JP2010265174A - Modified mesoporous oxide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a modified mesoporous oxide having a controlled property of the surface or the inside of a fine pore and excellent heat stability, and to provide the mesoporous oxide having uniform pores, high surface area and high crystallinity. <P>SOLUTION: The modified mesoporous oxide (A) is obtained by modifying a mesoporous oxide (a) using at least one modifying agent compound (b) selected from the group consisting of compounds having at least one structural unit selected from the group consisting of a tri-organo silane unit, a mono-oxy di-organo silane unit and a dioxy-organo silane unit, and the high crystallinity mesoporous oxide (B) is derived from the modified mesoporous oxide (A) by heat treatment. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a mesoporous oxide treated with a modifying agent having a special structure, and a highly crystalline mesoporous oxide having a high surface area with good uniformity of pores derived from the mesoporous oxide.

A mesoporous oxide is an oxide material having nano-sized pores. Mesoporous oxides are expected as materials having various physicochemical functions because of their uniform pore characteristics and high surface area.
In recent years, among these mesoporous oxides, non-silica mesoporous oxides, particularly mesoporous transition metal oxides, have attracted attention. This is because the transition metal, which is a constituent material, can be expected to act as various catalysts.
However, most of the mesoporous transition metal oxides synthesized so far are amorphous or low in crystallinity. When the crystallization treatment is performed at a high temperature so that the crystallinity of the mesoporous oxide is sufficiently high, There was a problem that the pore structure collapsed as the crystallization progressed.

In response to these problems, Japanese Patent Application Laid-Open No. 2003-321411 discloses that tetraethylorthosilicate (TEOS) or sodium silicate solution is filled into pores and then gelled at 80 to 100 ° C. and subjected to crystallization heat treatment, followed by acid or alkali. There has been proposed a method of forming a mesoporous film with improved crystallinity by removing a filler (gelated product) with water to which is added. However, in this method, it is difficult to selectively fill the pores with a gelled product, and it is impossible to selectively remove only those reacted outside the pores before the crystallization heat treatment. It was. For this reason, it is indispensable to remove the filler (gelated product) with water added with acid or alkali after crystallization heat treatment, and many of the pores of the generated mesoporous oxide are maintained, but most of them collapse. There was a problem to do. That is, a technique for highly crystallizing the pore walls while maintaining the periodicity of the pores and pores before crystallization of the mesoporous oxide has been desired.
On the other hand, controlling the surface of the mesoporous oxide and the properties in the pores can be expected to develop a wider range of applications of mesoporous oxide using the uniformity of the pores and the high surface area. However, until now, no method for effectively controlling these properties has been proposed.

JP 2003-321111 A

  An object of the present invention is to provide a mesoporous oxide excellent in thermal stability with controlled properties in the surface and pores, and having high crystallinity and high crystallinity with good pore uniformity and high surface area Is to provide.

（式中、Ｒは式（１）で定義した通りである。） As a result of intensive studies to solve the above problems, the present inventors have reached the present invention. That is, the present invention is as follows.
1. The mesoporous oxide (a) is represented by a triorganosilane unit represented by the formula (1), a monooxydiorganosilane unit represented by the formula (2), and a dioxyorganosilane unit represented by the formula (3). A modified mesoporous oxide (A) obtained by modifying with at least one modifier compound (b) selected from the group consisting of compounds having at least one structural unit selected from the group consisting of:
R ₃ Si- (1)
(In the formula, each R is independently a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a linear or branched carbon group having 1 to 30 carbon atoms. (A fluoroalkyl group, a linear or branched alkenyl group having 2 to 30 carbon atoms, a phenyl group, a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group.)
_{- (R 2 SiO) - (} 2)
(In the formula, R is as defined in formula (1).)

(In the formula, R is as defined in formula (1).)

2. 2. The modified mesoporous oxide (A) according to 1 above, wherein the mesoporous oxide (a) is a mesoporous oxide containing a transition metal.
3. 3. The modified mesoporous oxide (A) according to 1 or 2 above, wherein the modifier compound (b) is a Si-H group-containing silicon compound (b1) represented by the formula (4).
H _x R _y Q _z SiO _{(4-xyz) / 2} (4)
(In the formula, each R is independently a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a linear or branched carbon group having 1 to 30 carbon atoms. A fluoroalkyl group, a linear or branched alkenyl group having 2 to 30 carbon atoms, a phenyl group, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group is represented.
In the formula, Q is a group containing at least one functionality-imparting group selected from the group consisting of (a) to (u) below.
(A) At least one hydrophilic group selected from the group consisting of a carboxyl group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, an amino group or a salt thereof, and a polyoxyalkylene group.
(Ii) Epoxy group, acryloyl group, methacryloyl group, (cyclic) acid anhydride group, keto group, carboxyl group, hydrazine residue, isocyanate group, isothiocyanate group, hydroxyl group, amino group, cyclic carbonate group, thiol group, At least one reactive group selected from the group consisting of ester groups;
(Iii) At least one spectral sensitizing group.
Further, 0 <x <4, 0 <y <4, 0 ≦ z <4, and (x + y + z) ≦ 4. )

｛（式中、Ｒ¹ は各々独立して直鎖状または分岐状の炭素数が１〜３０個のアルキル基、
炭素数５〜２０のシクロアルキル基、直鎖状または分岐状の炭素数が１〜３０個のフルオロアルキル基、炭素数２〜３０のアルケニル基、フェニル基、炭素数１〜２０のアルコキシ基、水酸基、もしくは式（９）で表されるシロキシ基から選ばれた１種以上からなる基を表す。
−Ｏ−（Ｒ₂ ＳｉＯ）_n −ＳｉＲ₃ ・・・（９）
（式中、Ｒは各々独立に直鎖状または分岐状の炭素数１〜３０個のアルキル基、炭素数５〜２０のシクロアルキル基、直鎖状または分岐状の炭素数１〜３０個のフルオロアルキル基、直鎖状または分岐状の炭素数２〜３０個のアルケニル基、フェニル基、炭素数１〜２０のアルコキシ基、又は水酸基を表す。また、ｎは整数であり、０≦ｎ≦１０００である。）｝
Ｈ−（Ｒ¹ ₂ＳｉＯ）_m −ＳｉＲ¹ ₂−Ｑ ・・・（６）
（式中、Ｒ¹ は式（５）で定義した通りである。Ｑは、下記（あ）〜（う）からなる群より選ばれる少なくとも１つの機能性付与基を含有する基である。
（あ）カルボキシル基あるいはその塩、リン酸基あるいはその塩、スルホン酸基あるいはその塩、アミノ基あるいはその塩、ポリオキシアルキレン基からなる群から選ばれた少なくとも１つの親水性基。
（い）エポキシ基、アクリロイル基、メタアクリロイル基、（環状）酸無水物基、ケト基、カルボキシル基、ヒドラジン残基、イソシアネート基、イソチオシアネート基、水酸基、アミノ基、環状カーボネート基、チオール基、エステル基からなる群から選ばれた少なくとも１つの反応性基。
（う）少なくとも１つの分光増感基。
ｍは整数であり、０≦ｍ≦１０００である。）
Ｈ−（Ｒ¹ ₂ＳｉＯ）_m −ＳｉＲ¹ ₂−Ｈ ・・・（７）
（式中、Ｒ¹ は式（５）で定義した通りである。ｍは整数であり、０≦ｍ≦１０００である。）
（Ｒ¹ＨＳｉＯ）_a（Ｒ¹ ₂ＳｉＯ）_b（Ｒ¹ＱＳｉＯ）_c（Ｒ¹ ₃ＳｉＯ_1/2 ）_d・・・（８）
（式中、Ｒ¹ は式（５）で定義した通りであり、Ｑは式（６）で定義した通りである。ａは１以上の整数であり、ｂ及びｃは０又は１以上の整数であり、（ａ＋ｂ＋ｃ）≦１００００であり、そしてｄは０又は２である。但し、（ａ＋ｂ＋ｃ）が２以上の整数であり且つｄ＝０の場合、該Ｈシリコーン化合物は環状シリコーン化合物であり、ｄ＝２の場合、該Ｈシリコーン化合物は鎖状シリコーン化合物である。） 4). The modifier compound (b) is a mono-Si—H group-containing compound represented by the formula (5) or (6), a Si—H group-containing compound represented by the formula (7), a formula (8) The modified mesoporous oxide (A) according to 1 or 2 above, wherein the modified mesoporous oxide (A) is at least one Si-H group-containing silicon compound (b1) selected from the group consisting of H silicone compounds represented by

{(Wherein R ¹ is each independently a linear or branched alkyl group having 1 to 30 carbon atoms,
A cycloalkyl group having 5 to 20 carbon atoms, a linear or branched fluoroalkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a phenyl group, an alkoxy group having 1 to 20 carbon atoms, It represents a group consisting of one or more selected from a hydroxyl group or a siloxy group represented by formula (9).
—O— (R ₂ SiO) _n —SiR ₃ (9)
(In the formula, each R is independently a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a linear or branched carbon group having 1 to 30 carbon atoms. A fluoroalkyl group, a linear or branched alkenyl group having 2 to 30 carbon atoms, a phenyl group, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group, n is an integer, and 0 ≦ n ≦ 1000.)}
_{^{H- (R 1 2 SiO) m}} -SiR 1 2 -Q ··· (6)
(In the formula, R ¹ is as defined in Formula (5). Q is a group containing at least one functionality-imparting group selected from the group consisting of the following (A) to (U)).
(A) At least one hydrophilic group selected from the group consisting of a carboxyl group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, an amino group or a salt thereof, and a polyoxyalkylene group.
(Ii) Epoxy group, acryloyl group, methacryloyl group, (cyclic) acid anhydride group, keto group, carboxyl group, hydrazine residue, isocyanate group, isothiocyanate group, hydroxyl group, amino group, cyclic carbonate group, thiol group, At least one reactive group selected from the group consisting of ester groups;
(Iii) At least one spectral sensitizing group.
m is an integer, and 0 ≦ m ≦ 1000. )
_{^{H- (R 1 2 SiO) m}} -SiR 1 2 -H ··· (7)
(In the formula, R ¹ is as defined in Formula (5). M is an integer, and 0 ≦ m ≦ 1000.)
(R ¹ HSiO) _a (R ¹ ₂ SiO) _b (R ¹ QSiO) _c (R ¹ ₃ SiO _1/2 ) _d (8)
(In the formula, R ¹ is as defined in formula (5), Q is as defined in formula (6), a is an integer of 1 or more, and b and c are 0 or an integer of 1 or more. (A + b + c) ≦ 10000 and d is 0 or 2. provided that when (a + b + c) is an integer of 2 or more and d = 0, the H silicone compound is a cyclic silicone compound, When d = 2, the H silicone compound is a chain silicone compound.)

5). 5. The modified mesoporous oxide (A) according to any one of 1 to 4 above, which has a photocatalytic activity.
6). 1 to 5 above, wherein at least one transition metal selected from the group consisting of Pt, Rh, Ru, Ir, Cu, Sn, Ni, Fe, W, Co and / or an oxide of the transition metal is supported. The modified mesoporous oxide (A) according to any one of the above.
7). The highly crystalline mesoporous oxide (B) induced | guided | derived by heat-processing the modified | denatured mesoporous oxide (A) in any one of said 1-6.
8). A mesoporous oxide (B) having improved crystallinity induced by heat-treating the modified mesoporous oxide (A) according to any one of the above 1 to 6 with a solvent.
9. 9. The highly crystalline mesoporous oxide (B) according to 7 or 8 above, which is subjected to an acid and / or alkali treatment after the heat treatment.
10. 7 to 9 above, wherein at least one transition metal selected from the group consisting of Pt, Rh, Ru, Ir, Cu, Sn, Ni, Fe, W, and Co and / or an oxide of the transition metal is supported. The highly crystalline mesoporous oxide (B) according to any one of the above.

  Since the modified mesoporous oxide of the present invention has various functions and is excellent in thermal stability, the crystalline mesoporous oxide is easily improved in crystallinity while maintaining the pore structure and its uniformity by crystal heating treatment. Can be obtained.

2 shows an X-ray diffraction pattern of mesoporous niobium oxide obtained in Reference Example 1. 2 shows a nitrogen adsorption isotherm of mesoporous niobium oxide obtained in Reference Example 1. 2 shows a nitrogen adsorption isotherm of the modified mesoporous niobium oxide obtained in Example 1. The nitrogen adsorption isotherm of the modified mesoporous niobium oxide after THF washing obtained in Example 1 is shown. The X-ray diffraction pattern of the highly crystalline mesoporous niobium oxide obtained in Example 1 is shown. 2 shows a nitrogen adsorption isotherm of the highly crystalline mesoporous niobium oxide obtained in Example 1. The X-ray diffraction pattern of the mesoporous titanium oxide obtained in Reference Example 2 is shown. The nitrogen adsorption isotherm of the mesoporous titanium oxide obtained in Reference Example 2 is shown. The X-ray diffraction pattern of the highly crystalline mesoporous titanium oxide obtained in Example 2 is shown. The nitrogen adsorption isotherm of the highly crystalline mesoporous titanium oxide obtained in Example 2 is shown. The X-ray diffraction pattern of the mesoporous NbTa composite oxide obtained in Reference Example 3 is shown. The nitrogen adsorption isotherm of the mesoporous NbTa composite oxide obtained in Reference Example 3 is shown. The X-ray-diffraction pattern of the highly crystalline mesoporous NbTa complex oxide obtained in Example 4 is shown. The nitrogen adsorption isotherm of the highly crystalline mesoporous NbTa composite oxide obtained in Example 4 is shown. The X-ray-diffraction pattern of the highly crystalline mesoporous NbTa complex oxide after the alkali treatment obtained in Example 4 is shown. The nitrogen adsorption isotherm of the highly crystalline mesoporous NbTa composite oxide after alkali treatment obtained in Example 4 is shown. The X-ray diffraction pattern of the niobium oxide powder obtained in Comparative Example 1 is shown. The nitrogen adsorption isotherm of the niobium oxide powder obtained in Comparative Example 1 is shown.

Hereinafter, the present invention will be described in detail.
The modified mesoporous oxide (A) of the present invention is obtained by modifying the mesoporous oxide (a) with at least one modifier compound (b) described later, and has various functions and is thermally stable. It is characterized by excellent properties.
According to the present invention, the pores of the mesoporous oxide (a) are coated with the modifier compound (b) while controlling the coverage, or the pores are filled with the modifier compound (b). Can do. Furthermore, the modifier compound (b) not interacting with the mesoporous oxide (a) and its derivative (a compound derived from the modifier compound and water) can be easily removed by solvent washing or distillation. That is, the modified mesoporous oxide (A) provided in the present invention is one in which the degree of modification in the pores or on the surface is highly controlled depending on the purpose.
In the present invention, the modification means that at least one modifier compound (b) described later is immobilized on the surface (pore surface and particle surface) of the mesoporous oxide (a). Immobilization of the modifier compound on the surface of the mesoporous oxide (a) is based on van der Waals force (physical adsorption), Coulomb force or chemical bonding. In particular, the modification using chemical bonds has a strong interaction between the modifier compound (b) and the mesoporous oxide (a), and the modifier compound is firmly immobilized on the surface of the mesoporous oxide (a). preferable.

The mesoporous oxide (a) that can be suitably used in the present invention is prepared by adding a precursor of the mesoporous oxide (a) to a known method, for example, a solution in which a surfactant is dissolved in an organic solvent, and dissolving the precursor. Is hydrolyzed to obtain a high molecular weight and self-organized sol solution, and after obtaining a tissue-stabilized gel from the sol solution, the gel is preferably in an atmosphere in which oxygen is present, preferably at 300 ° C. to It can be obtained by baking at 700 ° C.
Here, examples of the organic solvent include alcohols such as isopropanol, butanol, ethanol, methanol, hexanol, ethylene glycol, butyl cellosolve, and butyl carbitol, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, tetrahydrofuran, and dioxane. Ethers, amides such as dimethylacetamide and dimethylformamide, aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, cyclohexane and heptane, esters such as ethyl acetate and n-butyl acetate, chloroform , Halogen compounds such as methylene chloride and carbon tetrachloride, dimethyl sulfoxide, nitrobenzene, and a mixture of two or more thereof. Among these, alcohols are particularly preferable because of the solubility of the surfactant and the precursor of the metal oxide.

In addition, as the surfactant that can be suitably used for obtaining the mesoporous oxide (a), either a nonionic surfactant or an ionic surfactant may be used, but the pores of the mesoporous oxide may be used. Nonionic surfactants are preferably used from the viewpoints of distribution control and removal and recovery of surfactants.
The nonionic surfactant is not particularly limited, and ether type, ether ester type, ester type, nitrogen-containing type can be used, but from the viewpoint of structural stability during synthesis of mesoporous oxide, Ether-type and nitrogen-containing types are preferred. Examples of ether type nonionic surfactants include polyoxyethylene alkyl ether, single chain length polyoxyethylene alkyl ether, polyoxyethylene secondary alcohol ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether , Polyoxyethylene lanolin derivatives, polyoxyethylene polyoxypropylene block copolymers, polyoxyethylene polyoxypropylene alkyl ether, polypropylene glycol, polyethylene glycol and the like. Examples of the nitrogen-containing nonionic surfactant include polyoxyethylene alkylamine. Specific examples of nonionic surfactants from Asahi Denka Kogyo Co., Ltd. include Adekapluronic (LpF series), Adekapluronic (TR series), Adekator (SO series), Adekator (LO series). ), Adekator (NP / OPL / OA / LA / SP / PC series), Adeka PEG series, and the like.

  Examples of the ionic surfactant include dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium chloride, tetradecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, hexadecyldimethylbenzylammonium. Examples include chloride, hexadecyldimethylbenzylammonium bromide, octadecyltrimethylammonium chloride, octadecyltrimethylammonium bromide, hexadecylpyridinium chloride, hexadecylpyridinium bromide, mesitylene and the like. Moreover, amphoteric surfactants such as carboxybetaine, aminocarboxylate, imidazoline betaine can also be mentioned.

In the present invention, examples of the oxide precursor that can be suitably used to obtain the mesoporous oxide (a) include metal and / or Si salts, alkoxides, chelate compounds, and the like, and mixtures thereof. Here, when a metal-containing material is selected as the precursor of the mesoporous oxide (a), the generated mesoporous oxide (a) is preferable because it can exhibit various catalytic actions. Although there is no restriction | limiting in particular as this metal, A transition metal can be used conveniently. Examples of the precursor of the mesoporous oxide (a) that can be most preferably used in the present invention include chlorides and / or alkoxides such as Ti, Ta, Nb, Zr, W, Mg, Al, and La. .
The shape of the mesoporous oxide (a) described above can be arbitrary, but is preferably a particle having a primary particle diameter of 1 nm to 100 μm. The size of the pores is 0.1 to 100 nm, preferably 1 to 50 nm.
Further, the mesoporous oxide (a) having photocatalytic activity is particularly preferable because it can be applied to fields such as environmental purification, antifouling, and antifogging. Here, the photocatalytic activity means that an oxidation or reduction reaction is caused by light irradiation. These photocatalytic activities can be determined, for example, by measuring the decomposability of organic substances such as pigments when the material surface is irradiated with light. A surface having photocatalytic activity exhibits excellent decomposition activity and contamination resistance of contaminating organic substances.

（式中、Ｒは式（１）で定義した通りである。） In the present invention, at least one modifier compound (b) used to obtain the modified mesoporous oxide (A) is represented by the triorganosilane unit represented by the formula (1), the formula (2). It is selected from the group consisting of compounds having at least one structural unit selected from the group consisting of monooxydiorganosilane units and dioxyorganosilane units represented by formula (3).
R ₃ Si- (1)
(In the formula, each R is independently a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a linear or branched carbon group having 1 to 30 carbon atoms. (A fluoroalkyl group, a linear or branched alkenyl group having 2 to 30 carbon atoms, a phenyl group, a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group.)
_{- (R 2 SiO) - (} 2)
(In the formula, R is as defined in formula (1).)

(In the formula, R is as defined in formula (1).)

  In the present invention, the modification treatment of the mesoporous oxide (a) with the modifier compound (b) is the same as the above-described mesoporous oxide (a) in the presence or absence of water and / or an organic solvent. The modifier compound (b) is preferably mixed at a mass ratio (a) / (b) = 0.0001 to 10000, more preferably (a) / (b) = 0.001 to 1000, preferably 0. It can be obtained by heating at ~ 300 ° C, more preferably at 10-150 ° C. At this time, the state of the modifier compound (b) may be any of a liquid, gas, solid, water and / or a state dissolved or dispersed in an organic solvent. Further, the unreacted modifier compound (b) after the modification treatment can be removed by distillation, filtration, extraction or the like, if necessary.

In the above modification treatment of the present invention, if the ratio of the mesoporous oxide (a) and the modifier compound (b) is less than 0.0001, the amount of the modifier compound (b) which does not react increases and the modification treatment becomes inefficient. It is not preferable. Further, if the ratio of the mesoporous oxide (a) to the modifier compound (b) is greater than 10,000, it is not preferable because the effect of the modification treatment cannot be sufficiently exhibited.
Here, when performing the above modification treatment, examples of organic solvents that can be preferably used include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, cyclohexane, and heptane, ethyl acetate, and n-butyl acetate. Esters, ethylene glycol, butyl cellosolve, alcohols such as isopropanol, n-butanol, ethanol, methanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethers such as tetrahydrofuran, dioxane, dimethylacetamide, dimethylformamide, etc. Examples thereof include amides, halogen compounds such as chloroform, methylene chloride, and carbon tetrachloride, dimethyl sulfoxide, nitrobenzene, and a mixture of two or more thereof.

Examples of the modifier compound (b) used to obtain the modified mesoporous oxide (A) of the present invention include Si—H groups, hydrolyzable silyl groups (alkoxysilyl groups, hydroxysilyl groups, silyl halides). Group, acetoxysilyl group, aminoxysilyl group, etc.), epoxy compounds, acetoacetyl groups, thiol groups, acid anhydride groups and other silicon compounds having reactivity with the mesoporous oxide (a).
Other examples of the modifier compound (b) include, for example, a structure that interacts with the mesoporous oxide (a) by van der Waals force, Coulomb force, etc., such as a polyoxyalkylene group, a sulfonic acid group, Examples thereof include a silicon compound having a carboxyl group.

In the present invention, when the Si-H group-containing silicon compound (b1) represented by the following formula (4) is used as the modifier compound (b), the surface of the mesoporous oxide (a) is modified very efficiently. This is preferable.
H _x R _y Q _z SiO _{(4-xyz) / 2} (4)
(In the formula, each R is independently a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a linear or branched carbon group having 1 to 30 carbon atoms. A fluoroalkyl group, a linear or branched alkenyl group having 2 to 30 carbon atoms, a phenyl group, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group is represented.
In the formula, Q is a group containing at least one functionality-imparting group selected from the group consisting of (a) to (u) below.
(A) At least one hydrophilic group selected from the group consisting of a carboxyl group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, an amino group or a salt thereof, and a polyoxyalkylene group.
(Ii) Epoxy group, acryloyl group, methacryloyl group, (cyclic) acid anhydride group, keto group, carboxyl group, hydrazine residue, isocyanate group, isothiocyanate group, hydroxyl group, amino group, cyclic carbonate group, thiol group, At least one reactive group selected from the group consisting of ester groups;
(Iii) At least one spectral sensitizing group.
Further, 0 <x <4, 0 <y <4, 0 ≦ z <4, and (x + y + z) ≦ 4. )

  In the present invention, the modification treatment of the above-described mesoporous oxide (a) with the Si—H group-containing silicon compound (b1) represented by the above formula (4) is performed in the presence or absence of water and / or an organic solvent. In the above, the compound (a) and the Si-H group-containing silicon compound (b1) are preferably in a mass ratio (a) / (b1) = 0.0001 to 10000, more preferably (a) / (b1) = 0. It can implement by mixing in the ratio of 001-1000, Preferably it is 0-200 degreeC. The mixing at this time may be in any of a liquid phase, a gas phase, and a solid phase. In addition, the reaction between the compound (a) and the Si—H group-containing silicon compound (b1) by the modification treatment can be quantified by measuring the amount of hydrogen gas generated with the reaction.

In the present invention, the modification treatment of the mesoporous oxide (a) with the Si—H group-containing silicon compound (b1) is preferably performed at 0 to 150 ° C. using a dehydrogenative condensation catalyst for the Si—H group. You can also.
In this case, the mesoporous oxide (a) is used as the dehydrogenative condensation catalyst in advance by a method such as a photoreduction method.
And may be modified with the Si-H group-containing silicon compound (b1) or the mesoporous oxide (a) with the Si-H group-containing compound silicon (b1) in the presence of a dehydrogenative condensation catalyst. May be modified.
Here, the dehydrogenation condensation catalyst for the Si—H group means a substance that accelerates the dehydrogenation condensation reaction between the Si—H group and the surface of the mesoporous oxide (a), further water, etc. By using the dehydrogenative condensation catalyst, the surface of the mesoporous oxide (a) can be modified under mild conditions.

Examples of the dehydrogenative condensation catalyst include platinum group catalysts, that is, ruthenium, rhodium, palladium, osmium, iridium, platinum simple substance and compounds thereof, and simple substances such as silver, iron, copper, cobalt, nickel, tin and compounds thereof. Can be mentioned. Of these, platinum group catalysts are preferred, and platinum alone and its compounds are particularly preferred.
Here, examples of the platinum compound include platinum chloride (II), tetrachloroplatinic acid (II), platinum chloride (IV), hexachloroplatinic acid (IV), hexachloroplatinum (IV) ammonium, hexachloroplatinum (IV). Potassium, platinum (II) hydroxide, platinum (IV) dioxide, dichloro-dicyclopentadienyl-platinum (II), platinum-vinylsiloxane complex, platinum-phosphine complex, platinum-olefin complex, etc. can be used. .

｛（式中、Ｒ１は各々独立して直鎖状または分岐状の炭素数が１〜３０個のアルキル基、炭素数５〜２０のシクロアルキル基、直鎖状または分岐状の炭素数が１〜３０個のフルオロアルキル基、炭素数２〜３０のアルケニル基、フェニル基、炭素数１〜２０のアルコキシ基、水酸基、もしくは式（９）で表されるシロキシ基から選ばれた１種以上からなる基を表す。
−Ｏ−（Ｒ₂ ＳｉＯ）_n −ＳｉＲ₃ ・・・（９）
（式中、Ｒは各々独立に直鎖状または分岐状の炭素数１〜３０個のアルキル基、炭素数５〜２０のシクロアルキル基、直鎖状または分岐状の炭素数１〜３０個のフルオロアルキル基、直鎖状または分岐状の炭素数２〜３０個のアルケニル基、フェニル基、炭素数１〜２０のアルコキシ基、又は水酸基を表す。また、ｎは整数であり、０≦ｎ≦１０００である。）｝
Ｈ−（Ｒ¹ ₂ＳｉＯ）_m −ＳｉＲ¹ ₂−Ｑ ・・・（６）
（式中、Ｒ¹ は式（５）で定義した通りである。Ｑは、下記（あ）〜（う）からなる群より選ばれる少なくとも１つの機能性付与基を含有する基である。
（あ）カルボキシル基あるいはその塩、リン酸基あるいはその塩、スルホン酸基あるいはその塩、アミノ基あるいはその塩、ポリオキシアルキレン基からなる群から選ばれた少なくとも１つの親水性基。
（い）エポキシ基、アクリロイル基、メタアクリロイル基、（環状）酸無水物基、ケト基、カルボキシル基、ヒドラジン残基、イソシアネート基、イソチオシアネート基、水酸基、アミノ基、環状カーボネート基、チオール基、エステル基からなる群から選ばれた少なくとも１つの反応性基。
（う）少なくとも１つの分光増感基。
ｍは整数であり、０≦ｍ≦１０００である。）
Ｈ−（Ｒ¹ ₂ＳｉＯ）_m −ＳｉＲ¹ ₂−Ｈ ・・・（７）
（式中、Ｒ¹ は式（５）で定義した通りである。ｍは整数であり、０≦ｍ≦１０００である。）
（Ｒ¹ＨＳｉＯ）_a（Ｒ¹ ₂ＳｉＯ）_b（Ｒ¹ ＱＳｉＯ）_c（Ｒ¹ ₃ＳｉＯ_1/2）_d・・・（８）
（式中、Ｒ¹ は式（５）で定義した通りであり、Ｑは式（６）で定義した通りである。ａは１以上の整数であり、ｂ及びｃは０又は１以上の整数であり、（ａ＋ｂ＋ｃ）≦１００００であり、そしてｄは０又は２である。但し、（ａ＋ｂ＋ｃ）が２以上の整数であり且つｄ＝０の場合、該Ｈシリコーン化合物は環状シリコーン化合物であり、ｄ＝２の場合、該Ｈシリコーン化合物は鎖状シリコーン化合物である。） Moreover, as a Si-H group containing silicon compound (b1) which can be used conveniently for this invention, the mono Si-H group containing compound represented by Formula (5) or Formula (6), for example, represented by Formula (7) And an Si-H group-containing compound having at least one selected from the group consisting of the Si-H group-containing compound at both ends and the H silicone compound represented by the formula (8).

{(In the formula, each R1 is independently a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a linear or branched carbon number of 1; From one or more selected from -30 fluoroalkyl groups, alkenyl groups having 2 to 30 carbon atoms, phenyl groups, alkoxy groups having 1 to 20 carbon atoms, hydroxyl groups, or siloxy groups represented by formula (9) Represents a group.
—O— (R ₂ SiO) _n —SiR ₃ (9)
(In the formula, each R is independently a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a linear or branched carbon group having 1 to 30 carbon atoms. A fluoroalkyl group, a linear or branched alkenyl group having 2 to 30 carbon atoms, a phenyl group, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group, n is an integer, and 0 ≦ n ≦ 1000.)}
^{_{H- (R 1 2 SiO) m}} -SiR 1 2 -Q ··· (6)
(In the formula, R ¹ is as defined in Formula (5). Q is a group containing at least one functionality-imparting group selected from the group consisting of the following (A) to (U)).
(A) At least one hydrophilic group selected from the group consisting of a carboxyl group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, an amino group or a salt thereof, and a polyoxyalkylene group.
(Ii) Epoxy group, acryloyl group, methacryloyl group, (cyclic) acid anhydride group, keto group, carboxyl group, hydrazine residue, isocyanate group, isothiocyanate group, hydroxyl group, amino group, cyclic carbonate group, thiol group, At least one reactive group selected from the group consisting of ester groups;
(Iii) At least one spectral sensitizing group.
m is an integer, and 0 ≦ m ≦ 1000. )
^{_{H- (R 1 2 SiO) m}} -SiR 1 2 -H ··· (7)
(In the formula, R ¹ is as defined in Formula (5). M is an integer, and 0 ≦ m ≦ 1000.)
(R ¹ HSiO) _a (R ¹ ₂ SiO) _b (R ¹ QSiO) _c (R ¹ ₃ SiO _1/2 ) _d (8)
(In the formula, R ¹ is as defined in formula (5), Q is as defined in formula (6), a is an integer of 1 or more, and b and c are 0 or an integer of 1 or more. (A + b + c) ≦ 10000 and d is 0 or 2. provided that when (a + b + c) is an integer of 2 or more and d = 0, the H silicone compound is a cyclic silicone compound, When d = 2, the H silicone compound is a chain silicone compound.)

  In the present invention, specific examples of the mono-Si—H group-containing compound represented by the above formula (5) include, for example, bis (trimethylsiloxy) methylsilane, bis (trimethylsiloxy) ethylsilane, bis (trimethylsiloxy) n-propylsilane. Bis (trimethylsiloxy) i-propylsilane, bis (trimethylsiloxy) n-butylsilane, bis (trimethylsiloxy) n-hexylsilane, bis (trimethylsiloxy) cyclohexylsilane, bis (trimethylsiloxy) phenylsilane, bis (triethylsiloxy) ) Methylsilane, bis (triethylsiloxy) ethylsilane, tris (trimethylsiloxy) silane, tris (triethylsiloxy) silane, pentamethyldisiloxane, 1,1,1,3,3,5,5-heptamethyltrisiloxy 1,1,1,3,3,5,5,6,6-nonamethyltetrasiloxane, trimethylsilane, ethyldimethylsilane, methyldiethylsilane, triethylsilane, phenyldimethylsilane, diphenylmethylsilane, cyclohexyldimethylsilane , T-butyldimethylsilane, di-t-butylmethylsilane, n-octadecyldimethylsilane, tri-n-propylsilane, tri-i-propylsilane, tri-i-butylsilane, tri-n-hexylsilane, triphenyl Silane, allyldimethylsilane, 1-allyl-1,1,3,3-tetramethyldisiloxane, chloromethyldimethylsilane, 7-octenyldimethylsilane, dimethylmethoxysilane, dimethylethoxysilane, methyldimethoxysilane, methyldiethoxy Silane, E cycloalkenyl dimethoxysilane, phenylmethyl silane, diphenyl silane, trimethoxysilane, triethoxysilane, mention may be made of tris (isopropoxy) silane.

  Among these mono-Si-H group-containing compounds, bis (trimethylsiloxy) methylsilane, tris (), because of the good reactivity (dehydrogenation condensation reaction) of the Si-H group during the modification treatment of the mesoporous oxide (a). Those having a siloxy group in the molecule such as trimethylsiloxy) silane, pentamethyldisiloxane, dimethylmethoxysilane, dimethylethoxysilane, methyldimethoxysilane, methyldiethoxysilane, phenyldimethoxysilane, diphenylmethoxysilane, triethoxysilane, etc. Those having an alkoxy group in the molecule are preferred. The mono-Si—H group-containing compound having a siloxy group in the molecule is particularly preferable because of excellent reaction selectivity with the surface of the mesoporous oxide (a).

  In the present invention, specific examples of the both-end Si—H group-containing compound represented by the above formula (7) include 1,1,3,3-tetramethyldisiloxane, 1,1,3,3,5, for example. , 5-hexamethyltrisiloxane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane and the like H-terminal polydimethylsiloxanes having a number average molecular weight of 50000 or less, Number average molecular weight of 50,000 or less such as 3-tetraethyldisiloxane, 1,1,3,3,5,5-hexaethyltrisiloxane, 1,1,3,3,5,5,7,7-octaethyltetrasiloxane H-terminal polydiethylsiloxanes, 1,1,3,3-tetraphenyldisiloxane, 1,1,3,3,5,5-hexaphenyltrisiloxane, 1,1,3,3,5,5 , 7,7-Octaf H-terminated polydiphenylsiloxanes having a number average molecular weight of 50000 or less such as nyltetrasiloxane, 1,3-diphenyl-1,3-dimethyl-disiloxane, 1,3,5-trimethyl-1,3,5-triphenyl -H-terminal polyphenylmethylsiloxanes having a number average molecular weight of 50000 or less, such as trisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetraphenyl-tetrasiloxane, dimethylsilane, ethylmethyl Examples thereof include silane, diethylsilane, phenylmethylsilane, diphenylsilane, cyclohexylmethylsilane, t-butylmethylsilane, di-t-butylsilane, n-octadecylmethylsilane, and allylmethylsilane.

As the Si-H group-containing compound represented by the above formula (7) used in the present invention, the reactivity (dehydrogenation condensation reaction) of the Si-H group during the modification treatment of the mesoporous oxide (a) is good. Therefore, a compound containing Si-H groups at both ends having a number average molecular weight of preferably 10,000 or less, more preferably 2000 or less, and still more preferably 1000 or less can be suitably used.
The H silicone compound represented by the above formula (8) that can be used in the present invention has a number average molecular weight of preferably 10,000 or less from the viewpoint of preventing aggregation of the mesoporous oxide (a) during the modification treatment. Preferably, an H silicone compound of 5000 or less, more preferably 2000 or less, can be suitably used.
Further, as the Si-H group-containing silicon compound (b1) represented by the general formula (4), those having a functional group-containing group (Q) (formula (6), formula (8) and c Is preferably a positive number of 1 or more, etc., because various functions can be imparted to the modified mesoporous oxide (A) obtained in the present invention.

Here, the functional group-containing group (Q) is preferably a group represented by the following formula (10).
-Z- (W) a (10)
(In the formula, Z represents a (a-1) -valent organic group having a molecular weight of 14 to 50,000, and W is selected from the group consisting of the functional groups (A) to (U) in the above formula (4). And a is an integer of 1 to 20.)
For example, as the functional group-containing group (Q), a monovalent group containing a carboxyl group or a salt thereof, a monovalent group containing a phosphate group or a salt thereof, a monovalent group containing a sulfonic acid group or a salt thereof, Modification obtained by selecting one having at least one hydrophilic group selected from the group consisting of a monovalent group containing an amino group or a salt thereof, or a polyoxyalkylene group [(A) in formula (4)] The dispersion stability of the mesoporous oxide (A) in water is very good.

Further, for example, as a functional group-containing group (Q), an epoxy group, an acryloyl group, a methacryloyl group, a cyclic acid anhydride group, an acyclic acid anhydride group, a keto group, a carboxyl group, a hydrazine residue, an isocyanate group, When a group containing at least one reactive group selected from the group consisting of an isothiocyanate group, a hydroxyl group, an amino group, a cyclic carbonate group, a thiol group and an ester group [(i) in formula (4)] is selected The modified mesoporous oxide (A) of the invention has crosslinkability.
Further, for example, when a group having a spectral sensitizing group is selected as the functional group-containing group (Q), when the modified mesoporous oxide (A) of the present invention has photocatalytic activity, the visible light region and / or red The photocatalytic activity and the photoelectric conversion function by irradiation of light in the outside light region can be improved.
Here, the spectral sensitizing group means a group derived from various metal complexes or organic dyes (that is, sensitizing dyes) having absorption in the visible light region and / or the infrared light region.
Examples of sensitizing dyes include xanthene dyes, oxonol dyes, cyanine dyes, merocyanine dyes, rhodocyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes, phthalocyanine dyes (including metal complexes), Porphyrin dyes (including metal complexes), triphenylmethane dyes, perylene dyes, coronene dyes, azo dyes, nitrophenol dyes, and further, for example, Japanese Patent Application Laid-Open No. 1-220380 Examples include a complex of ruthenium, osmium, iron, and zinc described in Japanese Patent No. 504023, and a metal complex such as ruthenium red.

Among these sensitizing dyes, there is absorption in a wavelength region of 400 nm or more, and the energy level of the lowest vacant orbit (the redox potential in the excited state) is higher than the energy level of the conduction band of the mesoporous oxide (a). What has the characteristic of being high is preferable. Such sensitizing dyes are characterized by the measurement of absorption spectra of light in the infrared, visible, and ultraviolet regions, and the measurement of redox potential by electrochemical methods (for example, T. Tani, Photogr. Sci. Eng., 14, 72 (1970); RWBerriman et al., Ibid., 17. 235 (1973); PBGilman Jr., ibid., 18, 475 (1974), etc.), energy level calculation using molecular orbital method (e.g. T .Tani et al., Photogr. Sci. Eng., 11, 129 (1967); DMSturmer et al., Ibid., 17. 146 (1973); ibid., 18, 49 (1974); RGSelby et al., J. Opt. Soc. Am., 33, 1 (1970), etc.), and Gratzel-type wet solar cells made with photocatalysts and spectral sensitizing dyes. it can.
Examples of sensitizing dyes having the above characteristics include compounds having a 9-phenylxanthene skeleton, ruthenium complexes having 2,2-bipyridine derivatives as ligands, compounds having a perylene skeleton, phthalocyanine metal complexes, porphyrins A metal complex etc. can be mentioned.

In the present invention, as a method of obtaining the Si—H group-containing silicon compound having the above-described functional group-containing group (Q),
(Q-1): a carbon-carbon non-carbon compound having a Si—H group-containing compound represented by the following general formula (11) and a functional group [(a) to (u) in the above formula (4)]. A method of hydrosilylating a saturated bond compound.
(Q-2): A carbon-carbon unsaturated bond compound having a Si—H group-containing silicon compound represented by the following general formula (11) and a reactive group [(i) in the above formula (4)]. Examples thereof include a method of reacting a functional group-containing compound having reactivity with the reactive group after obtaining a Si-H group-containing silicon compound having a reactive group through a hydrosilylation reaction.
H _{(x + z)} R _y SiO _{(4-XYZ) / 2} (11)
(In the formula, each R is independently a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a linear or branched carbon group having 1 to 30 carbon atoms. It represents a fluoroalkyl group, a linear or branched alkenyl group having 2 to 30 carbon atoms, a phenyl group, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group, and 0 <(x + z) <4, 0 <y <. 4 and (x + y + z) ≦ 4.)

First, as a method for obtaining a Si—H group-containing silicon compound having a functionality-imparting group (Q), the above-described method (Q-1) [hereinafter (Q-1) -method] will be described. In the (Q-1) -method, as the carbon-carbon unsaturated bond compound used for introducing a hydrophilic group as a functional group into the Si-H group-containing silicon compound represented by the above formula (11), At least one hydrophilic group selected from the group consisting of a carboxyl group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, an amino group or a salt thereof, a polyoxyalkylene group, and a cyclic acid anhydride. Examples thereof include olefins, allyl ethers, vinyl ethers, vinyl esters, (meth) acrylic acid esters, and styrene derivatives.
Preferable specific examples of the carbon-carbon unsaturated bond compound having a hydrophilic group include, for example, polyoxyethylene group-containing allyl ether represented by the formula (12), and further 5-norbornene-2,3-dicarboxylic acid anhydride And allyl succinic anhydride.
_{CH 2 = CHCH 2 O (CH} 2 CH 2 O) b R 5 (12)
(In the formula, b represents an integer of 1 to 1000. R ⁵ represents a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms.)

Moreover, as a carbon-carbon unsaturated bond compound used for introducing a reactive group into the Si—H group-containing silicon compound represented by the above formula (11), an epoxy group, a (meth) acryloyl group, (cyclic) Olefin having at least one reactive group selected from the group consisting of an acid anhydride group, keto group, carboxyl group, hydrazine residue, isocyanate group, isothiocyanate group, hydroxyl group, amino group, cyclic carbonate group, and ester group , Allyl ethers, allyl esters, vinyl ethers, vinyl esters, (meth) acrylic acid esters, styrene derivatives and the like.
Preferred specific examples of the carbon-carbon unsaturated bond compound having the reactive group include, for example, allyl glycidyl ether, glycidyl (meth) acrylate, allyl (meth) acrylate, diallyl ether, diallyl phthalate, vinyl (meth) acrylate. , Vinyl crotonic acid, ethylene glycol di (meth) acrylate, maleic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 5-hexen-2-one, allyl isocyanate, allyl alcohol, ethylene glycol monoallyl Examples include ether, allylamine, allyl isothiocyanate, allyl semicarbazide, (meth) acrylic acid hydrazide, 4-allyloxymethyl-2-oxo-1,3-dioxolane, and the like.

Moreover, as a carbon-carbon unsaturated bond compound used for introducing a spectral sensitizing group into the Si—H group-containing silicon compound represented by the above formula (11), olefins having the aforementioned spectral sensitizing dye, Examples include allyl ethers, allyl esters, vinyl ethers, vinyl esters, (meth) acrylic acid esters, styrene derivatives and the like. These can be easily obtained, for example, by reacting the above-described carbon-carbon unsaturated bond compound having a reactive group with a spectral sensitizing dye having reactivity with the reactive group.
For example, the reactive group of the carbon-carbon unsaturated bond compound having a reactive group is an epoxy group, (cyclic) acid anhydride, isocyanate group, isothiocyanate group, cyclic carbonate group, ester group, keto group, (meth) acryloyl. In the case of a group, it is a spectral sensitizing dye having at least one functional group selected from the group consisting of an amino group, a carboxyl group, a hydroxyl group, a hydrazine residue, and a (meth) acryloyl group, and has a reactive group. When the reactive group of the carbon-carbon unsaturated bond compound is an amino group, a carboxyl group, a hydroxyl group, a hydrazine residue, or a (meth) acryloyl group, an epoxy group, a (cyclic) acid anhydride, an isocyanate group, an isothiocyanate group, At least one functional group selected from the group consisting of a cyclic carbonate group, an ester group, a keto group, and a (meth) acryloyl group; Spectral sensitizing dye and the like.
The reaction between the carbon-carbon unsaturated bond compound having the reactive group and the spectral sensitizing dye having reactivity thereto is performed by changing reaction conditions such as reaction temperature, reaction pressure, and solvent according to the type of each reactive group. Can be selected and implemented. At that time, from the viewpoint of stability of the spectral sensitizing dye, the reaction temperature is preferably 300 ° C. or lower, more preferably 150 ° C. or lower and 0 ° C. or higher.

In the (Q-1) -method, the hydrosilylation reaction between the carbon-carbon unsaturated bond compound and the Si—H group-containing silicon compound represented by the formula (11) is preferably performed in the presence of a catalyst in an organic solvent. The carbon-carbon unsaturated bond compound (C) and the Si—H group-containing silicon compound (b1 ′) represented by the formula (11) at 0 to 200 ° C. in the presence or absence of a weight ratio (C) /(B1′)=0.01 or more, more preferably (C) / (b1 ′) = 0.01 to 2, more preferably (C) / (b1 ′) = 0.01 to 1. Can be performed.
As the catalyst for the hydrosilylation reaction, platinum group catalysts, that is, ruthenium, rhodium, palladium, osmium, iridium, and platinum compounds are suitable, and platinum compounds and palladium compounds are particularly suitable. Examples of platinum compounds include platinum (II) chloride, tetrachloroplatinic acid (II), platinum (IV) chloride, hexachloroplatinic acid (IV), hexachloroplatinum (IV) ammonium, hexachloroplatinum (IV) potassium, hydroxide Platinum (II), platinum dioxide (IV), dichloro-dicyclopentadienyl-platinum (II), platinum-vinylsiloxane complex, platinum-phosphine complex, platinum-olefin complex and platinum alone,
Examples include those in which solid platinum is supported on alumina, silica, or activated carbon. Examples of the palladium compound include palladium (II) chloride, ammonium tetraamminepalladium (II) chloride, and palladium (II) oxide.
Examples of the organic solvent that can be used in the hydrosilylation reaction include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, cyclohexane, and heptane, esters such as ethyl acetate and n-butyl acetate, Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethers such as tetrahydrofuran and dioxane, amides such as dimethylacetamide and dimethylformamide, halogen compounds such as chloroform, methylene chloride and carbon tetrachloride, dimethyl sulfoxide, nitrobenzene and the like A mixture of two or more of these may be mentioned.

Next, as a method for obtaining a Si—H group-containing silicon compound having a functional group, the above-described method (Q-2) [hereinafter (Q-2) -method] will be described.
Examples of the carbon-carbon unsaturated bond compound having a reactive group used in the (Q-2) -method include those described in the (Q-1) -method. The hydrosilylation reaction between the Si—H group-containing silicon compound represented by the above formula (11) and the carbon-carbon unsaturated bond compound having the reactive group was described in the (Q-1) -method. It can be carried out under the same conditions as the hydrosilylation reaction.
According to the (Q-2) -method, a Si—H group-containing silicon compound having a reactive group can be obtained by the hydrosilylation reaction. The reaction between the Si-H group-containing silicon compound having a reactive group and the functional group-containing compound having reactivity therewith is a reaction of reaction temperature, reaction pressure, solvent, etc. according to the type of each reactive group. It can be implemented by selecting conditions. At that time, from the viewpoint of the stability of the Si—H group, the reaction temperature is preferably 300 ° C. or lower, more preferably 150 ° C. or lower and 0 ° C. or higher.

The modified mesoporous oxide (A) obtained by the present invention has various functions such as organic solvent dispersibility, resin compatibility, and crosslinking performance, and has improved structural thermal stability. It is. Here, the structural thermal stability means the stability of the pore structure during heating, particularly during crystallization heat treatment.
Since the modified mesoporous oxide (A) of the present invention is excellent in structural thermal stability, a highly crystalline mesoporous oxide (B) in which the pore structure of the mesoporous oxide (a) before modification is highly maintained by heat treatment is obtained. Obtainable. The heat treatment conditions at this time are not limited as long as the mesoporous oxide (a) is crystallized. For example, in an atmosphere such as air, vacuum, nitrogen stream, argon stream, helium stream, It is preferable to hold at 300 to 2000 ° C, preferably 400 to 1500 ° C, preferably for 1 minute or more, and more preferably for 1 to 100 hours.
Further, when the modified mesoporous oxide (A) is washed with a solvent before heat treatment, the unreacted modifier compound (b) can be removed, so that the pore size of the highly crystalline mesoporous oxide (B) to be generated is The state of the mesoporous oxide (a) can be maintained at a higher level and is preferable because the surface area becomes high. Examples of the solvent include the above-described water and / or organic solvents that can be suitably used when the mesoporous oxide (a) is modified with the modifier compound (b).

In the present invention, the maintenance of the pore structure of the mesoporous oxide can be evaluated by measuring nitrogen adsorption isotherms before and after the modification treatment and before and after the heat treatment, TEM observation, and the like. The crystallinity of the mesoporous oxide can be evaluated by an ordinary method, for example, by X-ray diffraction (XRD).
In the present invention, the highly crystalline mesoporous oxide (B) obtained by heat treatment of the modified mesoporous oxide (A) is obtained by subjecting the pore size of the mesoporous oxide (a) before modification to an acid or alkali treatment or a combination treatment thereof. Can be maintained at a higher level.
Examples of the acid include hydrogen halides such as hydrochloric acid, carboxylic acids such as sulfuric acid, nitric acid and trichloroacetic acid, and p-toluenesulfonic acid.
Examples of the alkali include sodium alkoxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide, and sodium methylate, and potassium alkoxides such as potassium methylate.
The acid or alkali treatment of the highly crystalline mesoporous oxide (B) is preferably carried out in water and / or a hydrophilic solvent (alcohols, ethers, ketones, amides, dimethyl sulfoxide, etc.).

In the present invention, the highly crystalline mesoporous oxide (B) obtained by heat treatment of the modified mesoporous oxide (A) is a silicon atom derived from the modifier compound (b) present on the surface of the modified mesoporous oxide (A). In a state where at least a part (preferably 5 mol% or more, more preferably 50 mol% or more) of the organic group (R) bonded to is converted to a hydroxyl group and / or a siloxane bond formed by a dehydration condensation reaction of the hydroxyl group. is there.
In the modified mesoporous oxide (A) or the highly crystalline mesoporous oxide (B) of the present invention, those having semiconductor characteristics are hydrophilic and / or photocatalytic activity by irradiating light with energy higher than the band gap energy. Furthermore, the photoelectric conversion function is shown.

The modified mesoporous oxide (A) or highly crystalline mesoporous oxide (B) having photocatalytic activity is selected from the group consisting of Pt, Rh, Ru, Ir, Cu, Sn, Ni, Fe, W, and Co. It is possible to improve the photocatalytic activity by supporting at least one transition metal and / or oxide of the transition metal. As a method for supporting these transition metals and / or oxides of the transition metals, for example, the transition metal to be supported and / or the precursor of the oxide of the transition metal may be modified mesoporous oxide (A) or highly crystalline mesoporous oxide. Examples thereof include a method of heating in the presence of (B) (baking method), a method of irradiating light (photoelectric deposition method), and combinations thereof.
In the present invention, as a light source of light having energy higher than the band gap energy, in addition to light obtained in a general residential environment such as sunlight and indoor lighting, light such as black light, xenon lamp, mercury lamp, LED, etc. Is available.
The modified mesoporous oxide (A) or the highly crystalline mesoporous oxide (B) of the present invention, which has photocatalytic activity such as organic matter decomposition, has various functions such as antibacterial, antifouling, deodorizing, and NOx decomposition. It is highly preferred because it is expressed and can be used for environmental purification such as air and water.

The following examples, reference examples and comparative examples will specifically explain the present invention, but these do not limit the scope of the present invention.
In Examples, Reference Examples and Comparative Examples, various physical properties were measured by the following methods.
1. X-ray diffraction (XRD)
X-ray diffraction (XRD) was measured using RINT-2100 (Rigaku Co., Ltd.).
2. Nitrogen adsorption isotherm The nitrogen adsorption isotherm was measured using SA3100 (Coulter). The relative pressure (P / P0) (X axis) region in which the nitrogen adsorption amount (Y axis / volume (mL / g)) increases rapidly corresponds to the pore diameter. The degree of rise is related to the pore volume.
3. TEM observation TEM observation was performed using JEM2010F (manufactured by JEOL Co., Ltd.) at an acceleration voltage of 200 kV.
Apparatus: Hitachi HF2000 type Infrared absorption spectrum The infrared absorption spectrum was measured as a diffuse reflection spectrum using FT / IR-410 (manufactured by JASCO Corporation) with Dura Sampler IR (ST Japan Co., Ltd.).

5). Dispersibility of organic solvent 0.01 g of sample was added to 2 g of toluene and the mixture was sonicated for 1 minute and allowed to stand for 5 minutes. Then, based on the degree of dispersion of the sample (visual evaluation), It was evaluated in three stages.
A: The sample is completely dispersed.
○: The sample is slightly precipitated.
X: The sample is completely precipitated.
6). Photocatalytic activity 0.01 g of a sample was added to 10 g of a 0.01 mmol / l aqueous solution of methylene blue, and after irradiation with a FL20SBLB type black light made by Toshiba Lighting & Technology under stirring for 3 hours, the degree of decomposition of methylene blue (based on the degree of fading) ), The activity of the photocatalyst was evaluated in the following four stages.
The light intensity at this time was adjusted so that the ultraviolet intensity (using the UD-36 type light receiving part as the light receiving part) measured with a Topcon UVR-2 type ultraviolet intensity meter was 1 mW / cm ² . .
A: Blue of methylene blue disappears and becomes transparent.
○: Methylene blue slightly remains blue.
Δ: Blue color of methylene blue becomes lighter than before the test.
×: Blue color of methylene blue is almost the same as before the test.

[Reference Example 1]
Preparation of mesoporous niobium oxide As a surfactant, P123 [trade name, manufactured by BASF: (HO (CH ₂ CH ₂ O) ₂₀ (CH ₂ CH (CH ₃ ) O) ₇₀ (CH ₂ CH ₂ O) ₂₀ H) 1 g was charged into a beaker, 10 g of n-propanol was added thereto, and the mixture was stirred to dissolve the surfactant. To this, 1.89 g (7 mmol) of niobium pentachloride (NbCl5) was added and dissolved by stirring for 20 minutes. Next, 1.26 g (70 mmol) of water was added for hydrolysis, and the mixture was further stirred for 10 minutes. The obtained sol solution was transferred to a petri dish, aged for 7 days in a constant temperature bath at 40 ° C., and then baked at 450 ° C. for 5 hours in an electric furnace in an air atmosphere to obtain Compound (1).
The X-ray diffraction (XRD) of the obtained compound (1) is shown in FIG. FIG. 2 shows a nitrogen adsorption isotherm of the compound (1). From these results, it is found that the obtained compound (1) is amorphous mesoporous niobium oxide having a BET surface area of 205 m ² / g and a pore diameter of 6.0 nm. As a result of TEM observation, it was confirmed that mesoporous niobium oxide had a two-dimensional hexagonal structure.

[Example 1]
0.8 g of mesoporous niobium oxide synthesized in Reference Example 1 was added to a reactor having a reflux condenser, a thermometer, and a stirring device, and the temperature was raised to 70 ° C. To this, 4.0 g of bis (trimethylsiloxy) methylsilane was added with stirring at 70 ° C. over about 5 minutes, and stirring was further continued at 70 ° C. for 5 hours. The amount of hydrogen gas produced by the reaction of bis (trimethylsiloxy) methylsilane was 27.0 ml at 23 ° C. Subsequently, unreacted bis (trimethylsiloxy) methylsilane was removed from the reaction solution by heating under reduced pressure to obtain modified mesoporous niobium oxide. When an infrared absorption spectrum of the obtained modified mesoporous niobium oxide was measured, absorption of an Si—CH ₃ group (1271 cm ⁻¹ ) was observed.
The organic solvent dispersibility of the obtained modified mesoporous niobium oxide was good (◯), and the organic solvent dispersibility (x) of the mesoporous niobium oxide before modification was improved by the modification treatment.
0.1 g of the obtained modified mesoporous niobium oxide was put in 40 ml of tetrahydrofuran (THF), stirred at 60 ° C. for 30 minutes, and then filtered by suction to wash the modified mesoporous niobium oxide.

FIG. 3 shows the nitrogen adsorption isotherm of the modified mesoporous niobium oxide before washing with THF, and FIG. 4 shows the nitrogen adsorption isotherm after washing with THF. The BET surface area of the modified mesoporous niobium oxide before the THF cleaning was 35 m ² / g, whereas the BET surface area after the THF cleaning was 129 m ² / g, and the surface area increased by the THF cleaning.
Further, it was observed by X-ray diffraction (XRD) that the modified mesoporous niobium oxide was amorphous before and after the THF cleaning.
Subsequently, the modified mesoporous niobium oxide washed with THF was heat-treated in air at 670 ° C. for 3 hours. The X-ray diffraction (XRD) of the obtained compound is shown in FIG. Moreover, the measurement result of a nitrogen adsorption isotherm is shown in FIG. These results show that the obtained compound is highly crystalline mesoporous niobium oxide having a surface area of 136 m ² / g and a pore diameter of 6.0 nm. As a result of TEM observation, it was confirmed that the obtained highly crystalline mesoporous niobium oxide had a two-dimensional hexagonal structure.

[Reference Example 2]
Preparation of mesoporous titanium oxide As a surfactant, P85 [trade name, manufactured by BASF: HO (CH ₂ CH ₂ O) ₂₆ (CH ₂ CH (CH ₃ ) O) ₃₉ (CH ₂ CH ₂ O) ₂₆ H] 1 g In a beaker, 10 g of n-propanol was added thereto, and the mixture was stirred to dissolve the surfactant. To this, 2.84 g (10 mmol) of titanium tetraisopropoxide (Ti (i-PrO) ₄ ) was added and dissolved with stirring for 20 minutes. Next, 0.85 ml (0.01 mol) of 36 mass% hydrochloric acid was added, and the mixture was further stirred for 10 minutes. The obtained sol solution was transferred to a petri dish, aged in a constant temperature bath at 40 ° C. for 7 days, and then baked at 300 ° C. for 10 hours in an electric furnace under an air atmosphere to obtain a compound (2).
The X-ray diffraction (XRD) of the obtained compound (2) is shown in FIG. FIG. 8 shows a nitrogen adsorption isotherm of the compound (2). From these results, it is understood that the obtained compound (2) is amorphous mesoporous titanium oxide having a BET surface area of 291 m ² / g and a pore diameter of 3.7 nm. As a result of TEM observation, it was confirmed that mesoporous titanium oxide had a worm-hole structure.

[Example 2]
0.8 g of mesoporous titanium oxide synthesized in Reference Example 2 was added to a reactor having a reflux condenser, a thermometer, and a stirring device, and the temperature was raised to 70 ° C. To this, 4.0 g of bis (trimethylsiloxy) methylsilane was added with stirring at 70 ° C. over about 5 minutes, and stirring was further continued at 70 ° C. for 5 hours. The amount of hydrogen gas produced by the reaction of bis (trimethylsiloxy) methylsilane was 67.0 ml at 23 ° C. Subsequently, unreacted bis (trimethylsiloxy) methylsilane was removed from the reaction solution by heating under reduced pressure to obtain modified mesoporous titanium oxide. When the infrared absorption spectrum of the obtained modified mesoporous titanium oxide was measured, absorption (1271 cm ⁻¹ ) of Si—CH ₃ group was observed.
The organic solvent dispersibility of the obtained modified mesoporous titanium oxide was good (◯), and the organic solvent dispersibility (×) of the mesoporous titanium oxide before modification was improved by the modification treatment.
0.1 g of the obtained modified mesoporous titanium oxide was put in 40 ml of tetrahydrofuran (THF), stirred at 60 ° C. for 30 minutes, and then filtered by suction to wash the modified mesoporous titanium oxide.

Subsequently, the modified mesoporous niobium oxide washed with THF was heat-treated in air at 600 ° C. for 3 hours. The X-ray diffraction (XRD) of the obtained compound is shown in FIG. Moreover, the measurement result of a nitrogen adsorption isotherm is shown in FIG. From these results, it is understood that the obtained compound is crystalline (anatase type) mesoporous titanium oxide having a surface area of 274 m ² / g and a pore diameter of 3.5 nm. As a result of TEM observation, it was confirmed that the obtained highly crystalline mesoporous titanium oxide had a worm-hole structure. Moreover, when the photocatalytic activity evaluation of the obtained highly crystalline mesoporous titanium oxide was implemented, it was a favorable result ((circle)).

[Example 3]
After adding 2 g of a tetrahydrofuran solution containing 0.1% by mass of Ru ₃ (CO) ₁₂ to 0.2 g of the highly crystalline mesoporous titanium oxide obtained in Example 2, the mixture was stirred for 1 hour, and then the tetrahydrofuran was removed by evaporation. Further, by heating in the atmosphere at 400 ° C. for 3 hours, highly crystalline mesoporous titanium oxide carrying RuO ₂ was obtained.
When the photocatalytic activity of the obtained RuO ₂ -supported highly crystalline mesoporous titanium oxide was evaluated, the result was very good (◎).

[Reference Example 3]
Preparation of Mesoporous NbTa Composite Oxide As a surfactant, 1 g of P123 (trade name, manufactured by BASF) was charged into a beaker, 10 g of ethanol was added thereto, and the mixture was stirred to dissolve the surfactant. To this, 0.81 g (3 mmol) of niobium pentachloride and 1.07 g (3 mmol) of tantalum pentachloride were added and dissolved by stirring for 20 minutes. Next, 0.32 g (18 mmol) of water was added for hydrolysis, and the mixture was further stirred for 10 minutes. The obtained sol solution was transferred to a petri dish and aged in a constant temperature bath at 40 ° C. for 7 days, and then baked at 450 ° C. for 5 hours in an electric furnace under an air atmosphere to obtain a compound (3).
The X-ray diffraction (XRD) of the obtained compound (3) is shown in FIG. FIG. 12 shows a nitrogen adsorption isotherm of the compound (3). From these results, it can be seen that the obtained compound (3) is an amorphous mesoporous NbTa composite oxide having a BET surface area of 205 m ² / g and a pore diameter of 7.4 nm. As a result of TEM observation, it was confirmed that the mesoporous NbTa composite oxide had a two-dimensional hexagonal structure.

[Example 4]
0.7 g of the mesoporous NbTa composite oxide synthesized in Reference Example 3 was added to a reactor having a reflux condenser, a thermometer, and a stirring device, and the temperature was raised to 70 ° C. To this, 3.5 g of bis (trimethylsiloxy) methylsilane was added with stirring at 70 ° C. over about 5 minutes, and stirring was further continued at 70 ° C. for 5 hours. The amount of hydrogen gas produced by the reaction of bis (trimethylsiloxy) methylsilane was 26.0 ml at 23 ° C. Subsequently, unreacted bis (trimethylsiloxy) methylsilane was removed from the reaction solution by heating under reduced pressure to obtain a modified mesoporous NbTa composite oxide. Infrared absorption spectrum of the resulting modified mesoporous NbTa composite oxide was measured. Absorption of Si-CH ₃ groups (1271cm ^-1) were observed.
The organic solvent dispersibility of the obtained modified mesoporous NbTa composite oxide was good (◯), and the organic solvent dispersibility (×) of the mesoporous NbTa composite oxide before modification was improved by the modification treatment.

The obtained modified mesoporous NbTa composite oxide was heat-treated in air at 793 ° C. for 3 hours. The X-ray diffraction (XRD) of the obtained compound is shown in FIG. Moreover, the measurement result of a nitrogen adsorption isotherm is shown in FIG. From these results, it can be seen that the obtained compound is a highly crystalline mesoporous NbTa composite oxide having a surface area of 102 m ² / g and a pore diameter of 4.5 nm.
Furthermore, 0.1 g of the obtained highly crystalline mesoporous NbTa composite oxide was placed in 50 ml of an aqueous sodium hydroxide solution adjusted to pH 13, stirred at 100 ° C. for 30 minutes, cooled, and then filtered with suction to obtain a highly crystalline mesoporous The NbTa composite oxide was alkali treated. FIG. 15 shows the X-ray diffraction (XRD) of the highly crystalline mesoporous NbTa composite oxide after the alkali treatment, and FIG. 16 shows the nitrogen adsorption isotherm. The highly crystalline mesoporous NbTa composite oxide maintains the crystallinity by alkali treatment, while maintaining the BET surface area (138 m ² / g) and the pore diameter (6.
5 nm) was confirmed to increase. As a result of TEM observation, it was confirmed that the alkali-treated highly crystalline mesoporous NbTa composite oxide has a two-dimensional hexagonal structure.

[Comparative Example 1]
0.1 g of mesoporous niobium oxide obtained in Reference Example 1 was heat-treated at 570 ° C. for 3 hours in air. The X-ray diffraction (XRD) of the obtained compound is shown in FIG. 17, and the nitrogen adsorption isotherm is shown in FIG. From these results and TEM observation, it was confirmed that the obtained compound was a crystalline niobium oxide powder having a BET surface area of 59 m ² / g with a collapsed pore structure.
[Comparative Example 2]
The mesoporous titanium oxide 0.1 g obtained in Reference Example 2 was heat-treated at 600 ° C. for 3 hours in air. From the X-ray diffraction (XRD), nitrogen adsorption isotherm, and TEM observation, it was confirmed that the obtained compound was an anatase-type titanium oxide powder having a BET surface area of 12 m ² / g with a collapsed pore structure.
Moreover, the photocatalytic activity evaluation of the obtained anatase-type titanium oxide powder was Δ, which was inferior to the photocatalytic activity evaluation (◯) of the highly crystalline mesoporous titanium oxide obtained in Example 2.

[Comparative Example 3]
To a solution of 3.5 g of tetraethylorthosilicate (TEOS) dissolved in 10 g of ethanol, 0.7 g of the mesoporous NbTa composite oxide synthesized in Reference Example 3 was added and stirred at room temperature for 30 minutes. Next, after adding 0.85 ml (0.01 mol) of 36 mass% hydrochloric acid and further stirring for 5 hours, compound (4) was obtained by baking at 300 ° C. for 10 hours in an electric furnace under an air atmosphere.
The organic compound dispersibility of the obtained compound (4) was a bad result (x).
When the obtained compound (4) was heat-treated in air at 793 ° C. for 3 hours and the nitrogen adsorption isotherm was measured, the presence of pores was not observed.
Further, 0.1 g of the compound (5) heat-treated by the above method was placed in 50 ml of an aqueous sodium hydroxide solution adjusted to pH 13, stirred at 100 ° C. for 30 minutes, cooled, and then subjected to suction filtration to measure the nitrogen adsorption isotherm. However, the presence of pores was not observed.

The modified mesoporous oxide (A) and the highly crystalline mesoporous oxide (B) of the present invention are materials having a high uniformity of pores having various physicochemical functions and a high surface area. It can be used as a catalyst, for example, as an inorganic polymer having extremely excellent adsorption ability.
Furthermore, the modified mesoporous oxide (A) or the highly crystalline mesoporous oxide (B) of the present invention, which has photocatalytic activity such as organic matter decomposition, has various antibacterial, antifouling, deodorizing, NOx decomposition and the like. It exhibits its function and can be used for environmental purification such as air and water.
The modified mesoporous oxide (A) or the highly crystalline mesoporous oxide (B) of the present invention, wherein the contact angle with water at 20 ° C. is 60 ° or less (preferably 10 ° or less) by light irradiation. Materials (hydrophilic film and base material coated with the hydrophilic film, etc.) for anti-fogging technology to prevent fogging of mirrors and glass, and further to antifouling technology and antistatic technology for building exteriors, etc. Can be applied.

Examples of application of the modified mesoporous oxide (A) or highly crystalline mesoporous oxide (B) having photocatalytic activity of the present invention to the antifouling technology field include, for example, building materials, building exteriors, building interiors, window frames, and window glass. , Structural members, building facilities such as houses, especially toilets, bathtubs, washstands, lighting fixtures, lighting covers, kitchenware, tableware, dishwashers, dish dryers, sinks, cooking ranges, kitchen hoods, ventilation fans, etc., vehicles Depending on the application, it can also be used for interiors, and it is effective for use in parts that require transparency, such as covers for vehicle lighting, window glass, instruments, display panels, etc. Exterior of goods, dust cover and painting, display equipment, its covers, traffic signs, various display devices, display objects such as advertising towers, sound insulation walls for roads, railways, etc., bridges, exterior and painting of guardrails, tunnels Exterior and exterior of electronic and electrical equipment such as decoration and painting, insulators, solar battery covers, solar water heater heat collection covers, especially transparent members, exteriors of greenhouses, greenhouses, especially transparent members, and indoors Even if it exists, the use of the environment which may be contaminated, for example, facilities for medical and physical education, apparatus, etc. can be mentioned.

  Examples of the application of the modified mesoporous oxide (A) or highly crystalline mesoporous oxide (B) having photocatalytic activity of the present invention to the anti-fogging technology field include, for example, mirrors (vehicle rear-view mirrors, bathroom mirrors, wash basins) Mirrors, dental mirrors, road mirrors, etc.), lenses (glasses lenses, optical lenses, illumination lenses, semiconductor lenses, photocopier lenses, vehicle rear-view camera lenses, etc.), prisms, windows in buildings and towers Glass, vehicle window glass (automobiles, railway vehicles, aircraft, ships, submersibles, snow vehicles, ropeway gondola, amusement park gondola, spacecraft, etc.), vehicle windshields (automobiles, motorcycles, rail vehicles, aircraft, Ships, submersibles, snow vehicles, snowmobiles, ropeway gondola, amusement park gondola, spacecraft, etc.), protective goggles, sports goggles, protective mask seals , Sports mask shield, helmet shield, glass for frozen food display case, glass for insulated food display case, cover for measuring device, cover for vehicle rear-view camera lens, focusing lens for laser dental treatment device, inter-vehicle distance Applications of a sensor for detecting laser light such as a distance sensor, a cover for an infrared sensor, and a filter for a camera can be given.

  Examples of application of the modified mesoporous oxide (A) or highly crystalline mesoporous oxide (B) having photocatalytic activity of the present invention to the antistatic technical field include, for example, cathode ray tubes, magnetic recording media, optical recording media, and magneto-optical recording. Media, audio tapes, video tapes, analog records, household electrical appliance housings and parts, exterior and coating, OA equipment housings and parts, exterior and coating, building materials, building exteriors, building interiors, window frames, window glass, Applications such as structural members, exterior and painting of vehicles, exteriors of mechanical devices and articles, dustproof covers and painting can be mentioned.

  Examples of the application of the modified mesoporous oxide (A) or highly crystalline mesoporous oxide (B) having photocatalytic activity of the present invention to the antibacterial and antifungal technical fields include, for example, building materials, building exteriors, building interiors, window frames, Structural members, building facilities such as houses, especially toilets, bathtubs, wash basins, lighting fixtures, lighting covers, kitchenware, tableware, dishwashers, dish dryers, sinks, cooking ranges, kitchen hoods, ventilation fans, cupboards, display cabinets, Bathrooms, washroom walls, ceilings, door knobs, medical and public facilities, such as hospital components, ambulance components, food / pharmaceutical factories, public facilities such as schools / gymnasiums / stations, public baths, public For hygiene management in toilets, inns, hotels, etc., there can be listed applications such as walls, floors and ceilings, various fixtures, fixtures, and door knobs. In particular, it can be widely used as a hospital infection prevention method for members in hospitals. As the members in the hospital, for example, floors, walls, ceilings, handrails, door handles, water taps in places where an unspecified number of people come into contact, such as hospital rooms, examination rooms, corridors, stairs, elevators, waiting rooms, washrooms, etc. Examples include various medical equipment. In addition, the antibacterial and antifungal properties can be effectively imparted not only in hospitals but also to various members in places requiring hygiene such as ambulances, food storage rooms, and food cooking rooms.

A modified mesoporous oxide (A) or highly crystalline mesoporous oxide (B) having photocatalytic activity provided by the present invention, which has a contact angle with water at 20 ° C. of 70 ° or more (preferably 90 ° by light irradiation). Hydrophobic products (hydrophobic molded products, hydrophobic membranes, and substrates coated with the hydrophobic membranes, etc.) that have become more than (°) are provided with drip-proofing and drainage properties, and prevention of adhesion of water-based soils. It can be applied to antifouling technology using water and washability, as well as anti-icing and snow prevention technology, such as window glass, windshield glass, mirrors, lenses, goggles, covers, insulators, building materials, building exteriors, building interiors, Applications such as structural members, exterior and painting of vehicles, exteriors of machinery and goods, various display devices, lighting devices, housing equipment, tableware, kitchen appliances, household electrical appliances, roofing materials, antennas, power transmission lines, ice and snow slides, etc. Can be used for

The modified mesoporous oxide (A) or highly crystalline mesoporous oxide (B) provided by the present invention and having a photoelectric conversion function can exhibit functions such as solar energy power conversion. It can be used for applications such as optical semiconductor electrodes used in (wet) solar cells and the like.
In addition, what is provided by the present invention and changes in wettability with water by light irradiation (change from hydrophobic to hydrophilic, or from hydrophilic to hydrophobic) can be applied to an offset printing original plate or the like. Very useful for application.

Claims (5)

The mesoporous oxide (a) is represented by a triorganosilane unit represented by the formula (1), a monooxydiorganosilane unit represented by the formula (2), and a dioxyorganosilane unit represented by the formula (3). By immobilizing the surface of the mesoporous oxide (a) with at least one modifier compound (b) selected from the group consisting of compounds having at least one structural unit selected from the group consisting of A highly crystalline mesoporous oxide (B) derived by heat-treating the resulting modified mesoporous oxide (A ) .
R ₃ Si- (1)
(In the formula, each R is independently a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a linear or branched carbon group having 1 to 30 carbon atoms. (A fluoroalkyl group, a linear or branched alkenyl group having 2 to 30 carbon atoms, a phenyl group, a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group.)
_{- (R 2 SiO) - (} 2)
(In the formula, R is as defined in formula (1).)

(In the formula, R is as defined in formula (1).)   A highly crystalline mesoporous oxide (B) derived by washing the modified mesoporous oxide (A) according to claim 1 with a solvent, followed by heat treatment.     The highly crystalline mesoporous oxide (B) according to claim 2 or 3, which is subjected to an acid and / or alkali treatment after the heat treatment.   The highly crystalline mesoporous oxide (B) according to any one of claims 1 to 3, wherein the mesoporous oxide (a) is a mesoporous oxide containing a transition metal.   The at least one transition metal selected from the group consisting of Pt, Rh, Ru, Ir, Cu, Sn, Ni, Fe, W, and Co and / or an oxide of the transition metal are supported. 5. The highly crystalline mesoporous oxide (B) according to any one of 4 above.

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