document 4 (Japanese Patent Laid-Open No. 2015-34106), an aqueous dispersion of titanium oxide particles coated with silicon hydrated oxide is reacted with a silane coupling agent. Thus, an organosol having a nano-order particle size is obtained. The particles obtained by the above method exhibit high dispersibility in alcohols and polyether polar organic solvents. On the other hand, for dispersion in a nonpolar solvent such as toluene, it is necessary to add a small amount of a polar solvent such as alcohol as a stabilizer.

  In addition to the above-described dehydration condensation between silanols, surface treatment using hydrogen bonding between functional groups and electrostatic interaction, Non-Patent Document 1 (Journal of The American Chemical Society 2014, Vol. 131, No. 33, 11570-11573). By using a dehydrogenation reaction between a silanol group on the glass surface and a low-molecular silane compound having a hydrosilyl group, an effective surface treatment is achieved in a short time. Such a dehydrogenation reaction is an excellent surface treatment method, but there are the following problems when applying to the surface treatment method of inorganic oxide particles stably dispersed in a solvent. (1) This reaction must be performed in a nonpolar solvent such as toluene, and is difficult to adapt to inorganic oxide particles that aggregate in a nonpolar solvent. (2) Even if inorganic oxide particles are stably dispersed in a non-polar solvent using a compatibilizing agent such as alcohol or a dispersing agent, a dispersing agent present in the system, a stabilizing agent such as alcohol, water, etc. The reaction point is deactivated by the reaction between the impurity and the low molecular weight silane compound. (3) In general, the surface treatment with a low molecular weight dispersant has less steric hindrance generated on the particle surface as compared with the high molecular weight dispersant, and the direct contact between the particles cannot be suppressed and tends to aggregate. For the above reasons, there is no example in which the above dehydrogenation reaction is used for the surface treatment of inorganic oxide particles stably dispersed in a solvent.

Japanese Patent No. 3906933 Japanese Patent No. 5337393 JP 2010-143806 A JP-A-2015-34106

Journal of The American Chemical Society 2014 Vol. 131, No. 33, 11570-11573

  The present inventors considered these background technologies and found one problem. That is, in order to obtain inorganic oxide particles having high dispersibility, it is necessary to coat the particle surface with a hydrophobic compound at a high density to inhibit direct contact between the particles. In high-density coating on the particle surface, it is effective to use a dehydrogenation reaction or dealkane reaction having high reactivity as seen in Non-Patent Document 1, but many inorganic oxide particles are hydrophilic. Yes, the surface treatment is performed in a state dispersed in water or a protic polar organic solvent. Accordingly, the reaction point is deactivated by the reaction of the dispersant, alcohol, water, and low molecular weight silane compound present in the system, and the surface treatment does not proceed. If such problems can be overcome and high-density coating on the particle surface can be achieved by dehydrogenation or dealkane reaction, inorganic oxide particles having high dispersibility in nonpolar solvents can be developed. Can be expected.

A clear technical idea that overcomes such problems and is dispersible in a nonpolar solvent, has high utility, and contributes to the development of the industrial field has not been submitted so far.
Accordingly, an object of the present invention is to provide surface-treated inorganic oxide particles having high dispersibility in a nonpolar solvent, a dispersion thereof, and a production method thereof.

  As a result of intensive studies to solve the above-described problems in the surface-treated inorganic oxide particles, the present inventors have used a polymer, hydrogenpolysiloxane, as a surface treatment agent, thereby allowing a dehydrogenation reaction or a dealkane reaction. It was found that the inorganic oxide particles can be coated using, and the obtained particles have high dispersibility in nonpolar solvents. This result shows that by using a hydrogen polysiloxane having a large number of reactive sites in one molecule, even if some of the hydrosilyl groups disappear due to the reaction with the dispersion stabilizer, the remaining hydrosilyl groups remain in contact with the particles. The direct contact of the particle surface is strongly suppressed by the effect of the loop train structure formed by the unit that is capable of reacting and the unit that is bonded to the particle surface and the unit that is not bonded, which is a feature of the polymer dispersant. Seems to have greatly influenced. The present invention has been made based on the above findings.

（式（Ｉ）中において、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸及びＲ⁹は、それぞれ同一又は異なっていてもよく、（メタ）アクリル基、オキシラニル基もしくはフッ素原子で置換されていてもよい炭素数１以上２０以下のアルキル基と、炭素数２以上２０以下のアルケニル基と、炭素数６以上２０以下のアリール基と、及びケイ素数５０以下の（ポリ）ジメチルシロキシ基とからなる群から選ばれる置換基又は水素原子であり、ｋは５以上の正の整数、ｍは０又は正の整数であり、ｋ＋ｍは該ハイドロジェンポリシロキサンの２５℃における粘度を１０〜１，０００，０００ｍＰａ・ｓの範囲とする数である。）
〔２〕
前記無機酸化物が、Ａｌ、Ｂ、Ｉｎ、Ｓｉ、Ｇｅ、Ｓｎ、Ｔｉ、Ｍｎ、Ｚｎ、Ｙ、Ｚｒ、Ｈｆ、Ｔａ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｔｂ、Ｄｙ、Ｙｂの群から選ばれる１種以上の元素の酸化物を含むことを特徴とする〔１〕に記載の表面処理無機酸化物粒子。
〔３〕
前記無機酸化物が、酸化チタン粒子を核とし、該核の外側に酸化ケイ素の殻を有するコアシェル粒子であることを特徴とする〔１〕又は〔２〕に記載の表面処理無機酸化物粒子。
〔４〕
前記無機酸化物が、スズ及びマンガンを固溶した正方晶系酸化チタン固溶体粒子を核とし、該核の外側に酸化ケイ素の殻を有するコアシェル型正方晶系酸化チタン粒子であることを特徴とする〔１〕又は〔２〕に記載の表面処理無機酸化物粒子。
〔５〕
前記一般式（Ｉ）で表されるハイドロジェンポリシロキサンと、前記表面にオルガノシリル残基を有する無機酸化物粒子との結合が、該ハイドロジェンポリシロキサン上のヒドロシリル基と、無機粒子表面上もしくは粒子表面のオルガノシリル残基上のヒドロキシル基との脱水素反応又はアルコキシ基との脱アルカン反応による結合であることを特徴とする〔１〕〜〔４〕のいずれかに記載の表面処理無機酸化物粒子。
〔６〕
更に、式（Ｉ）のハイドロジェンポリシロキサンのヒドロシリル基と、不飽和結合を有する化合物との付加反応、ヒドロキシ基を有する化合物との脱水素反応、又はアルコキシ基を有する化合物との脱アルカン反応による表面修飾部を有する〔１〕〜〔５〕のいずれかに記載の表面処理無機酸化物粒子。
〔７〕
〔１〕〜〔６〕のいずれかに記載の表面処理無機酸化物粒子が、分散媒体に対して０．０１〜５０質量％含まれることを特徴とする分散液。
〔８〕
前記分散媒体が、炭素数５以上３０以下の炭化水素化合物、アルコール化合物、エーテル化合物、エステル化合物、ケトン化合物、シロキサン化合物、及びアミド化合物からなる群から選ばれる１種以上であることを特徴とする〔７〕に記載の分散液。
〔９〕
前記分散媒体が、１種以上のシロキサン化合物であることを特徴とする〔８〕に記載の分散液。
〔１０〕
（Ａ）無機酸化物粒子を、シランカップリング剤及び／又はその（部分）加水分解縮合物によって表面処理した後、極性有機溶媒分散媒に分散する工程、
（Ｂ）蒸留及び／又は限外ろ過によって極性有機溶媒を除去しながら非プロトン性の有機溶媒で分散媒を置換し、非プロトン性有機溶媒に対する極性有機溶媒のモル分率が１〜１５ｍｏｌ％になるまで前記極性有機溶媒を除去する工程、及び
（Ｃ）下記一般式（Ｉ）で示されるハイドロジェンポリシロキサンと反応させる工程を含む表面処理無機酸化物粒子の製造方法。

（式（Ｉ）中において、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸及びＲ⁹は、それぞれ同一又は異なっていてもよく、（メタ）アクリル基、オキシラニル基もしくはフッ素原子で置換されていてもよい炭素数１以上２０以下のアルキル基と、炭素数２以上２０以下のアルケニル基と、炭素数６以上２０以下のアリール基と、及びケイ素数５０以下の（ポリ）ジメチルシロキシ基とからなる群から選ばれる置換基又は水素原子であり、ｋは５以上の正の整数、ｍは０又は正の整数であり、ｋ＋ｍは該ハイドロジェンポリシロキサンの２５℃における粘度を１０〜１，０００，０００ｍＰａ・ｓの範囲とする数である。）
〔１１〕
前記無機酸化物が、Ａｌ、Ｂ、Ｉｎ、Ｓｉ、Ｇｅ、Ｓｎ、Ｔｉ、Ｍｎ、Ｚｎ、Ｙ、Ｚｒ、Ｈｆ、Ｔａ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｔｂ、Ｄｙ、Ｙｂの群から選ばれる１種以上の元素の酸化物を含むことを特徴とする〔１０〕に記載の表面処理無機酸化物粒子の製造方法。
〔１２〕
前記無機酸化物が、酸化チタン粒子を核とし、該核の外側に酸化ケイ素の殻を有するコアシェル粒子であることを特徴とする〔１０〕又は〔１１〕に記載の表面処理無機酸化物粒子の製造方法。
〔１３〕
前記無機酸化物が、スズ及びマンガンを固溶した正方晶系酸化チタン固溶体粒子を核とし、該核の外側に酸化ケイ素の殻を有するコアシェル型正方晶系酸化チタン粒子であることを特徴とする〔１０〕又は〔１１〕に記載の表面処理無機酸化物粒子の製造方法。
〔１４〕
前記工程（Ａ）における前記極性有機溶媒がメタノール、エタノール、イソプロピルアルコール、ｎ−プロピルアルコールからなる群から選ばれる１種以上であることを特徴とする〔１０〕〜〔１３〕のいずれかに記載の表面処理無機酸化物粒子の製造方法。
〔１５〕
前記工程（Ｂ）における前記非プロトン性有機溶媒がベンゼン、トルエン、ｏ−キシレン、ｍ−キシレン及びｐ−キシレンからなる群から選ばれる１種以上であることを特徴とする〔１０〕〜〔１４〕のいずれかに記載の表面処理無機酸化物粒子の製造方法。
〔１６〕
前記工程（Ｃ）において、前記一般式（Ｉ）で表されるハイドロジェンポリシロキサンと、前記表面にオルガノシリル残基を有する無機酸化物粒子との結合が、該ハイドロジェンポリシロキサン上のヒドロシリル基と、無機酸化物粒子表面上もしくは粒子表面のオルガノシリル残基上のヒドロキシル基との脱水素反応又はアルコキシ基との脱アルカン反応によって形成されることを特徴とする〔１０〕〜〔１５〕のいずれかに記載の表面処理無機酸化物粒子の製造方法。
〔１７〕
前記脱水素反応又は前記脱アルカン反応が、トリス（ペンタフルオロフェニル）ボランを触媒とすることを特徴とする〔１６〕に記載の表面処理無機酸化物粒子の製造方法。
〔１８〕
更に、（Ｄ）前記無機酸化物粒子上に結合した前記一般式（Ｉ）で表されるハイドロジェンポリシロキサンに由来するヒドロシリル基と、不飽和結合を有する化合物との付加反応、ヒドロキシル基を有する化合物との脱水素反応、又はアルコキシ基を有する化合物との脱アルカン反応を行う工程を有することを特徴とする〔１０〕〜〔１７〕のいずれかに記載の表面処理無機酸化物粒子の製造方法。 Accordingly, the present invention provides the following inorganic oxide particles, dispersions thereof, and production methods as particles that are highly useful and dispersible in nonpolar solvents.
[1]
Surface-treated inorganic oxide particles having an organosilyl residue on the surface and further bonded with hydrogen polysiloxane represented by the following general formula (I).

(In the formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ may be the same or different from each other, and a (meth) acryl group An oxiranyl group or an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a silicon number of 50 The substituent is selected from the group consisting of the following (poly) dimethylsiloxy groups or a hydrogen atom, k is a positive integer of 5 or more, m is 0 or a positive integer, and k + m is the hydrogen polysiloxane. (The number at which the viscosity at 25 ° C. is in the range of 10 to 1,000,000 mPa · s.)
[2]
The inorganic oxide is selected from the group consisting of Al, B, In, Si, Ge, Sn, Ti, Mn, Zn, Y, Zr, Hf, Ta, La, Ce, Pr, Nd, Tb, Dy, and Yb. The surface-treated inorganic oxide particles according to [1], comprising an oxide of one or more elements.
[3]
The surface-treated inorganic oxide particle according to [1] or [2], wherein the inorganic oxide is a core-shell particle having a titanium oxide particle as a nucleus and a silicon oxide shell outside the nucleus.
[4]
The inorganic oxide is a core-shell type tetragonal titanium oxide particle having, as a nucleus, tetragonal titanium oxide solid solution particles in which tin and manganese are dissolved, and having a silicon oxide shell outside the nucleus. The surface-treated inorganic oxide particles according to [1] or [2].
[5]
The bond between the hydrogenpolysiloxane represented by the general formula (I) and the inorganic oxide particle having an organosilyl residue on the surface is a bond between the hydrosilyl group on the hydrogenpolysiloxane and the surface of the inorganic particle or The surface-treated inorganic oxidation according to any one of [1] to [4], which is a bond by dehydrogenation reaction with a hydroxyl group on an organosilyl residue on the particle surface or dealkane reaction with an alkoxy group Particle.
[6]
Furthermore, by an addition reaction between the hydrosilyl group of the hydrogenpolysiloxane of formula (I) and a compound having an unsaturated bond, a dehydrogenation reaction with a compound having a hydroxy group, or a dealkane reaction with a compound having an alkoxy group. The surface-treated inorganic oxide particle according to any one of [1] to [5], which has a surface modification portion.
[7]
[1]-[6] The dispersion liquid characterized by including the surface treatment inorganic oxide particle in 0.01-50 mass% with respect to a dispersion medium.
[8]
The dispersion medium is at least one selected from the group consisting of hydrocarbon compounds having 5 to 30 carbon atoms, alcohol compounds, ether compounds, ester compounds, ketone compounds, siloxane compounds, and amide compounds. [7] The dispersion according to [7].
[9]
The dispersion liquid according to [8], wherein the dispersion medium is one or more siloxane compounds.
[10]
(A) Step of dispersing inorganic oxide particles in a polar organic solvent dispersion medium after surface treatment with a silane coupling agent and / or (partial) hydrolysis condensate thereof,
(B) The dispersion medium is replaced with an aprotic organic solvent while removing the polar organic solvent by distillation and / or ultrafiltration, and the molar fraction of the polar organic solvent to the aprotic organic solvent is 1 to 15 mol% The manufacturing method of the surface treatment inorganic oxide particle including the process of removing the said polar organic solvent until it becomes, and the process made to react with the hydrogen polysiloxane shown by (C) following general formula (I).

(In the formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ may be the same or different from each other, and a (meth) acryl group An oxiranyl group or an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a silicon number of 50 The substituent is selected from the group consisting of the following (poly) dimethylsiloxy groups or a hydrogen atom, k is a positive integer of 5 or more, m is 0 or a positive integer, and k + m is the hydrogen polysiloxane. (The number at which the viscosity at 25 ° C. is in the range of 10 to 1,000,000 mPa · s.)
[11]
The inorganic oxide is selected from the group consisting of Al, B, In, Si, Ge, Sn, Ti, Mn, Zn, Y, Zr, Hf, Ta, La, Ce, Pr, Nd, Tb, Dy, and Yb. The method for producing surface-treated inorganic oxide particles according to [10], comprising an oxide of one or more elements.
[12]
The surface-treated inorganic oxide particle according to [10] or [11], wherein the inorganic oxide is a core-shell particle having titanium oxide particles as a nucleus and a silicon oxide shell outside the nucleus. Production method.
[13]
The inorganic oxide is a core-shell type tetragonal titanium oxide particle having, as a nucleus, tetragonal titanium oxide solid solution particles in which tin and manganese are dissolved, and having a silicon oxide shell outside the nucleus. [10] The method for producing surface-treated inorganic oxide particles according to [11].
[14]
The polar organic solvent in the step (A) is one or more selected from the group consisting of methanol, ethanol, isopropyl alcohol, and n-propyl alcohol, [10] to [13] A method for producing surface-treated inorganic oxide particles.
[15]
[10] to [14], wherein the aprotic organic solvent in the step (B) is at least one selected from the group consisting of benzene, toluene, o-xylene, m-xylene and p-xylene. ] The manufacturing method of the surface treatment inorganic oxide particle in any one of.
[16]
In the step (C), the bond between the hydrogenpolysiloxane represented by the general formula (I) and the inorganic oxide particles having an organosilyl residue on the surface is a hydrosilyl group on the hydrogenpolysiloxane. And [10] to [15], which are formed by a dehydrogenation reaction with a hydroxyl group on an inorganic oxide particle surface or an organosilyl residue on the particle surface or a dealkane reaction with an alkoxy group. The manufacturing method of the surface treatment inorganic oxide particle in any one.
[17]
The method for producing surface-treated inorganic oxide particles according to [16], wherein the dehydrogenation reaction or the dealkane reaction uses tris (pentafluorophenyl) borane as a catalyst.
[18]
Further, (D) an addition reaction between a hydrosilyl group derived from the hydrogen polysiloxane represented by the general formula (I) bonded to the inorganic oxide particles and a compound having an unsaturated bond, and having a hydroxyl group The method for producing surface-treated inorganic oxide particles according to any one of [10] to [17], comprising a step of performing a dehydrogenation reaction with a compound or a dealkane reaction with a compound having an alkoxy group .

  According to the present invention, it is possible to obtain surface-treated inorganic oxide particles exhibiting high dispersibility in a nonpolar organic solvent without agglomerating from an aqueous dispersion colloidal solution. Further, the obtained particles have high dispersion stability because siloxane is strongly bonded to the surface. Therefore, the inorganic oxide particles obtained in the present invention can be introduced into various resins having no polar group without impairing the transparency of the resin due to its high dispersibility. Can be greatly expanded. From this, the present invention is considered to contribute to industrial development in this field.

It is an infrared-light absorption (IR) spectrum of the surface treatment titanium oxide (E-1) synthesize | combined at the process A of Example 1, and a raw material titanium oxide particle (W-1). It is IR spectrum of the surface treatment titanium oxide (E-1) synthesize | combined at the process A of Example 1, and the surface treatment titanium oxide (OT-1) synthesize | combined in Example 1. FIG. It is IR spectrum of the surface treatment titanium oxide (OT-1) synthesize | combined in Example 1, and the surface treatment titanium oxide (OT-6) synthesize | combined in Example 6. It is a thermogravimetric curve of the surface treatment titanium oxide (OT-1) synthesize | combined in Example 1, and the surface treatment titanium oxide (OT-6) synthesize | combined in Example 6. FIG. It is IR spectrum of the surface treatment titanium oxide (OT-1) synthesize | combined in Example 1, and the surface treatment titanium oxide (OT-7) synthesize | combined in Example 7. 4 is a thermogravimetric curve of the surface-treated titanium oxide (OT-1) synthesized in Example 1 and the surface-treated titanium oxide (OT-7) synthesized in Example 7. FIG. IR spectrum of surface-treated titanium oxide (OT-1) synthesized in Example 1, surface-treated titanium oxide (OT-2) synthesized in Example 2, and surface-treated titanium oxide (OT-3) synthesized in Example 3 It is.

  The surface-treated inorganic oxide particles of the present invention, the dispersion containing the particles, and the production method thereof will be described in detail below.

[Surface treatment inorganic oxide particles]
The surface-treated inorganic oxide particles in the present invention are inorganic oxide particles in which hydrogen polysiloxane is bonded to inorganic oxide particles having an organosilyl residue on the surface.

<Inorganic oxide particles>
The inorganic oxide particles used in the present invention are inorganic oxides having an organosilyl residue on the surface. The elements constituting the nucleus of the inorganic oxide are preferably 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.

  In the present invention, the inorganic oxide is a group of Al, B, In, Si, Ge, Sn, Ti, Mn, Zn, Y, Zr, Hf, Ta, La, Ce, Pr, Nd, Tb, Dy, and Yb. It is preferable that the oxide of 1 or more types of elements chosen from these is included.

If the inorganic oxide used by this invention is chosen from the group of the said metal oxide, what was compounded individually by 1 type or 2 types or more can be used. 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 via a chemical bond refers to a form represented by the following general formula (II).
(M ¹ O _x ) _m (M ² O _y ) _n (II)

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. Any 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 any one element and is not the same element selected in 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 a core-shell particle (a particle having a metal oxide particle as a nucleus and a shell of another metal oxide outside the nucleus), For example, it is formed by hydrolyzing a plurality of types of metal alkoxides in stages according to the type.

  As the inorganic oxide particles prepared in the present invention, in particular, one or a combination of two or more of the above-described metal element oxides is used as a nucleus, and the above-described metal element oxide is formed outside the nucleus. It is preferable to use core-shell particles having a shell of a single type or a combination of two or more types. As such a core-shell particle, a core-shell particle having titanium oxide, cerium oxide or the like as a nucleus and a shell of silicon oxide, aluminum oxide, zirconium oxide or the like outside the nucleus, particularly a titanium oxide particle as a nucleus, The core-shell particle which has the shell of a silicon oxide on the outer side is mentioned. The core-shell particles (core-shell type tetragonal titanium oxide solid solution) that are particularly preferably used in the present invention will be described in detail below.

  The core-shell type tetragonal titanium oxide solid solution is preferably a core-shell type tetragonal titanium oxide solid solution having tetragonal titanium oxide particles having solid solution of tin and manganese as nuclei and having a silicon oxide shell outside the nuclei. .

  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 preferably used as a solid solvent for manganese.

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.
On the other hand, any tin component may be used as long as it is derived from a tin compound, and examples thereof include tin chalcogenides such as tin oxide and tin sulfide, and tin oxide is preferable. Examples of tin compounds 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, tin oxide and the like can be used, but it is preferable to use tin chloride from the viewpoint of stability and availability. In addition, tin in the tin salt can be selected from divalent to tetravalent valences, but it is particularly preferable to use tetravalent tin.

  When tin and manganese are solid-dissolved in tetragonal titanium oxide, the solid solution amount of the tin component is 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 component is 10 to 1,000, more preferably 20 to 200, in terms of a molar ratio with titanium (Ti / Mn). 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 deactivated sufficiently, and the crystal system becomes an anatase type having a small visible absorption ability, which is not preferable.

  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, F centers that cause coloring are easily formed, and since the symmetry around the metal ions is poor, the Frank-Condon factor of vibronic transition in the metal ions also increases, and it becomes easy to absorb visible light. Therefore, the substitution type is preferable.

  The shell of silicon oxide formed outside the core of tetragonal titanium oxide particles with solid solution of tin and manganese is mainly composed of silicon oxide and may contain other components such as tin and aluminum. It may be formed by such a method. 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 carried out 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 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 tetragonal titanium oxide particles solidly dissolved in tin and manganese as a nucleus and having a silicon oxide shell outside the nucleus is 20 -50 mass%, preferably 25-45 mass%, more preferably 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, aggregation of the particles is promoted and the dispersion is opaque, which is not preferable.

In a core-shell type tetragonal titanium oxide solid solution, a volume-based 50% cumulative distribution diameter of tetragonal titanium oxide particles in which tin and manganese as solid nuclei measured by a dynamic light scattering method using laser light (D ₅₀ ) is 30 nm or less, more preferably 20 nm or less, and the 50% cumulative distribution diameter (D ₅₀ ) based on volume 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 values of the core particles and the core-shell type solid solution exceed the upper limit, the dispersion is not preferable because it is opaque. Although not particularly limited, the lower limit of D ₅₀ of the core particles, 5 nm or more, D ₅₀ the lower limit of the core-shell type solid solution is 6nm or more. In addition, as an apparatus for measuring such a volume-based 50% cumulative distribution diameter (D ₅₀ , hereinafter referred to as “average particle diameter”), for example, Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) And the like.

<Organosilyl residue>
The organosilyl residue present on the particle surface is a single functional group such as an alkyl group, an alkoxy group, a vinyl group, a phenyl group, an epoxy group, an acrylic group, a methacryl group, or a styryl group on a silicon atom, or It has a substituent by 2 or more types of composites.

  The organosilyl residue on the particle surface can be evaluated by confirming a peak characteristic of the organosilyl residue by IR spectrum or solid state NMR spectrum. The introduction amount of the organosilyl residue can be estimated from the difference between the weight reduction rate of the surface treatment particles having no organosilyl residue and the weight reduction rate of the surface treatment particles having an organosilyl residue. From the viewpoint of imparting dispersibility to an organic solvent, it is preferably 2% by mass or more of the treated particles, more preferably 5 to 30% by mass, and still more preferably 5 to 20% by mass.

（式（Ｉ）中において、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸及びＲ⁹は、それぞれ同一又は異なっていてもよく、（メタ）アクリル基、オキシラニル基もしくはフッ素原子で置換されていてもよい炭素数１以上２０以下のアルキル基と、炭素数２以上２０以下のアルケニル基と、炭素数６以上２０以下のアリール基と、及びケイ素数５０以下の（ポリ）ジメチルシロキシ基とからなる群から選ばれる置換基又は水素原子であり、ｋは５以上の正の整数、ｍは０又は正の整数であり、ｋ＋ｍは該ハイドロジェンポリシロキサンの２５℃における粘度を１０〜１，０００，０００ｍＰａ・ｓの範囲とする数である。） <Hydrogen polysiloxane>
The hydrogen polysiloxane that modifies the particle surface is represented by the following general formula (I). Units that are capable of effectively modifying the particle surface by using a polymer material having a large number of reactive sites as the surface treatment agent, and that are not bonded to the unit that is bonded to the particle surface, which is a feature of the polymer dispersant. The direct contact of the particle surface is strongly suppressed by the effect of the loop train structure formed by, and inorganic oxide particles having high dispersibility can be obtained.

(In the formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ may be the same or different from each other, and a (meth) acryl group An oxiranyl group or an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a silicon number of 50 The substituent is selected from the group consisting of the following (poly) dimethylsiloxy groups or a hydrogen atom, k is a positive integer of 5 or more, m is 0 or a positive integer, and k + m is the hydrogen polysiloxane. (The number at which the viscosity at 25 ° C. is in the range of 10 to 1,000,000 mPa · s.)

In this case, the alkyl group for R ^{1 to} R ⁹ is preferably an alkyl group having 1 to 6 carbon atoms, particularly a methyl group or an ethyl group, and the alkenyl group is preferably one having 2 to 6, particularly a vinyl group. And aryl groups, and aryl groups include those having 6 to 10 carbon atoms, particularly phenyl groups. Further, the silicon number of the (poly) dimethylsiloxy group is preferably 1 to 50, particularly 1 to 30. Moreover, although k is an integer greater than or equal to 5, Preferably it is 5-200, More preferably, it is 5-100, More preferably, it is 5-50. On the other hand, m is preferably 0 to 100, more preferably 0 to 50, and the viscosity at 25 ° C. is preferably 10 to 1,000,000 mPa · s, particularly preferably 10 to 10,000 mPa · s. The viscosity is a value measured by a rotational viscometer.

  Specific examples of the hydrogenpolysiloxane represented by the general formula (I) include trimethylsiloxy group-blocked methylhydrogenpolysiloxanes (trade names “KF-99” and “KF-9901” manufactured by Shin-Etsu Chemical Co., Ltd.). ), Trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer, both ends trimethylsiloxy group-capped methylphenylsiloxane / methylhydrogensiloxane copolymer, both terminal trimethylsiloxy group-capped diphenylsiloxane / methylhydrogensiloxane copolymer Copolymer, trimethylsiloxy group-capped dimethylsiloxane / phenylhydrogensiloxane copolymer, both ends trimethylsiloxy group-capped methylphenylsiloxane / phenylhydrogensiloxane copolymer, Terminal trimethylsiloxy group-blocked diphenylsiloxane / phenylhydrogensiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked methylphenylsiloxane / methylhydrogen Siloxane copolymer, dimethylhydrogensiloxy group-blocked diphenylsiloxane / methylhydrogensiloxane copolymer, dimethylhydrogensiloxy-blocked dimethylpolysiloxane at both ends, dimethylhydrogensiloxy-blocked methylphenylpolysiloxane at both ends, both Terminal dimethylhydrogensiloxy group-blocked diphenylpolysiloxane, both ends dimethylhydrogensiloxy group-blocked dimethylsilane Xylene / methylphenylsiloxane copolymer, dimethylhydrogensiloxy group-blocked dimethylsiloxane / diphenylsiloxane copolymer, dimethylhydrogensiloxy group-blocked methylphenylsiloxane / diphenylsiloxane copolymer, dimethylhydrogensiloxy at one end Blocked dimethylpolysiloxane, single-ended dimethylhydrogensiloxy-blocked methylphenylpolysiloxane, single-ended dimethylhydrogensiloxy-blocked diphenylpolysiloxane, single-ended dimethylhydrogensiloxy-blocked dimethylsiloxane / methylphenylsiloxane copolymer, piece Terminal dimethylhydrogensiloxy group-capped dimethylsiloxane / diphenylsiloxane copolymer, one-end dimethylhydrogensiloxy group-capped Examples thereof include a chain methylphenylsiloxane / diphenylsiloxane copolymer.

The above-mentioned modification with hydrogen polysiloxane is a dehydrogenation reaction or dealkane reaction in which a hydroxyl group or alkoxy group on the particle and an organosilyl residue reacts with a hydrosilyl group on the hydrogen polysiloxane to form a siloxane bond. is there.
Examples of the catalyst include transition metal compounds such as platinum catalysts, rhodium catalysts, ruthenium catalysts, and palladium catalysts, and Lewis acidic compounds. Specific examples include Wilkinson's catalyst, tris (dibenzylideneacetone) dipalladium, bis (triphenylphosphine) palladium (II) dichloride, tetrakis (triphenylphosphine) palladium (0), and tris (pentafluorophenyl) borane. In particular, tris (pentafluorophenyl) borane is preferred. The amount of the catalyst used is a catalyst amount, but is preferably 0.01% by mass or more and 20% by mass or less, more preferably 0.1% by mass with respect to the solid content mass of the inorganic oxide colloidal dispersion. It is 10 mass% or less, More preferably, it is 1 mass% or more and 5 mass% or less. If the addition amount is more than 20% by mass, the reaction proceeds rapidly and may be difficult to control, and if the addition amount is less than 0.01% by mass, the reaction may not proceed.

The surface-treated inorganic oxide particles obtained by modification with the hydrogen polysiloxane may have a hydrosilyl residue derived from hydrogen polysiloxane on the surface, and the presence thereof is determined by infrared absorption (IR) spectrum. It can be confirmed by the presence or absence (2,175 cm ⁻¹ ) of an absorption peak derived from a hydrosilyl group.

  The amount of hydrogen polysiloxane used for the surface modification is preferably 10% by mass or more and 200% by mass or less, more preferably 50% by mass or more and 120% by mass or less, and still more preferably with respect to the inorganic oxide particles. Is 70 mass% or more and 100 mass% or less. If the amount added is more than 200% by mass, gelation may occur. When the addition amount is less than 10% by mass, the coating may not proceed and may aggregate.

The inorganic oxide particles obtained in the present invention include a hydrosilyl residue generated after hydrogenpolysiloxane modification, a silane compound represented by the following general formula (III) or a partial hydrolysis condensate thereof, or a unit price or a polyhydric alcohol. It may be further modified by dehydrogenation reaction or dealkane reaction with a system compound.
R ¹⁰ _p Si (OR ¹¹ ) _4-p (III)
(In the formula, each R ¹⁰ may be the same or different and is substituted with a functional group such as a (meth) acryl group, a (meth) acryloyl group, an oxiranyl group, a fluorine atom, an amino group, a mercapto group, or an isocyanate group. An alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a (poly) dimethylsiloxy group having 50 to silicon atoms. And R ¹¹ is a hydrogen atom or an alkyl group having 6 or less carbon atoms, and p is 1, 2 or 3.)

  Specific examples of p = 1 in the silane compound represented by the general formula (III) include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriethoxysilane. Isopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltriisopropoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltri Ethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) E) Ethyltrimethoxysilane, γ-chloropropyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, γ -Mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (2-aminoethyl) aminopropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltri Partial hydrolysis of ethoxysilane, tris (3-trimethoxysilylpropyl) isocyanurate, tris (3-triethoxysilylpropyl) isocyanurate, and trimethylsilane Condensates (trade names “KC-89S”, “X-40-9220” manufactured by Shin-Etsu Chemical Co., Ltd.), partial hydrolysis condensates of methyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane (trade names) “X-41-1056” manufactured by Shin-Etsu Chemical Co., Ltd.).

  Specific examples of p = 2 in the silane compound represented by the general formula (III) include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, methylpropyldimethoxysilane, Methylpropyldiethoxysilane, diisopropyldimethoxysilane, phenylmethyldimethoxysilane, vinylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ) Ethylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxy Orchids, .gamma.-aminopropyl methyl diethoxy silane, N- (2- aminoethyl) and aminopropyl methyl dimethoxy silane and the like.

  Specific examples of p = 3 in the silane compound represented by the general formula (III) include trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, n-propyldimethylmethoxysilane, n-propyldiethylmethoxysilane, iso- Propyldimethylmethoxysilane, iso-propyldiethylmethoxysilane, propyldimethylethoxysilane, n-butyldimethylmethoxysilane, n-butyldimethylethoxysilane, n-hexyldimethylmethoxysilane, n-hexyldimethylethoxysilane, n-pentyldimethylmethoxy Silane, n-pentyldimethylethoxysilane, n-hexyldimethylmethoxysilane, n-hexyldimethylethoxysilane, n-decyldimethylmethoxysilane, n-decyl Methylethoxysilane, trimethylsilanol, triethylsilanol, n-propyldimethylsilanol, n-propyldiethylsilanol, iso-propyldimethylsilanol, iso-propyldiethylsilanol, propyldimethylsilanol, n-butyldimethylsilanol, n-hexyldimethylsilanol, Examples thereof include n-pentyldimethylsilanol and n-decyldimethylsilanol.

  Specific examples of unit prices and polyhydric alcohol compounds used include methanol, ethanol, 1-propanol, 2-propanol, pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 1-heptanol, ethylene glycol, Examples include propylene glycol, β-thiadiglycol, butylene glycol, and glycerin.

  As a catalyst used for the dehydrogenation reaction or dealkane reaction of the silane compound or alcohol compound represented by the general formula (III), transition metallization such as a platinum catalyst, a rhodium catalyst, a ruthenium catalyst, and a palladium catalyst is a compound or Lewis acidic compounds, specifically, Wilkinson's catalyst, tris (dibenzylideneacetone) dipalladium, bis (triphenylphosphine) palladium (II) dichloride, tetrakis (triphenylphosphine) palladium (0) and tris ( Pentafluorophenyl) borane and the like, and tris (pentafluorophenyl) borane is particularly preferable.

  The inorganic oxide particles obtained in the present invention may be further modified by a hydrosilylation reaction between a hydrosilyl residue generated after hydrogenpolysiloxane modification and a compound having an unsaturated bond, and the added unsaturated bond Specific examples of the compound having benzene include compounds having a long-chain alkyl such as pentene, hexene and octene, compounds having an aromatic ring such as styrene and pentafluorostyrene, 3,3,4,4,4-pentafluoro-1 A compound containing a fluoroalkyl group such as butene, 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and 1H, 1H, 2H-heptadecafluoro-1-decene, Examples include compounds containing a siloxy group such as trimethylvinylsilane.

  Examples of the catalyst used in the hydrosilylation reaction include transition metal compounds such as platinum catalysts, rhodium catalysts, and ruthenium catalysts, and Lewis acidic compounds. Wilkinson's catalyst, Karstedt's catalyst, Spiel's catalyst, Tris ( Pentafluorophenyl) borane and the like are preferable.

[Dispersion containing surface-treated inorganic oxide particles]
The inorganic oxide colloidal solution has 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 control, ultraviolet shielding, radiation shielding, fluorescence, etc. Optical characteristics that can be applied, and electrical characteristics that can impart electrical conductivity and dielectric constant. As described above, the inorganic oxide colloid solution has various functions as long as the types of elements constituting the inorganic oxide colloid solution are various. However, the aspect of chemical engineering as a colloidal solution is similar. Therefore, when considering solvent replacement of an inorganic oxide colloidal solution, one inorganic oxide such as the metal oxide mentioned here is used alone. Or what combined 2 or more types can be handled as one group. A chemical engineering aspect is a physical property handled in the category of powder engineering or migration phenomenology, such as the particle size of a dispersoid, the zeta potential, and the like. As long as these physical quantities are used for observation, the inorganic oxide colloidal solution can be compared with each other and recognized as a parallel set, even if the types of elements constituting the dispersoid are different. Therefore, colloidal solutions that are not described in the present specification and examples are not described in detail for all types and / or combinations of inorganic oxide (metal oxide) colloidal solutions. Does not prevent it from being included in the range.

<Dispersed quality>
Dispersoids in the colloidal solution are the above-mentioned surface-treated inorganic oxide particles, such as silicon oxide, aluminum oxide, titanium oxide, zinc oxide, cerium oxide, tin oxide, boron oxide, and indium oxide surface-treated with hydrogen polysiloxane Is mentioned. When these colloidal solutions are added to, for example, coating paints, one or more kinds of metal oxides are usually used depending on the purpose. Therefore, the colloidal solution in the present invention contains a plurality of kinds of metal oxides. Does not interfere with inclusion. Examples of the purpose of adding the colloidal solution 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 at least one kind 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 as colloidal solutions are similar, and therefore, solvent replacement of inorganic oxide dispersions. Can be handled as a group of metal oxides listed here alone or in combination of two or more.

The particle size (average cumulative particle size) of the dispersoid in the colloidal solution can be measured by various methods. The range of the particle diameter in the present invention uses 50% cumulative distribution diameter (D ₅₀ ) based on the volume of an object measured by a dynamic light scattering method using laser light, but is observed using an electron microscope as evidence. It is also possible to do. 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 adding a dispersion 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, more preferably 1 to 100 nm. More preferably, it is -80nm, and it is especially preferable that it is 1-50nm. 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 becomes extremely large, which may make it difficult to handle the colloidal solution.

<Dispersion medium>
Various liquids can be used as the dispersion medium in the colloidal solution. Specific examples include decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, icosane, eicosane, docosan, 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-thiadiglycol Unit price and polyhydric alcohols such as butylene glycol and 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 glycol monopropyl Ethers such as ether and 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, diethyl malonate, malon Dipropyl acid, dibutyl malonate, ethylene glycol diformate, ethylene glycol diacetate, ethylene glycol dipropionate, ethylene glycol dibutyrate, propylene glycol diacetate, propylene Esters such as ethylene 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 Ketones such as acetone, diacetone alcohol, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, methyl normal butyl ketone, dibutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone; dimethylformamide, dimethylacetamide, tetra Acetylethylenediamide, tetraacetyl Amides such as hexamethylenetetramide and N, N-dimethylhexamethylenediamine diacetate; hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopenta Siloxane, dodecamethylcyclohexasiloxane, hexaphenylcyclotrisiloxane, octaphenylcyclotetrasiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, 1,3,5-tris (3,3,3-trifluoro Propyl) -1,3,5-trimethylcyclotrisiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, etc. Mixed A liquid can be mentioned. Among the above, the surface-treated inorganic oxide particles of the present invention can be suitably used for polysiloxane or cyclic siloxane.

  In this case, the dispersion medium may be at least one selected from the group consisting of hydrocarbon compounds having 5 to 30 carbon atoms, alcohol compounds, ether compounds, ester compounds, ketone compounds, siloxane compounds, and amide compounds. Particularly preferred is one or more siloxane compounds.

<Dispersion>
The dispersion contains from 0.01% by weight to 50% by weight, preferably from 0.1% by weight to 30% by weight, and more preferably from 1% by weight to 20% by weight. When the content of the dispersoid is less than 0.01% by mass, the effect when mixed with the resin is hardly obtained. When the content of the dispersoid exceeds 50% by mass, the storage stability of the dispersion may be insufficient.

[Method for producing surface-treated inorganic oxide particles]
In the method for producing surface-treated inorganic oxide particles in the present invention, (A) inorganic oxide particles are surface-treated with a silane coupling agent and / or (partial) hydrolysis condensate, and then dispersed in a polar organic solvent dispersion medium. And (B) replacing the dispersion medium with an aprotic organic solvent while removing the polar organic solvent by distillation and / or ultrafiltration, and (C) reacting with hydrogenpolysiloxane. It is characterized by that.

<Raw material colloid dispersion>
The production of the surface-treated inorganic oxide particles in the present invention is preferably carried out using a colloidal dispersion of inorganic oxide particles. The raw material colloidal dispersoid used is preferably a group 13 element, a group 14 element (excluding carbon), a first series transition element, a second series transition element, or a third series transition as an element constituting the nucleus of the inorganic oxide. One type selected from the group of metal oxides such as elements and lanthanoids, or a combination of two or more types. In particular, a single element or a combination of two or more of the metal element oxides described above is used as a nucleus, and one or more of the metal element oxides described above are combined outside the nucleus. It is preferable to use core-shell particles having a shell. Examples of such core-shell particles include core-shell particles having a titanium oxide-tin oxide-manganese oxide composite oxide (titanium oxide particles in which tin and manganese are dissolved) as a nucleus and a silicon oxide shell outside the nucleus. It is done.

  The raw material colloidal dispersion prepared in 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. The ion-exchanged water can be produced using a pure water producing device (for example, product made by Organo Corporation, product name “FW-10”, Merck Millipore Corporation, product name “Direct-QUV3”, etc.). Further, the dispersion medium may contain a monohydric alcohol that is arbitrarily miscible with water in the step of producing an aqueous dispersion colloidal solution as described below. The monohydric alcohol optionally miscible with water may be contained as a co-solvent in producing the core-shell particles and the origin as a hydrolysis by-product of the metal alkoxide in the sol-gel reaction.

  The concentration of the raw material colloid solution prepared in the present invention is preferably 1% by mass to 35% by mass, more preferably 5% by mass to 30% by mass, and still more preferably 10% by mass to 25% by mass. If the concentration of the colloidal solution is lower than 1% by mass, the production efficiency may not be good, which is not preferable. When the concentration of the colloidal solution is higher than 35% by mass, gelation may be easily caused depending on conditions such as pH and temperature.

[Step (A)]
In the step (A), the surface of the inorganic oxide particles is treated with a silane compound and / or a (partial) hydrolysis condensate of the silane compound (A-1), the solvent substitution with a polar organic solvent (A-2) ). Details will be described below.

[Step (A-1)]
Step (A-1) is a step of modifying the particle surface by adding a silane compound represented by the following general formula (IV) and / or a (partial) hydrolysis condensate of the silane compound. Thereby, it reacts with OH groups and the like on the particle surface, and the residue of the silane compound or its (partial) hydrolyzate or (partial) hydrolysis condensate is bonded to the particle surface via an oxygen atom. In addition, in the following formula (IV), when q is 1 or 2, it can be bonded to 3 or 2 oxygen atoms on the particle surface, but X or X hydrolyzed OH does not condense on the particle surface. This is not the case because it may remain.
R ¹² _q Si (X) _4-q (IV)
(In the formula, each R ¹² may be the same or different and may be substituted with a functional group such as a (meth) acryl group, an oxiranyl group, a fluorine atom, an amino group, a mercapto group, or an isocyanate group). Selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a (poly) dimethylsiloxy group having 50 or less silicon atoms And X is a substituent selected from the group consisting of an alkoxy group, an allyl group, an acetoxy group, an enol group, and a chlorine atom, and q is 1, 2 or 3.)

  In this case, the alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, particularly a methyl group or an ethyl group, and the aryl group is an alkyl group having 6 to 10 carbon atoms, particularly a phenyl group. Further, the silicon number of the (poly) dimethylsiloxy group is preferably 1 to 50, particularly 1 to 30.

  Specific examples of q = 1 in the silane compound represented by the general formula (IV) include hydrogen trimethoxy silane, hydrogen triethoxy silane, methyl trimethoxy silane, methyl triethoxy silane, methyl triisopropoxy silane, ethyl tri Methoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltriisopropoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, γ-methacryloxypropyl Trimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glyci Doxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-chloropropyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-tri Fluoropropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (2-aminoethyl) aminopropyltrimethoxy Silane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, tris (3-trimethoxysilyl) in which isocyanate groups are bonded to each other (Lopyl) isocyanurate, tris (3-triethoxysilylpropyl) isocyanurate, methyltrimethoxysilane partially hydrolyzed condensate (trade names “KC-89S”, “X-40-9220” manufactured by Shin-Etsu Chemical Co., Ltd.) ), Alkoxysilanes such as partially hydrolyzed condensate of methyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane (trade name “X-41-1056” manufactured by Shin-Etsu Chemical Co., Ltd.); triallylmethylsilane , Allylsilanes such as triallylethylsilane, triallylisopropylsilane; acetoxysilanes such as triacetoxymethylsilane, triacetoxyethylsilane, triacetoxypropylsilane, triacetoxyphenylsilane; trichloromethylsilane, trichloroethylsilane, trichloropropyl Shi And chlorosilanes such as trichlorophenylsilane; enol silanes such as triisopropenyloxymethylsilane, ethyltriisopropenyloxysilane, triisopropenyloxypropylsilane, and phenyltriisopropenyloxysilane .

In the silane compound represented by the general formula (IV), specific examples in the case where q = 1 and R ¹² is polydimethylsiloxane include compounds represented by the following general formula (V). In general formula (V), preferably r is an integer of 0 to 50, more preferably r is an integer of 5 to 40, and more preferably r is an integer of 10 to 30. When r 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 following general formula (V), a compound having an average structure of r = 30 can be obtained as a trade name “X-24-9822” (manufactured by Shin-Etsu Chemical Co., Ltd.). Me represents a methyl group.

  Specific examples in the case of q = 2 in the silane compound represented by the general formula (IV) include methylhydrogendimethoxysilane, methylhydrogendiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, diethyl Dimethoxysilane, diethyldiethoxysilane, methylpropyldimethoxysilane, methylpropyldiethoxysilane, diisopropyldimethoxysilane, phenylmethyldimethoxysilane, vinylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyl Diethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacrylo Alkoxysilanes such as xylpropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) aminopropylmethyldimethoxysilane, diphenyldimethoxysilane, diethoxydiphenylsilane Allylsilanes such as diallyldimethylsilane, diallyldiethylsilane, diallyldiisopropylsilane; acetoxysilanes such as diacetoxydimethylsilane, diacetoxydiethylsilane, diacetoxydipropylsilane, diacetoxydiphenylsilane; dichlorodimethylsilane, dichlorodiethyl Chlorosilanes such as silane, dichlorodipropylsilane, dichlorodiphenylsilane; diisopropenyloxydimethylsilane, diethyldiiso Examples include enolsilanes such as propenyloxysilane, diisopropenyloxydipropylsilane, and diphenyldiisopropenyloxysilane.

  Specific examples of q = 3 in the silane compound represented by the general formula (IV) include trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, n-propyldimethylmethoxysilane, n-propyldiethylmethoxysilane, iso- Propyldimethylmethoxysilane, iso-propyldiethylmethoxysilane, propyldimethylethoxysilane, n-butyldimethylmethoxysilane, n-butyldimethylethoxysilane, n-hexyldimethylmethoxysilane, n-hexyldimethylethoxysilane, n-pentyldimethylmethoxy Silane, n-pentyldimethylethoxysilane, n-hexyldimethylmethoxysilane, n-hexyldimethylethoxysilane, n-decyldimethylmethoxysilane, n-decyldi Alkoxysilanes such as tilethoxysilane, triphenylmethoxysilane, triphenylethoxysilane; allyltrimethylsilane, allyltriethylsilane, allyltriisopropylsilane, allyl (tert-butyl) dimethylsilane, allyl (chloromethyl) dimethylsilane, etc. Allylsilanes; acetoxysilanes such as acetoxytrimethylsilane, acetoxytriethylsilane, acetoxytripropylsilane, and acetoxytriphenylsilane; chlorosilanes such as chlorotrimethylsilane, chlorotriethylsilane, chlorotripropylsilane, and chlorotriphenylsilane; Nyloxytrimethylsilane, triethylisopropenyloxysilane, isopropenyloxytripropylsilane, triphenylisopropyl Such as enol silanes such as Bae oxy silane can be exemplified.

  The addition amount of the silicon compound to be added is preferably 0.5 times or more and 50 times or less, more preferably 1 time or more and 25 times or less, with respect to the solid content weight of the raw material colloid water dispersion. Preferably it is 2 times or more and 10 times or less. If the amount added is more than 50 times the solid content weight of the inorganic oxide, gelation may occur. When the addition amount is less than 0.5 times, the coating may not be sufficiently performed and aggregation may occur.

  The addition method of a silicon compound can implement dripping in a liquid, dripping outside a liquid, a potion addition, etc., and it is preferable that it is dripping in a liquid.

  In the step (A-1), an acid or base catalyst for promoting the surface treatment can be added as necessary. Specific examples of the base catalyst include potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate and basic ion exchange resin. Examples of the acid catalyst include hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, acetic acid, and a cationic ion exchange resin. Examples of the cationic ion exchange resin include Amberlite (manufactured by Organo), Levacit (manufactured by LANXESS), Purolite (manufactured by Purolite), Muromac (manufactured by Muromachi Chemical Co., Ltd.), and the like. Preferably it is 0.01 mass% or more and 20 mass% or less with respect to solid content mass of an inorganic oxide colloid dispersion liquid, More preferably, it is 0.1 mass% or more and 10 mass% or less, More preferably, it is 1 mass. % To 5% by mass. If the addition amount is more than 20% by mass, the reaction proceeds rapidly and may be difficult to control, and if the addition amount is less than 0.01% by mass, the reaction may not proceed.

  The liquid temperature when adding the silicon compound 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. If the liquid temperature is lower than 0 ° C., the inorganic oxide colloidal aqueous dispersion may change in quality through freezing, which is not preferable. When the liquid temperature is higher than 45 ° C., the added silane may cause an unexpected hydrolysis condensation reaction, which is not preferable. As a result of hydrolysis condensation, the temperature of the reaction solution may reach a level not exceeding 70 ° C.

  In the step (A-1), the reaction solution may be diluted with an organic solvent as necessary, and the diluting solvent is preferably a monohydric alcohol such as methanol, ethanol, isopropyl alcohol, or butanol; ethylene glycol, propylene glycol Polyhydric alcohols such as glycerin; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, glyme and diglyme; ketones such as acetone and methyl isobutyl ketone; esters such as ethyl acetate and propylene glycol monomethyl ether acetate; Reactive esters such as hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate; , In particular, ethanol, isopropyl alcohol is preferred. Dilution is preferably performed in order to avoid the solvent shock in the next step (A-2), but it is not always essential. The dilution factor is preferably 1 to 20 times, more preferably 2 to 15 times, and still more preferably 3 to 10 times. If the ratio is smaller than 1, the intended solvent shock mitigation effect may not be sufficient. If it is greater than 20, it may take a lot of processing time in the next step.

[Step (A-2)]
Step (A-2) is a step of substituting the dispersion medium in the reaction liquid with a polar organic solvent, and by leaching the dispersion medium of the dispersion liquid by ultrafiltration, concentration can be performed as necessary. . The dispersion medium is derived from the water contained in the aqueous dispersion produced in the step (A-1), the added silicon compound and / or the hydrolyzed condensate of the silicon compound and / or the silicate ester produced by the hydrolytic condensation. Alcohols and organic solvents can be included. By exuding such a composite dispersion, the solid concentration of the dispersion in the filtration chamber is preferably 1 to 30% by mass, more preferably 5 to 25% by mass, and still more preferably 10 to 20% by mass. Concentrate to The dispersion medium that exudes in this system forms a complex mixture, but a porous ceramic filter can be preferably used. In the conventional method, a hollow fiber membrane is suitably used for removing salts in water, but there is a risk of clogging in the particle dispersion system. Organic polymer ultrafiltration membranes are often used in areas such as particle removal, concentration, and solid-liquid separation. However, when organic solvents are contained, the filtration membrane may swell and become unusable. An inorganic ceramic filter is useful for solid-liquid separation and concentration of a sample containing an organic solvent.

In ultrafiltration, it is preferable to use a filter plate having an inorganic ceramic membrane having an average pore diameter of 5 nm or more and less than 20 nm, more preferably 6 nm or more and less than 18 nm, and most preferably 7 nm. It is preferable that the filter plate has a disk shape that can rotate. The porous inorganic ceramic membrane can be produced by a known method. Examples of the material of the porous inorganic ceramic film include spinel, alumina, titania, and zirconia. For example, in the case of a spinel system, a known method (Ueno, S, et al., Journal of Physics: Conference Series 2009, 165, No. 1, Fabrication of porous spinal digisigandi sir di gen sig ine sig ine sig ine, 2000, 2000, No. 03, MgAl ₂ O Ultrafiltration Ceramic Membrane Derived from Mg-Al Double Alkoxide, etc.). It is preferable to control the pore diameter by controlling the synthesis conditions and crystal growth of spinel. The filter plate is preferably formed by epitaxially growing a surface layer having a uniform pore diameter on a porous disc-shaped unglazed plate made of alumina or the like by a sol-gel method. As a porous disk made of alumina or the like, it is preferable to use a material having a pore diameter of 0.05 to 1 μm as a substrate. The surface layer has an average pore diameter of 5 nm or more and less than 20 nm, more preferably 6 nm or more and less than 18 nm, and most preferably 7 nm. The size of the disc-shaped filter plate is preferably 100 mm or more and less than 500 mm, more preferably 120 mm or more and less than 300 mm, and still more preferably 140 mm or more and 200 mm. When the diameter is less than 100 mm, it is difficult to apply a shear stress when rotating, and it is difficult to secure an area, which may not be preferable. If the diameter is 500 mm or more, the torque required for rotation may increase. Moreover, when too large, it may become easy to break and may become difficult to handle. The thickness of the filter plate is preferably 1 mm or more and less than 10 mm, and more preferably 3 mm or more and less than 5 mm. If the filter plate is less than 1 mm, the mechanical strength may not be ensured. If the filter plate is 10 mm or more, it may not be preferable in terms of securing the volume of the filtration chamber. Such a filter may be manufactured by a known method, or a commercially available filter may be used.

  The pore size of the filter used in the solvent replacement step is preferably determined by electron microscopy. Examples of electron microscopes that can be used for such purposes include scanning electron microscopes, transmission electron microscopes, and atomic force microscopes.

  In the solvent replacement step, the disperse solution is leached by a static pressure of preferably less than 0.5 MPa, more preferably less than 0.4 MPa, still more preferably less than 0.3 MPa, and most preferably less than 0.2 MPa and 0.03 MPa or more. When the static pressure is 0.5 MPa or more, the interface selection of the filtration device may be limited. If it is less than 0.03 MPa, it may not exude efficiently. The static pressure is preferably achieved by hydraulic and compressed air pressure in a head tube or closed system whose surface is in contact with the atmosphere. In particular, the method using the compressed air pressure is preferable because the apparatus can be made compact. The compressed air can be easily produced using a known method or a commercially available compressor.

In the solvent replacement step, a shear stress of preferably 0.1 Pa to 10 Pa, more preferably 0.5 Pa to 5 Pa, and still more preferably 1 Pa to 5 Pa is applied to the filter plate. The shear stress may be achieved by the flow of the dispersion or may be achieved by rotating a disk-shaped filter plate. In particular, when shear stress is applied by rotation of the filter plate, the shear rate of the surface of the filter plate is increased, which is preferable. The shear stress can be calculated from the distance between the walls in the filter chamber and the rotational speed. In addition, an appropriate baffle (baffle plate) can be provided in the filter chamber as necessary. The baffle is preferably installed for the purpose of reducing the distance between the walls in the filter chamber. Increasing the shear stress by rotation and baffle is a known means. The maximum shear stress (τ) acting on the circumference is the diameter of the disk-shaped filter plate (φ [m]), the rotation speed of the filter plate (ω [rps]), and the distance between the filter plate and the filtration chamber wall (L [m]), the circumference is (π), and the viscosity of the dispersion is (η [Pa · s]), for example, it can be calculated as in Equation (1).
τ = (η · π · φ · ω) / L [Pa] (1)
For example, the diameter φ = 0.15 [m], the rotational speed of the filter plate ω = 16.7 [rps] (≈1,000 [rpm]), the circumference π = 3.14, the viscosity η of the dispersion liquid = Τ = (0.001 × 3.14 × 0.15 × 16.7) /0.003≈2. When 0.001 [Pa · s] and the inter-wall distance L = 0.003 [m]. 6 [Pa]. The shear stress can be given by changing each parameter of φ, ω, and L so that the preferred range is reached.

The rotational energy applied to the dispersion in the solvent replacement step is preferably defined by shear stress, but can also be defined in the state of fluid. The state of the fluid can also be defined by the Reynolds number. The stirring Reynolds number is preferably 3,000 to 5,000,000, more preferably 5,000 to 1,000,000, and still more preferably 10,000 to 500,000. If it is less than 3,000, laminar stirring may occur and efficient dispersion may be difficult, and if it exceeds 5,000,000, the energy required for stirring is unnecessarily large, which is not preferable from the viewpoint of industrial efficiency. Sometimes. The Reynolds number (Re) can be obtained from Equation (2). In Equation (2), ρ represents density (kg / m ³ ), ω represents rotational speed (rps), φ represents filter plate diameter (m), and η represents viscosity (Pa · s).
Re = ρ · ω · φ ² / η ... Formula (2)

In the titanium oxide dispersion treated in the present invention, ρ is 900 to 2,000 (kg / m ³ ), preferably 1,000 to 1,500 (kg / m ³ ), and η is 0.001 to 0.05 (Pa S), preferably 0.002 to 0.01 (Pa · s). For example, a 0.15 (m) disk-shaped filter plate is treated with a titanium oxide dispersion having 16.7 (rps), ρ of 1,000 (kg / m ³ ), and η of 0.001 (Pa · s). In this case, Re is about 3.8 × 10 ⁵ . By appropriately selecting ω and φ, it can be adjusted to be within the desired range of Re.
Moreover, you may implement the improvement method of stirring efficiency by using the reactor which installed the baffle for stirring.

In a solvent substitution process, Preferably it implements at 5-80 degreeC, More preferably, it is 10-60 degreeC, More preferably, it is 15-50 degreeC, Most preferably, it implements at 20-40 degreeC. If it is lower than 5 ° C, the dispersion may freeze. When the temperature is higher than 80 ° C., there may be a problem in working environment due to volatilization of the dispersion medium and / or reaction energy when reactive esters are used, which may cause gelation. The viscosity of the dispersion generally depends on the temperature. Since the viscosity affects the rotational torque, the viscosity may be adjusted by adjusting the temperature so that the electromagnetic rotating machine and / or the motor is not overloaded.
In the solvent replacement step, unreacted compounds and by-products can be removed as necessary by continuous ultrafiltration.

  Here, specific examples of the organic solvent include unit price and polyhydric alcohol such as methanol, ethanol, 1-propanol, 2-propanol, cyclopentanol, ethylene glycol, propylene glycol, β-thiadiglycol, butylene glycol, glycerin and the like. 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 Ethers such as coal monopropyl ether, propylene glycol monobutyl ether, butylene glycol monomethyl ether, butylene glycol monoethyl ether, butylene glycol 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, diethyl malonate, dipropyl malonate, dibutyl malonate, Ethylene glycol diformate, ethylene glycol diacetate, ethylene glycol dipropionate, ethylene glycol dibutyrate, propylene glycol diacetate, propylene glycol dipropionate, propylene glycol dibutyrate, ethylene glycol methyl ether acetate, propylene glycol methyl ether acetate, Esters such as butylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol ethyl ether acetate, butylene glycol monoethyl ether acetate; acetone, diacetone alcohol, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, methyl normal butyl ketone, dibutyl Ketone Ketones such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone; amides such as dimethylformamide, dimethylacetamide, tetraacetylethylenediamide, tetraacetylhexamethylenetetramide, N, N-dimethylhexamethylenediamine diacetate; Can be mentioned respectively.

  The amount of the organic solvent used in the solvent replacement step is preferably 1 to 20 times the volume of the filtration chamber capacity, more preferably 2 to 10 times the volume, and even more preferably 3 to 8 times the volume. If the amount is less than 1 volume, solvent replacement may not be sufficient. If it is more than 20 times volume, it may not be preferable in terms of industrial efficiency.

[Step (B)]
Step (B) is a step in which the polar organic solvent derived from the dispersion medium of the inorganic oxide particle dispersion prepared in step (A) is removed and replaced with a nonpolar (aprotic) organic solvent. Solvent replacement is preferably carried out by distillation and / or ultrafiltration.

  The distillation is preferably performed at 200 mmHg or more and 760 mmHg or less, more preferably 300 mmHg or more and 760 mmHg or less, and further preferably 400 mmHg or more and 760 mmHg or less. At a pressure lower than 200 mmHg, the mixture may suddenly boil and be difficult to control, and at a pressure higher than 760 mmHg, the polar organic solvent may be difficult to evaporate.

  The distillation is preferably performed at 50 ° C. or more and 250 ° C. or less, more preferably 60 ° C. or more and 200 ° C. or less, and further preferably 80 ° C. or more and 150 ° C. or less. When the temperature is lower than 50 ° C., it may take time for distillation, and when the temperature is lower 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.

  As the heating required for distillation, various methods of heating by contact with a heat medium, induction heating, and heating by microwaves can be used.

Specific examples of the nonpolar (aprotic) organic solvent used in the step (B) include 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 The hydrocarbon compound of 30 or less can be mentioned.
In this case, the aprotic organic solvent in the step (B) is preferably at least one selected from the group consisting of benzene, toluene, o-xylene, m-xylene and p-xylene.

  In the step (B), ultrafiltration can be carried out instead of (or in combination with) distillation. Ultrafiltration can be performed by passing through pores provided on the surface of an inorganic and / or organic substrate. The material is not specified as long as it is a substrate having such pores, but those having an average pore diameter of preferably 5 nm to 50 nm, more preferably 5 nm to 30 nm can be used. If the pore diameter is 5 nm or less, the filtration rate may be slow, and if it is 30 nm or more, the sol dispersoid 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.

  In the solvent substitution step of the step (B), it is desirable to leave the polar solvent in an amount of about 1 to 15 mol% with respect to the nonpolar solvent without completely removing the polar solvent. The concentration of the polar solvent in the nonpolar solvent can be estimated from the integral value of proton NMR when any solvent contains a hydrogen atom. If the concentration of the polar solvent is higher than 15 mol%, most of the hydrosilyl groups on the hydrogenpolysiloxane may react with the polar solvent and the surface modification may not proceed. If the concentration is less than 1 mol%, the dispersion stability is insufficient. Some particles may agglomerate. If necessary, a polar organic solvent may be added so that the amount of the polar organic solvent is about 1 to 15 mol% with respect to the nonpolar 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. Examples of 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 (B) is preferably reduced to 1,000 ppm or less, more preferably 500 ppm or less. The lower limit of the water concentration in this step is not particularly defined, but is about 100 ppm. When dehydration is required exceeding 100 ppm, it is not usually necessary except for special applications, so it is not considered in the present invention.

  The dehydration can be carried out by a method involving physical adsorption using a zeolite having a pore diameter of preferably 3 to 10 mm.

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) x [Al x Si 12-x 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) x [Al x Si 16-x 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 _x Ca _{(1.5-0.5 x)} Those having a chemical composition such as [Al ₃ Si ₃ O ₁₂ ] and Ca [Al ₂ Si ₆ O ₁₆ ] can be mentioned, and those having these chemical compositions, preferably 3 to 10 cm. What has the pore diameter of this can be used. The range of the pore diameter is preferably 3 to 10 mm, more preferably 4 to 8 mm, and still more preferably 4 to 6 mm. If the pore diameter is smaller than 3 mm, water may not be sufficiently adsorbed, which is not preferable. If the pore diameter is larger than 10 mm, it may not be preferable because 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, The 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 the LTA-type zeolite, “catalog number 25958-08” manufactured by Kanto Chemical Co., Inc. can be used.

  Zeolite is preferably used in an amount of 1% by mass to 20% by mass, more preferably 2% by mass to 15% by mass, and still more preferably 5% by mass to 10% by mass with respect to the obtained organosol. 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 it is not practical to use any more.

（式（Ｉ）中において、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸及びＲ⁹は、それぞれ同一又は異なっていてもよく、（メタ）アクリル基、オキシラニル基もしくはフッ素原子で置換されていてもよい炭素数１以上２０以下のアルキル基と、炭素数２以上２０以下のアルケニル基と、炭素数６以上２０以下のアリール基と、及びケイ素数５０以下の（ポリ）ジメチルシロキシ基とからなる群から選ばれる置換基又は水素原子であり、ｋは５以上の正の整数、ｍは０又は正の整数であり、ｋ＋ｍは該ハイドロジェンポリシロキサンの２５℃における粘度を１０〜１，０００，０００ｍＰａ・ｓの範囲とする数である。） [Step (C)]
Step (C) is a step of adding hydrogen polysiloxane represented by the following general formula (I).

(In the formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ may be the same or different from each other, and a (meth) acryl group An oxiranyl group or an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a silicon number of 50 The substituent is selected from the group consisting of the following (poly) dimethylsiloxy groups or a hydrogen atom, k is a positive integer of 5 or more, m is 0 or a positive integer, and k + m is the hydrogen polysiloxane. (The number at which the viscosity at 25 ° C. is in the range of 10 to 1,000,000 mPa · s.)

In this case, the alkyl group of R ^{1 to} R ⁹ is preferably an alkyl group having 1 to 6 carbon atoms, particularly a methyl group or an ethyl group, and preferably an alkenyl group having 2 to 6, particularly a vinyl group, An aryl group etc. are mentioned, As an aryl group, a C6-C10 thing, especially a phenyl group are mentioned. Further, the silicon number of the (poly) dimethylsiloxy group is preferably 1 to 50, particularly 1 to 30. Moreover, although k is an integer greater than or equal to 5, Preferably it is 5-200, More preferably, it is 5-100, More preferably, it is 5-50. On the other hand, m is preferably 0 to 100, more preferably 0 to 50, and the viscosity at 25 ° C. is preferably 10 to 1,000,000, particularly preferably 10 to 10,000. The viscosity is a value measured by a rotational viscometer.

  Specific examples of the hydrogenpolysiloxane represented by the general formula (I) include trimethylsiloxy group-blocked methylhydrogenpolysiloxanes (trade names “KF-99” and “KF-9901” manufactured by Shin-Etsu Chemical Co., Ltd.). ), Trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer, both ends trimethylsiloxy group-capped methylphenylsiloxane / methylhydrogensiloxane copolymer, both terminal trimethylsiloxy group-capped diphenylsiloxane / methylhydrogensiloxane copolymer Copolymer, trimethylsiloxy group-capped dimethylsiloxane / phenylhydrogensiloxane copolymer, both ends trimethylsiloxy group-capped methylphenylsiloxane / phenylhydrogensiloxane copolymer, Terminal trimethylsiloxy group-blocked diphenylsiloxane / phenylhydrogensiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked methylphenylsiloxane / methylhydrogen Examples thereof include a siloxane copolymer, a dimethylhydrogensiloxy group-blocked diphenylsiloxane / methylhydrogensiloxane copolymer having both ends.

  The concentration of the colloidal solution prepared in the step (C) of the present invention is preferably 1% by mass to 20% by mass, more preferably 5% by mass to 10% by mass. When the concentration of the colloidal solution is lower than 1% by mass, the production efficiency may be poor, and when the concentration of the colloidal solution is higher than 20% by mass, gelation may be easily caused. The concentration here should be understood as the ratio of the mass of the dispersoid contained in the entire colloidal solution (the sum of the masses 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 colloidal solution is weighed and the dispersion medium is forced to dry.

  Examples of the catalyst used in the step (C) include transition metal compounds such as platinum catalysts, rhodium catalysts, ruthenium catalysts, and palladium catalysts, and Lewis acidic compounds. Specific examples include Wilkinson's catalyst, tris (dibenzylideneacetone) dipalladium, bis (triphenylphosphine) palladium (II) dichloride, tetrakis (triphenylphosphine) palladium (0), and tris (pentafluorophenyl) borane. In particular, tris (pentafluorophenyl) borane is preferred.

  The addition amount of the catalyst to be added is preferably 0.01% by mass or more and 20% by mass or less, and more preferably 0.1% by mass with respect to the solid mass of the inorganic oxide colloidal dispersion liquid in the step (C). It is 10 mass% or less, More preferably, it is 1 mass% or more and 5 mass% or less. If the addition amount is more than 20% by mass, the reaction proceeds rapidly and may be difficult to control, and if the addition amount is less than 0.01% by mass, the reaction may not proceed.

  The amount of hydrogen polysiloxane to be added is preferably 10% by mass or more and 200% by mass or less, and more preferably 50% by mass or more and 120% by mass with respect to the solid content of the inorganic oxide colloidal dispersion in step (C). It is not more than mass%, and more preferably not less than 70 mass% and not more than 100 mass%. If the amount added is more than 200% by mass, gelation may occur. When the addition amount is less than 10% by mass, the coating may not proceed and may aggregate.

  The addition method of hydrogen polysiloxane can be dripped in liquid, dripped out of liquid, addition of a portion, etc., and is preferably dripped in liquid.

  The liquid temperature when hydrogenpolysiloxane is added is preferably 0 ° C. or higher and 120 ° C. or lower, more preferably 50 ° C. or higher and 100 ° C. or lower, and further preferably 60 ° C. or higher and 90 ° C. or lower. When the liquid temperature is lower than 0 ° C., the reaction may not proceed. When the liquid temperature is higher than 120 ° C., the reaction may be difficult to control. As a result of the dehydrogenation reaction or dealkane reaction, the temperature of the reaction solution may reach the boiling point of the nonpolar solvent.

In the present invention, if necessary, (D) a hydrosilyl group derived from a hydrogenpolysiloxane on the particle surface and a silane compound represented by the following general formula (III), or a hydroxyl on a unit price or polyhydric alcohol compound Further surface modification is possible by performing a dehydrogenation reaction or a dealkane reaction with a group or an alkoxy group. In this case, the amount of the silane compound represented by the formula (III), the unit price or the polyhydric alcohol compound is preferably 50 mol% or more, more preferably 100, based on the hydrosilyl group derived from hydrogen polysiloxane. In this case, the unreacted silane compound represented by the formula (III), the unit price or the polyhydric alcohol compound can be removed by a technique such as distillation. The upper limit is not particularly limited, but is preferably 500 mol% or less, particularly preferably 300 mol% or less.
R ¹⁰ _p Si (OR ¹¹ ) _4-p (III)
(In the formula, each R ¹⁰ may be the same or different and may be substituted with a functional group such as a (meth) acryl group, an oxiranyl group, a fluorine atom, an amino group, a mercapto group, an isocyanate group, etc. A substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a polydimethylsiloxy group having 50 or less silicon atoms. R ¹¹ is a hydrogen atom or an alkyl group having 6 or less carbon atoms, and p is 1, 2 or 3.)

  Specific examples of p = 1 in the silane compound represented by the general formula (III) include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriethoxysilane. Isopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltriisopropoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltri Ethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) E) Ethyltrimethoxysilane, γ-chloropropyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, γ -Mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (2-aminoethyl) aminopropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltri Partial hydrolysis of ethoxysilane, tris (3-trimethoxysilylpropyl) isocyanurate, tris (3-triethoxysilylpropyl) isocyanurate, and trimethylsilane Condensates (trade names “KC-89S”, “X-40-9220” manufactured by Shin-Etsu Chemical Co., Ltd.), partial hydrolysis condensates of methyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane (trade names) “X-41-1056” manufactured by Shin-Etsu Chemical Co., Ltd.).

  Specific examples of p = 2 in the silane compound represented by the general formula (III) include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, methylpropyldimethoxysilane, Methylpropyldiethoxysilane, diisopropyldimethoxysilane, phenylmethyldimethoxysilane, vinylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ) Ethylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxy Orchids, .gamma.-aminopropyl methyl diethoxy silane, N- (2- aminoethyl) and aminopropyl methyl dimethoxy silane and the like.

  Specific examples of p = 3 in the silane compound represented by the general formula (III) include trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, n-propyldimethylmethoxysilane, n-propyldiethylmethoxysilane, iso- Propyldimethylmethoxysilane, iso-propyldiethylmethoxysilane, propyldimethylethoxysilane, n-butyldimethylmethoxysilane, n-butyldimethylethoxysilane, n-hexyldimethylmethoxysilane, n-hexyldimethylethoxysilane, n-pentyldimethylmethoxy Silane, n-pentyldimethylethoxysilane, n-hexyldimethylmethoxysilane, n-hexyldimethylethoxysilane, n-decyldimethylmethoxysilane, n-decyl Methylethoxysilane, trimethylsilanol, triethylsilanol, n-propyldimethylsilanol, n-propyldiethylsilanol, iso-propyldimethylsilanol, iso-propyldiethylsilanol, propyldimethylsilanol, n-butyldimethylsilanol, n-hexyldimethylsilanol, Examples thereof include n-pentyldimethylsilanol and n-decyldimethylsilanol.

  Specific examples of unit prices and polyhydric alcohol compounds used include methanol, ethanol, 1-propanol, 2-propanol, pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 1-heptanol, ethylene glycol, Examples include propylene glycol, β-thiadiglycol, butylene glycol, and glycerin.

  Examples of the catalyst used in the above step include transition metal compounds such as platinum catalyst, rhodium catalyst, ruthenium catalyst, palladium catalyst, and Lewis acidic compounds, but Wilkinson's catalyst, tris (dibenzylideneacetone) dipalladium and bis ( Triphenylphosphine) palladium (II) dichloride, tetrakis (triphenylphosphine) palladium (0) and tris (pentafluorophenyl) borane are desirable, and tris (pentafluorophenyl) borane is particularly desirable. The amount of use is preferably 0.01% by mass or more and 20% by mass or less, more preferably 0.1% by mass or more and 10% by mass with respect to the solid content mass of the inorganic oxide colloidal dispersion liquid in the step (D). % Or less, and more preferably 1% by mass or more and 5% by mass or less. If the addition amount is more than 20% by mass, the reaction proceeds rapidly and may be difficult to control, and if the addition amount is less than 0.01% by mass, the reaction may not proceed.

  In the above process, the addition of the silane compound, the unit price or the polyhydric alcohol compound represented by the general formula (III) may be carried out in the same container after the hydrogen polysiloxane is added and reacted. Any of the cases in which the organosol after the addition of the polysiloxane is recovered and then reacted independently in different containers is possible.

  In the step (D) of the present invention, further surface modification can be performed by hydrosilylation of a hydrosilyl group derived from hydrogen polysiloxane on the particle surface and a compound having an unsaturated bond. In this case, the amount of the compound used is preferably 50 mol% or more, more preferably 100 mol% or more with respect to the hydrosilyl group derived from hydrogen polysiloxane. The compound having a bond can also be removed by a technique such as distillation. The upper limit is preferably 500 mol% or less, more preferably 300 mol% or less.

  Specific examples of the compound having an unsaturated bond to be added include compounds having a long chain alkyl such as pentene, hexene, and octene, compounds having an aromatic ring such as styrene and pentafluorostyrene, 3, 3, 4, 4, and the like. Fluoroalkyl such as 4-pentafluoro-1-butene, 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and 1H, 1H, 2H-heptadecafluoro-1-decene Examples thereof include compounds containing a group and compounds containing a siloxy group such as trimethylvinylsilane.

  Examples of the catalyst used in the above process include transition metal compounds such as platinum catalysts, rhodium catalysts and ruthenium catalysts, and Lewis acidic compounds, but Wilkinson's catalyst, Karstedt's catalyst, Spiel's catalyst and Tris (pentafluoro). Phenyl) borane and the like are particularly desirable. In this case, the amount of the catalyst used is preferably 0.01% by mass or more and 20% by mass or less, more preferably 0.1% by mass with respect to the solid content mass of the inorganic oxide colloid dispersion liquid in the step (D). The content is from 10% by mass to 10% by mass, and more preferably from 1% by mass to 5% by mass. If the addition amount is more than 20% by mass, the reaction proceeds rapidly and may be difficult to control, and if the addition amount is less than 0.01% by mass, the reaction may not proceed.

  In the above step, the liquid temperature at the time of addition of the silane compound represented by formula (III), the unit price or polyhydric alcohol compound, or the compound having an unsaturated bond is preferably 0 ° C. or higher and 120 ° C. or lower, more preferably Is from 50 ° C. to 100 ° C., more preferably from 60 ° C. to 90 ° C. When the liquid temperature is lower than 0 ° C., the reaction may not proceed. When the liquid temperature is higher than 120 ° C., it may be difficult to control the reaction, and as a result of the dehydrogenation reaction, dealkane reaction or hydrosilylation reaction, the temperature of the reaction liquid may reach the boiling point of the solvent.

In the above process, the addition of the silane compound represented by formula (III), the unit price or polyhydric alcohol compound, or the compound having an unsaturated bond is continuously added to the same container after the addition of hydrogen polysiloxane. Both the case of reacting and the case of reacting independently in different containers after collecting the organosol after addition of hydrogen polysiloxane are possible.
In addition, after the step (C) or after the step (D), another solvent may be added to the nonpolar (aprotic) organic solvent, or the nonpolar (aprotic) organic solvent may be added. What was removed and substituted with another solvent can also be used as the dispersion medium of the dispersion.

  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.

  Infrared light absorption (IR) spectrum measurement was performed using a Nicolet-6700 apparatus manufactured by Thermo Scientific. An IR spectrum was obtained by a diffuse reflection method using a powder obtained by mixing a small amount of a solid sample in potassium bromide and pulverizing the mixture in a mortar. The solid sample was purified by distilling off the solvent in the synthesized organosol under reduced pressure, and then washing away unreacted components with hexane.

  Thermogravimetric (Tg) measurement was performed using a Thermo Plus apparatus manufactured by Rigaku. The solid sample for measurement was prepared in the same manner as the above IR sample. The measurement was performed up to 25 to 1,000 ° C. in a nitrogen atmosphere using a platinum pan.

[Example 1]
[Synthesis of Organosol (OT-1)]
[Step (A)]
Obtained by a method described in Example 1 of Japanese Patent No. 5704133 as a metal oxide particle aqueous dispersion in a 4-neck 2 L separable flask equipped with a Dimroth condenser, a nitrogen inlet, a thermometer, and a mechanical stirring blade. The resulting aqueous dispersion of core-shell type tetragonal titanium oxide particles having tetragonal titanium oxide solid solution particles solidly dissolved in tin and manganese and having a silicon oxide shell on the outside (W-1, solid concentration 1. 3 g of a sulfonic acid-based cationic ion exchange resin as a catalyst was added. Methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name “KBM-13”, 225 g) was added thereto and stirred vigorously (250 rpm). It was observed that the dispersion and methyltrimethoxysilane reacted and became uniform by stirring. At that time, it was observed that the temperature of the dispersion increased from 25 ° C to 52 ° C. After stirring for 2 hours so that the temperature of the dispersion became 50 ° C., ethanol (750 g) was added to the dispersion while stirring (250 rpm) to dilute. The diluted dispersion was introduced into a Dynafilter (product name “DyF152 / S” manufactured by Mitsubishi Chemical Corporation, product of MgAl ₂ O with an average pore diameter of 7 nm [ANDRITZ KMPT GmbH, product number 2065181, type φ152 / 7 nm]). . The rotating shaft connected to the filter was rotated (1,000 rpm) while applying a static pressure of 0.2 MPa with compressed air. It was observed that the dispersion exuded through the ceramic filter. A receiver (5,000 mL) was provided at the filter outlet, and 800 g of exudate was collected. An organic solvent (ethanol) was continuously supplied (0.2 MPa) to the concentrated dispersion. The rotating shaft connected to the filter was rotated (1,000 rpm) while applying a static pressure of 0.2 MPa with compressed air. It was observed that the dispersion exuded through the ceramic filter. A receiver (5,000 mL) was provided at the filter outlet, and ethanol was pressurized and supplied until the exudate reached 800 g. The dispersion liquid was taken out from the filtration chamber, and an ethanol dispersion liquid (E-1) of core-shell particles was obtained. The solid content concentration of E-1 was 5.5% by mass and the water concentration was 1.1% by mass. Regarding E-1, the volume average 50% cumulative distribution diameter was determined to be 10 nm by the dynamic light scattering method (manufactured by Nikkiso Co., Ltd., device name “Nanotrack”). Moreover, the vibration peak characteristic of alkylsilane was confirmed in the IR spectrum, and it was confirmed that the surface treatment with the silane coupling agent was effectively performed (FIG. 1).

[Step (B)]
In a 300 mL eggplant flask equipped with a Dean-Stark apparatus, a reflux tube and a stir bar, 200 g of an ethanol dispersion (E-1, solid concentration 5.5% by mass) of the core-shell particles prepared in the previous step (A) was added. After 20 g of ethanol was distilled off by pressure distillation, 20 g of toluene was added. This operation is repeated until the molar fraction of ethanol to toluene determined by NMR measurement is 8 mol%, and a dispersion of core-shell particles (T-1, solid content concentration: 5.0 mass%, moisture: 449 ppm) is obtained. Obtained. Thereafter, 200 g of the obtained dispersion was treated with molecular sieve 4A (“25958-08”, 5 g, manufactured by Kanto Chemical Co., Inc.). The molar fraction of ethanol with respect to toluene in T-1 was 8 mol%, the solid content concentration was 5.0 mass%, and the water concentration was 316 ppm. At this time, no aggregation was observed, and it became clear that the molecular sieve treatment was useful for reducing water.

[Step (C)]
10 g of the core-shell particle dispersion (T-1) obtained in the previous step was transferred to a 100 mL eggplant flask, and 10 mg of tris (pentafluorophenyl) borane was added as a catalyst. Stirring with a magnetic stir bar (350 rpm) and heating the solution to 80 ° C., hydrogenpolysiloxane (in formula (I), R ^{1 to} R ⁹ are methyl groups, k = 30 to 40, m = 0, viscosity = 20 mm ² / s, manufactured by Shin-Etsu Chemical Co., Ltd., product name “KF-99”, 0.5 g) is added dropwise to T-1 in an amount of 100% by mass, and heated and stirred for 15 minutes. -1) was obtained. In addition, it was confirmed that the reaction was progressing because gas derived from hydrogen and methane was generated after the addition of KF-99. With respect to OT-1, the volume average 50% cumulative distribution diameter was found to be 33.2 nm by the dynamic light scattering method (manufactured by Nikkiso Co., Ltd., device name “Nanotrack”). In addition, since a vibration peak characteristic of the hydrosilyl group was observed in the IR spectrum, it became clear that the particle surface was coated with KF-99 and the hydrosilyl group derived from KF-99 was present. (FIG. 2).

[Example 2]
The same operation as in Example 1 was performed except that KF-99 was used in an amount of 80% by mass with respect to T-1 in Step (C) performed in Example 1 to obtain an organosol (OT-2). . The results are summarized in Table 1.

[Example 3]
The same operation as in Example 1 was performed except that KF-99 was used in an amount of 120% by mass with respect to T-1 in the step (C) performed in Example 1 to obtain an organosol (OT-3). . The results are summarized in Table 1.

[Example 4]
In the step (C) performed in Example 1, using a dispersion of core-shell particles (T-4, solid content concentration: 5.0 mass%) in which the ethanol concentration in toluene was adjusted to 3 mol%, KF-99 was used. An organosol (OT-4) was obtained in the same manner as in Example 1 except that the content was 50% by mass based on T-4. The results are summarized in Table 1.

[Example 5]
An organosol (OT-5) was obtained in the same manner as in Example 1 except that the step (B ′) was carried out instead of the step (B) in Example 1. The results are summarized in Table 1.
[Step (B ′)]
Add an ethanol dispersion of core-shell particles (E-1, 200 g, solid content concentration: 5.5% by mass) to a 300 mL eggplant flask equipped with a Dimroth condenser, Dean-Stark apparatus, and stir bar, and the following general formula (V ), A compound having an average structure of r = 30 (manufactured by Shin-Etsu Chemical Co., Ltd., product name “X-24-9822”, 6 g) and a sulfonic acid-based cationic ion exchange resin (2 g) are stirred vigorously ( 350 rpm). Ion exchange water (20 g) was added thereto and refluxed for 3 hours. After allowing the solution to cool, 20 g of toluene was added, and 20 g of ethanol was distilled off by atmospheric distillation using a Dean-Stark apparatus. This operation is repeated until the molar fraction of ethanol to toluene determined by NMR measurement is 10 mol%, and a dispersion of core-shell particles (T-5, solid content concentration: 5.4 mass%, moisture: 334 ppm) is obtained. Obtained.

[Example 6]
An organosol (OT-6) was obtained in the same manner as in Example 1 except that the step (C ′) was carried out instead of the step (C) in Example 1. The results are summarized in Table 1.
[Step (C ′)]
10 g of a dispersion of core-shell particles (T-1, solid content concentration: 5.0% by mass) was transferred to a 100 mL eggplant flask, and 10 mg of tris (pentafluorophenyl) borane was added as a catalyst. The mixture was stirred with a magnetic stir bar (350 rpm), and KF-99 was added dropwise by 100% by mass with respect to T-1 in a state where the solution was heated to 80 ° C., followed by stirring with heating for 15 minutes. Subsequently, 2 g of 1-hexanol was dropped, and the mixture was heated and stirred for 1 hour, and then stirred at room temperature for 12 hours to obtain an organosol (OT-6). It was confirmed that the vibration peak characteristic of the hydrosilyl group was reduced in the IR spectrum (FIG. 3). In addition, as a result of Tg measurement, the weight loss was increased in the particles after addition (OT-6) as compared with organosol (OT-1) to which hexanol was not added. This is thought to be because the weight reduction due to the decomposition of the hexyloxy group was added to the weight reduction of OT-6 because the hexanol added was coated on the particle surface. From the above results, it was confirmed that the hydrosilyl group on the particles was converted to a hexyloxy group by a dehydrogenation reaction with hexanol (FIG. 4).

[Example 7]
An organosol (OT-7) was obtained in the same manner as in Example 1 except that the step (C ″) was carried out instead of the step (C) in Example 1. The results are summarized in Table 1.
[Process (C '')]
10 g of core-shell particles (T-1, solid content concentration: 5.0% by mass) were transferred to a 100 mL eggplant flask, and 10 mg of tris (pentafluorophenyl) borane was added as a catalyst. The mixture was stirred with a magnetic stir bar (350 rpm), KF-99 was added dropwise by 100% by mass with respect to T-1 while the solution was heated to 80 ° C., and the mixture was stirred with heating for 15 minutes. Subsequently, 2 g of platinum catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., product name “CAT-PL-50T”, 10 mg) and 1-hexene are dropped at room temperature, and the mixture is stirred at room temperature for 12 hours to obtain organosol (OT-7). Obtained. It was confirmed that the vibration peak characteristic of the hydrosilyl group was reduced in the IR spectrum (FIG. 5). Moreover, as a result of Tg measurement, the weight loss was increased in the particles after addition (OT-7) as compared with the organosol (OT-1) to which hexene was not added. This is considered to be because the weight reduction due to the decomposition of the hexyl group was added to the weight reduction of OT-7 because the hexene added was coated on the particle surface. From the above results, it was confirmed that the hydrosilyl group on the particles was converted to a hexyl group by a hydrosilylation reaction with hexene (FIG. 6).

[Example 8]
In the step (C) performed in Example 1, using a dispersion of core-shell particles (T-8, solid content concentration: 5.0 mass%) in which the ethanol concentration in toluene was adjusted to 10 mol%, KF-99 was used. An organosol (OT-8) was obtained in the same manner as in Example 1 except that 50% by mass was used relative to T-8.

[Example 9]
In Example (C) performed in Example 1, hydrogen polysiloxane represented by the following general formula (VI) was used in place of KF-99, using 100% by mass with respect to T-1, and Example The same operation as 1 was performed to obtain an organosol (OT-9). The results are summarized in Table 1.

[Comparative Example 1]
Regarding the aqueous dispersion (W-1) of the raw material core-shell particles used in the step (A) performed in Example 1, as a result of direct ethanol substitution without performing treatment with KBM-13, particle aggregation was observed. .

[Comparative Example 2]
In the solvent replacement step in the step (B) performed in Example 1, the solvent replacement was performed until the molar fraction of ethanol to toluene determined by NMR measurement was 60 mol%, which was the same as Example 1. In operation (C), coating with KF-99 was attempted, but the start of the reaction was not confirmed and particle aggregation was observed.

[Comparative Example 3]
In the step (C) carried out in Example 1, the same procedure as in Example 1 was carried out except that 100% by mass of dimethylpolysiloxane having both ends dimethylhydrogensiloxy group blocked with respect to T-1 was used instead of KF-99. Was performed. As a result, no progress of the reaction was confirmed and no improvement in dispersibility was observed.

[Comparative Example 4]
Example except that in the step (C) performed in Example 1, hydrogen polysiloxane described by the following general formula (VII) was used in place of KF-99 by 100% by mass with respect to T-1. The same operation as 1 was performed. As a result, the progress of the reaction was not confirmed, and no improvement in dispersibility was observed.

  In Examples 1 to 9, in step (A), an aqueous dispersion (W-1) of raw material core-shell particles is reacted with a silane coupling agent (methyltrimethoxysilane) to obtain an organosol using ethanol as a dispersion medium. . As is apparent from the results of Comparative Example 1, if the particles are not hydrophobized by this step, an organosol cannot be prepared, and subsequent coating with hydrogen polysiloxane becomes difficult. As is apparent from the results of Comparative Example 2, in the solvent substitution step of step (B), when the molar fraction of ethanol to toluene is 60 mol%, the hydrosilyl group derived from hydrogen polysiloxane and the hydroxyl group of ethanol A dehydrogenation reaction occurs between the group and the surface of the particle does not proceed. In addition, when both ends dimethylhydrogensiloxy group-blocked dimethylpolysiloxane having only two reaction points are used (Comparative Example 3), or when hydrogenpolysiloxane having three reaction points is used ( In Comparative Example 4), the hydrosilyl group is consumed by the reaction with ethanol, and the coating of the particle surface does not proceed. On the other hand, in the sample from which ethanol has been completely distilled off, the particles are aggregated due to insufficient hydrophobicity of the particles. From the above results, in the present invention, a nonpolar organic solvent-dispersed sol containing a small amount of alcohol as a stabilizer is prepared so that particles are not aggregated, and hydrogen polysiloxane having many reaction points is used in the system. By reacting a small amount of alcohol with both silanol groups and methoxy groups on the particle surface, a dehydrogenation reaction or dealkane reaction on the surface of the dispersed particles, which has been considered difficult in the past, has been achieved. By carrying out the hydrogen polysiloxane coating of the step (C) through the steps (A) and (B) as described above, the demethanation / alkane reaction of the inorganic particle dispersion which has not been achieved so far can be carried out. The surface treatment used has been achieved, and this production method is considered to have both high utility and uniqueness.

In Examples 1 to 3, particles in which the amount of KF-99 to be coated is changed with respect to the weight of the inorganic oxide particles are synthesized. From the results of IR measurement, a vibration peak characteristic of the hydrosilyl group derived from KF-99 was observed in the particles produced in Examples 1 to 3, and an increase in vibration peak intensity was confirmed as the amount added increased (Fig. 7). From this, it was found that KF-99 was effectively coated on the particle surface, and the amount of hydrosilyl groups on the particle surface could be controlled by the addition amount.
In Example 5, in addition to methyltrimethoxysilane as a silane coupling agent, a surface treatment with a polydimethylsiloxane-substituted silane coupling agent (X-24-9822) was added to achieve coating with KF-99. ing. This indicates that the hydrogen polysiloxane coating can be applied to particles treated with various silane coupling agents.

  In Example 6 and Example 7, the particles were obtained by dehydrogenation reaction (Example 6) of hydrosilyl groups remaining on the particle surface with hydrogen polysiloxane coating and alcohol and hydrosilylation reaction of alkene (Example 7). It has succeeded in introducing further substituents on the surface. Thus, the particle | grains coat | covered with hydrogen polysiloxane can introduce | transduce various functional groups on the remaining hydrosilyl group in the state which maintained the dispersion state. This result means that many commercially available compounds having hydroxyl groups and unsaturated bonds can be modified on the particles, and various functionalities can be imparted to the inorganic oxide particles. Such inorganic oxide particles having high functional group adaptability are unprecedented and are considered to have high industrial utility.

In the following Examples 10-18 and Comparative Examples 5-7, the dispersibility of each inorganic oxide particle with respect to toluene and octamethylcyclotetrasiloxane (D4) was evaluated.
Dispersibility: When titanium oxide particles were mixed in toluene or D4, “◯” = obtained stable organosol without agglomeration, “×” = agglomerated and particles settled.
Particle size: 50% cumulative distribution diameter of volume average measured by dynamic light scattering method.

[Example 10]
The organosol (OT-1) produced in Example 1 was added to the cyclic siloxane (D4), and toluene was distilled off under reduced pressure to prepare a D4 dispersion. As a result, no aggregation of particles was observed. The results are summarized in Table 1.

[Example 11]
About the organosol (OT-2) produced in Example 2, the dispersibility in D4 was evaluated using the same operation as in Example 1. As a result, no aggregation of particles was observed. The results are summarized in Table 1.

[Example 12]
About the organosol (OT-3) produced in Example 3, the dispersibility in D4 was evaluated using the same operation as in Example 1. As a result, no aggregation of particles was observed. The results are summarized in Table 1.

[Example 13]
About the organosol (OT-4) produced in Example 4, the dispersibility in D4 was evaluated using the same operation as in Example 1. As a result, no aggregation of particles was observed. The results are summarized in Table 1.

[Example 14]
About the organosol (OT-5) produced in Example 5, the dispersibility in D4 was evaluated using the same operation as in Example 1. As a result, no aggregation of particles was observed. The results are summarized in Table 1.

[Example 15]
About the organosol (OT-6) produced in Example 6, the dispersibility in toluene and D4 was evaluated using the same operation as in Example 1. As a result, no aggregation of particles was observed. The results are summarized in Table 1.

[Example 16]
About the organosol (OT-7) produced in Example 7, the dispersibility in toluene and D4 was evaluated using the same operation as in Example 1. As a result, aggregation of particles was observed in D4. The results are summarized in Table 1.

[Example 17]
About the organosol (OT-8) produced in Example 8, the dispersibility in toluene and D4 was evaluated using the same operation as in Example 1. As a result, aggregation of particles was observed in D4. The results are summarized in Table 1.

[Example 18]
About the organosol (OT-9) produced in Example 9, the dispersibility in toluene and D4 was evaluated using the same operation as in Example 1. As a result, aggregation of particles was observed in D4. The results are summarized in Table 1.

[Comparative Example 5]
With respect to a commercially available butanol dispersion of titanium oxide (product name “RTTDNB 15 wt% -E88”, 15 mass%, manufactured by CIK Nanotech Co., Ltd.), the dispersibility in toluene and D4 was measured using the same operation as in Example 1. evaluated. As a result, aggregation of titanium oxide particles was observed when any of the dispersions was prepared. The results are summarized in Table 2.

[Comparative Example 6]
As a result of adding the ethanol dispersion (E-1) of the core-shell particles obtained by the step (A) performed in Example 1 to toluene, aggregation of particles was observed. In addition, when E-1 was added to D4 and ethanol was distilled off under reduced pressure, particle aggregation was similarly observed. The results are summarized in Table 2.

[Comparative Example 7]
As a result of adding the toluene dispersion (T-5) of the core-shell particles obtained by the step (B ′) performed in Example 5 to toluene and completely removing a small amount of ethanol, aggregation of particles was observed. . Further, when T-5 was added to D4 and toluene was distilled off under reduced pressure, particle aggregation was similarly observed. The results are summarized in Table 2.

When inorganic oxide particles not coated with KF-99 are used (Comparative Examples 5 to 7), they are agglomerated and settled in toluene, whereas titanium oxide particles coated with KF-99 are stable. Maintained a dispersed state. This is not a surface modification using an equilibrium reaction in a polar solvent as seen in the modification of a conventional silane coupling agent, but a dehydrogenation reaction or a dealkane reaction which is an irreversible reaction with high reactivity. Thus, polar groups such as silanol remaining on the particle surface are considered to be caused by high-density substitution with highly hydrophobic polysiloxane, and the results strongly represent the characteristics of the present invention. I can say that.
When attention is paid to the particle size of each particle in toluene, when particles coated only with KF-99 are used (Examples 10 to 14 and 17), the particle size is 50 nm or less. It was confirmed that no aggregation occurred. In D4, all of the particles increased in particle size to about 200 nm and a slight secondary aggregation behavior was observed, but a stable dispersion state was maintained without settling.
Further, when particles treated with hexanol after coating with KF-99 were used (Example 15), the particle size was smaller in D4 than the particles before treatment (Example 10). This result has shown that the secondary aggregation in D4 is suppressed more because the hydrosilyl group on the particle | grain surface is converted into the hexyloxy group. On the other hand, in the case of particles treated with hexene (Example 16), the particle size increased in toluene compared to the particles before coating (Example 10), and aggregated and settled in D4. This result indicates that the dispersibility in a nonpolar solvent is reduced by the conversion of the hydrosilyl group on the particle surface into a hexyl group. As described above, the particles produced according to the present invention can be controlled in dispersibility and physical properties and imparted functionality by introducing various substituents onto the particle surface, and can be expected to be applied in many fields.
These Examples and Comparative Examples are typical examples for showing the usefulness of the present invention, and do not limit the scope of the invention.

  The inorganic oxide particles obtained by the present invention can be applied to coating compositions, light-emitting element sealing materials, thermal conductive compositions, and the like. In these fields, various mechanical techniques have been used to highly disperse inorganic oxide particles. However, using organosols with excellent compatibility with binders contributes to simplification of composition techniques. 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. The inorganic oxide particles have a polar group such as a silicone resin or a polystyrene resin without impairing transparency, as can be seen from the fact that the inorganic oxide particles have high dispersibility with respect to the siloxane compound. It is possible to introduce into no resin material. In addition, the inorganic oxide particles can impart various characteristics while maintaining a dispersed state by reacting hydrosilyl groups present on the surface with various organic compounds. Therefore, the present invention can greatly expand the range of material selection at the time of composition, and is considered to contribute to industrial development in this field.

Claims (16)

Surface-treated inorganic oxide particles having an organosilyl residue on the surface and further bonded with hydrogen polysiloxane represented by the following general formula (I):
The bond between the hydrogenpolysiloxane represented by the general formula (I) and the inorganic oxide particle having an organosilyl residue on the surface is a bond between the hydrosilyl group on the hydrogenpolysiloxane and the surface of the inorganic particle or A surface-treated inorganic oxide particle characterized by being bonded by a dehydrogenation reaction with a hydroxyl group on an organosilyl residue on the particle surface or a dealkane reaction with an alkoxy group.

(In the formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ may be the same or different from each other, and a (meth) acryl group An oxiranyl group or an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a silicon number of 50 The substituent is selected from the group consisting of the following (poly) dimethylsiloxy groups or a hydrogen atom, k is a positive integer of 5 or more, m is 0 or a positive integer, and k + m is the hydrogen polysiloxane. (The number at which the viscosity at 25 ° C. is in the range of 10 to 1,000,000 mPa · s.)   The inorganic oxide is selected from the group consisting of Al, B, In, Si, Ge, Sn, Ti, Mn, Zn, Y, Zr, Hf, Ta, La, Ce, Pr, Nd, Tb, Dy, and Yb. The surface-treated inorganic oxide particles according to claim 1, comprising an oxide of one or more elements.   The surface-treated inorganic oxide particles according to claim 1 or 2, wherein the inorganic oxide is a core-shell particle having titanium oxide particles as nuclei and having a silicon oxide shell outside the nuclei.   The inorganic oxide is a core-shell type tetragonal titanium oxide particle having, as a nucleus, tetragonal titanium oxide solid solution particles in which tin and manganese are dissolved, and having a silicon oxide shell outside the nucleus. The surface-treated inorganic oxide particles according to claim 1 or 2.   Furthermore, by an addition reaction between the hydrosilyl group of the hydrogenpolysiloxane of formula (I) and a compound having an unsaturated bond, a dehydrogenation reaction with a compound having a hydroxy group, or a dealkane reaction with a compound having an alkoxy group. The surface-treated inorganic oxide particle according to any one of claims 1 to 4, which has a surface modification part.   A dispersion liquid, wherein the surface-treated inorganic oxide particles according to any one of claims 1 to 5 are contained in an amount of 0.01 to 50 mass% with respect to the dispersion medium.   The dispersion medium is at least one selected from the group consisting of hydrocarbon compounds having 5 to 30 carbon atoms, alcohol compounds, ether compounds, ester compounds, ketone compounds, siloxane compounds, and amide compounds. The dispersion according to claim 6.   The dispersion liquid according to claim 7, wherein the dispersion medium is one or more siloxane compounds. (A) Step of dispersing inorganic oxide particles in a polar organic solvent dispersion medium after surface treatment with a silane coupling agent and / or (partial) hydrolysis condensate thereof,
(B) The dispersion medium is replaced with an aprotic organic solvent while removing the polar organic solvent by distillation and / or ultrafiltration, and the molar fraction of the polar organic solvent to the aprotic organic solvent is 1 to 15 mol% A method for producing surface-treated inorganic oxide particles, which comprises a step of removing the polar organic solvent until it is, and a step of (C) reacting with hydrogenpolysiloxane represented by the following general formula (I):
In the step (C), the bond between the hydrogenpolysiloxane represented by the general formula (I) and the surface-treated inorganic oxide particles is a combination of a hydrosilyl group on the hydrogenpolysiloxane and an inorganic oxidation. A method for producing surface-treated inorganic oxide particles, wherein the surface-treated inorganic oxide particles are formed by a dehydrogenation reaction with a hydroxyl group on an object particle surface or an organosilyl residue on the particle surface or a dealkane reaction with an alkoxy group.

(In the formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ may be the same or different from each other, and a (meth) acryl group An oxiranyl group or an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a silicon number of 50 The substituent is selected from the group consisting of the following (poly) dimethylsiloxy groups or a hydrogen atom, k is a positive integer of 5 or more, m is 0 or a positive integer, and k + m is the hydrogen polysiloxane. (The number at which the viscosity at 25 ° C. is in the range of 10 to 1,000,000 mPa · s.)   The inorganic oxide is selected from the group consisting of Al, B, In, Si, Ge, Sn, Ti, Mn, Zn, Y, Zr, Hf, Ta, La, Ce, Pr, Nd, Tb, Dy, and Yb. The method for producing surface-treated inorganic oxide particles according to claim 9, comprising an oxide of one or more elements.   The method for producing surface-treated inorganic oxide particles according to claim 9 or 10, wherein the inorganic oxide is core-shell particles having titanium oxide particles as nuclei and having a silicon oxide shell outside the nuclei. .   The inorganic oxide is a core-shell type tetragonal titanium oxide particle having, as a nucleus, tetragonal titanium oxide solid solution particles in which tin and manganese are dissolved, and having a silicon oxide shell outside the nucleus. The manufacturing method of the surface treatment inorganic oxide particle of Claim 9 or 10.   The polar organic solvent in the step (A) is at least one selected from the group consisting of methanol, ethanol, isopropyl alcohol, and n-propyl alcohol. A method for producing surface-treated inorganic oxide particles.   The aprotic organic solvent in the step (B) is at least one selected from the group consisting of benzene, toluene, o-xylene, m-xylene and p-xylene. The manufacturing method of the surface treatment inorganic oxide particle of any one of Claims 1.   The method for producing surface-treated inorganic oxide particles according to claim 9, wherein the dehydrogenation reaction or the dealkane reaction uses tris (pentafluorophenyl) borane as a catalyst.   Further, (D) an addition reaction between a hydrosilyl group derived from the hydrogen polysiloxane represented by the general formula (I) bonded to the inorganic oxide particles and a compound having an unsaturated bond, and having a hydroxyl group The method for producing surface-treated inorganic oxide particles according to any one of claims 9 to 15, further comprising a step of performing a dehydrogenation reaction with a compound or a dealkane reaction with a compound having an alkoxy group. .

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