JP5599134B2 - Organic / inorganic composite composition using polyfunctional silane - Google Patents

Description

The present invention relates to an organic / inorganic composite composition capable of forming an organic / inorganic composite having excellent weather resistance, chemical resistance, optical properties, antifouling properties, antifogging properties, antistatic properties and the like. . The organic / inorganic composite composition of the present invention is particularly useful as a coating agent for architectural exteriors, automobiles, displays, lenses and the like.
In recent years, research on organic / inorganic composite materials has been conducted with the aim of combining the advantages of organic polymers such as good processability, flexibility and adhesion with the advantages of inorganic substances such as weather resistance, flame retardancy, and chemical resistance. Many have been done. However, since organic polymers are generally incompatible with inorganic polymers, these composites are heterogeneous, and the characteristics of organic polymers and inorganic substances are often not expressed effectively.

To meet these challenges, organic and inorganic composite materials that are homogeneous and transparent on the micro level have also been proposed.
For example, in Patent Document 1, in the presence of a non-reactive polymer having an amide bond such as poly (N-acetylethyleneimine) or polyvinylpyrrolidone, a hydrolyzable polymerizable organometallic compound is hydrolyzed and gelled, It is disclosed to obtain an organic / inorganic composite transparent homogeneous material in which a non-reactive polymer having an amide bond is uniformly dispersed in the three-dimensional fine network structure of the metal oxide gel produced.
Patent Document 2 discloses a method for producing an oxazoline / silica composite molded article in which an oxazoline polymer having a hydrolyzable polymerizable silyl group and hydrolyzable polymerizable silane are hydrolyzed.

  These prior documents also describe that tetraalkoxysilane or the like is used as the hydrolyzable compound, and that the composite can be formed into a film or the like. However, these composites are all inferior in film formability, moldability and spinnability, and it is difficult to obtain a uniform film or yarn continuously and efficiently by coating or spinning. For this reason, the use of the composite has been limited in spite of the excellent properties of being transparent and microscopically homogeneous.

As a method for solving these problems, Patent Document 3 and Patent Document 4 each propose a method in which colloidal silica and an aqueous binder are used in combination. However, all have problems that the stability of the coating material, the transparency of the film, and the stain resistance are insufficient.
On the other hand, Patent Document 5 discloses a method of forming a highly transparent film with a coating material containing inorganic oxide fine particles and a surfactant. However, there is a problem that the surfactant remains in the film and chemical resistance is lowered, and there is a problem that a crack is easily generated when the film is formed on the organic substrate.

Japanese Patent Laid-Open No. 3-212451 Japanese Patent Laid-Open No. 3-56535 JP-A-7-26165 JP-A-11-1893 JP 2003-206416 A

  The object of the present invention is to easily prepare an organic / inorganic composite excellent in weather resistance, chemical resistance, optical characteristics, antifouling property, antifogging property, antistatic property, etc. without using a special device. It is to provide an organic / inorganic composite composition that can be formed with a small environmental load and is excellent in film formability and moldability.

As a result of intensive studies aimed at solving the above problems, the present inventors have reached the present invention.
That is, the present invention is as follows.
(1) Inorganic oxide particles (A) composed of one kind selected from silicon oxide, aluminum oxide, antimony oxide, and composite oxides thereof, polymer emulsion particles (B), and the following formula (1) It is an organic / inorganic composite composition comprising polyfunctional silane (C) having 3 to 20 atomic groups (c1) represented in one molecule,
R ¹ _n SiX _3-n A- (1)
{Wherein R ¹ represents hydrogen or an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, or an aryl group. Moreover, you may have a halogen group, a hydroxy group, a mercapto group, an amino group, a (meth) acryloyl group, and an epoxy group on these substituents. X represents a hydrolyzable group, and n is an integer of 0-2. A is a site containing 2 to 20 methylene groups. } The polymer emulsion particles (B) polymerize a hydrolyzable silicon compound (b1) and a vinyl monomer (b2) having a secondary amide group and / or a tertiary amide group in the presence of water and an emulsifier. An organic / inorganic composite composition obtained by
(2) The organic / inorganic composite composition as described in (1) above, wherein the polyfunctional silane (C) is a reaction product of aminosilane and isocyanate silane.
(3) The organic / inorganic composite composition as described in (1) above, wherein the polyfunctional silane (C) is a reaction product of polyamine and isocyanate silane.
(4) The organic / inorganic composite composition as described in (1) above, wherein the polyfunctional silane (C) is a reaction product of a polyol and an isocyanate silane.
(5) The organic / inorganic composite composition as described in (1) above, wherein the polyfunctional silane (C) is tris- (3-trialkoxysilylpropyl) isocyanurate.
(6) The organic / inorganic composite composition according to any one of (1) to (5), wherein the polymer emulsion particles (B) have a core / shell structure formed of two or more layers. object.
_{(7) TiO 2, ZnO,} SrTiO 3, BaTiO 3, BaTiO 4, BaTi 4 O 9, K 2 NbO 3, Nb 2 O 5, Fe 2 O 3, Ta 2 O 5, K 3 Ta 3 Si 2 O 3 , WO ₃ , SnO ₂ , Bi ₂ O ₃ , BiVO ₄ , NiO, Cu ₂ O, RuO ₂ , CeO ₂ , a metal oxide (D) having a photocatalytic activity, and inorganic oxide particles The organic / inorganic composite composition according to any one of (1) to (6) above, comprising (A).
(8) An aqueous composition comprising the organic / inorganic composite composition according to any one of (1) to (7) above.
(9) An organic / inorganic composite comprising a solid content of the composition according to any one of (1) to (8) above.
(10) An organic / inorganic composite comprising the solid content of the composition according to any one of (1) to (8) above.
(11) A continuous layer is formed in a state where the shell phase of the inorganic oxide particles (A) and the core / shell structured polymer emulsion particles (B) interacts, and the particulate core phase is present in the continuous layer. The organic / inorganic composite according to (9) or (10) above.
(12) A functional composite having the organic / inorganic composite according to any one of (9) to (11) above on a substrate.
(13) The functional complex according to (12), wherein the substrate is an organic substrate.
(14) The functional composite according to (12), wherein the base material is a resin base material.
(15) The functional composite according to any one of (12) to (14), wherein the functional composite is a functional composite for building exterior.

  The organic / inorganic composite composition of the present invention has excellent weather resistance, chemical resistance, optical properties, antifouling properties, antifogging properties, antistatic properties, etc., without using organic solvents or special equipment. Organic / inorganic composites can be formed.

Hereinafter, the present invention will be described in detail.
The organic / inorganic composite composition of the present invention is characterized by comprising inorganic oxide particles (A), polymer emulsion particles (B), and polyfunctional silane (C). The inorganic oxide particles (A) improve the contamination resistance of the organic / inorganic composite formed from the organic / inorganic composite composition due to the hydrophilicity of the hydroxyl group on the particle surface. The polymer emulsion particles (B) impart flexibility to the organic / inorganic composite, and make it difficult to cause cracks particularly when a film is formed on an organic substrate. Since only the inorganic oxide particles (A) and the polymer emulsion particles (B) do not provide sufficient chemical resistance, the polyfunctional silane (C) is used, while maintaining stain resistance and flexibility. Improve chemical properties.
In the organic / inorganic composite composition of the present invention, the inorganic oxide particles (A), the polymer emulsion particles (B), and the polyfunctional silane (C) interact with each other to provide weather resistance, chemical resistance, and optical properties. In addition, it is possible to form an organic / inorganic composite having excellent antifouling properties, antifogging properties, antistatic properties and the like.

  Here, the interaction includes condensation between hydroxyl groups and hydrogen bonds, and condensation between hydroxyl groups and hydrolyzable groups of the inorganic oxide particles (A), the polymer emulsion particles (B) and the polyfunctional silane (C). Can be mentioned. When the polymer emulsion particles (B) have functional groups capable of forming hydrogen bonds such as secondary and / or tertiary amide groups and hydroxyl groups, these functional groups and the inorganic oxide particles (A) Examples thereof include a hydrogen bond between a hydroxyl group. Moreover, when polyfunctional silane has a urea group and / or a urethane group, the hydrogen bond of those functional groups and the functional group which inorganic oxide particle (A) and polymer emulsion particle (B) have is mentioned.

  Examples of inorganic oxide particles (A) that can be suitably used in the present invention include silicon oxide (silica), aluminum oxide (alumina), calcium silicate, magnesium oxide, antimony oxide, zirconium oxide, and composite oxides thereof. Can be used. Among them, silicon oxide, aluminum oxide, antimony oxide, and composite oxides thereof having a large number of surface hydroxyl groups are preferable, and colloidal silica that is a dispersion of water or water-soluble solvent of silica based on silicon dioxide is more preferable. preferable.

  Colloidal silica can be prepared and used by a sol-gel method, and a commercially available product can also be used. For preparation by the sol-gel method, Werner Stober et al; Colloid and Interface Sci. , 26, 62-69 (1968), Rickey D .; Badley et al; Lang muir 6, 792-801 (1990), Color Material Association Journal, 61 [9] 488-493 (1988), and the like.

The inorganic oxide particles (A) preferably have a particle size of 1 to 400 nm, more preferably 1 to 100 nm, still more preferably 5 to 50 nm, and most preferably 8 to 20 nm. When the particle diameter is 1 nm or more, the storage stability of the coating liquid is good, and when it is 400 nm or less, the transparency is good.
When colloidal silica is used as the inorganic oxide particles (A), the colloidal silica having a particle diameter in the above range can be used in the state of an aqueous dispersion, whether acidic or basic. It can select suitably according to the stable area | region of emulsion particle | grains (B) and / or polyfunctional silane (C). From the viewpoint that the hydrolysis and / or condensation reaction of the polyfunctional silane (C) is gentle and the organic / inorganic composite composition is easy to handle, acidic colloidal silica is preferable.

Examples of the acidic colloidal silica using water as a dispersion medium include, as commercial products, Snowtex (trademark) -O manufactured by Nissan Chemical Industries, Ltd., Snowtex-OS, Adelite (trademark) AT- manufactured by Asahi Denka Kogyo Co., Ltd. 20Q, Clariant Japan Co., Ltd. clebosol (trademark) 20H12, clebosol 30CAL25, etc. can be used.
Examples of basic colloidal silica include silica stabilized by addition of alkali metal ions, ammonium ions, and amines. For example, SNOWTEX-20, SNOWTEX-30, SNOWTEX-C, and SNOWTEX-C manufactured by Nissan Chemical Industries, Ltd. Tex-C30, Snotex-CM40, Snotex-N, Snotex-N30, Snotex-K, Snotex-XL, Snotex-YL, Snotex-ZL, Snotex PS-M, Snotex PS-L Adelite AT-20, Adelite AT-30, Adelite AT-20N, Adelite AT-30N, Adelite AT-20A, Adelite AT-30A, Adelite AT-40, Adelite AT-50, etc. manufactured by Asahi Denka Kogyo Co., Ltd. Clariant Japan Co., Ltd. Kurebozoru 30R9, Kurebozoru 30R50, such Kurebozoru 50R50, DuPont Ludox (TM) HS-40, Ludox HS-30, Ludox LS, and the like Ludox SM-30.

Examples of colloidal silica using a water-soluble solvent as a dispersion medium include MA-ST-M (methanol dispersion type having a particle size of 20 to 25 nm), IPA-ST (particle size of 10) manufactured by Nissan Chemical Industries, Ltd. ˜15 nm isopropyl alcohol dispersion type), EG-ST (ethylene glycol dispersion type with particle diameter of 10 to 15 nm), EG-ST-ZL (ethylene glycol dispersion type with particle diameter of 70 to 100 nm), NPC-ST (particles) And ethylene glycol monopropyl ether dispersion type having a diameter of 10 to 15 nm).
These colloidal silicas may be used alone or in combination. As a minor component, alumina, sodium aluminate or the like may be contained. Colloidal silica may contain an inorganic base (such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or ammonia) or an organic base (such as tetramethylammonium) as a stabilizer.

In producing the polymer emulsion particles (B) of the present invention, it is preferable to use a hydrolyzable silicon compound (b1). Examples of the hydrolyzable silicon compound (b1) include compounds represented by the following formula (2), condensation products thereof, and silane coupling agents.
SiW _x R _y (2)
(In the formula, W represents an alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, an acetoxy group having 1 to 20 carbon atoms, a halogen atom, a hydrogen atom, an oxime group having 1 to 20 carbon atoms, an enoxy group, an aminoxy group, and an amide group. Represents at least one selected group, wherein R represents a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, and an unsubstituted or carbon atom. It represents at least one hydrocarbon group selected from an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom, where x is 1 or more and 4; And y is an integer of 0 or more and 3 or less, and x + y = 4.)
Here, the silane coupling agent is a hydrolyzable silicon compound in which a functional group having reactivity with an organic substance such as a vinyl polymerizable group, an epoxy group, an amino group, a methacryl group, a mercapto group, or an isocyanate group exists in the molecule. Represents (b1).

Specific examples of the silicon alkoxide and silane coupling agent include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane; Methoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane, n -Butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysilane Vinyltriethoxysilane, allyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3, 3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2- Hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltrimethoxysilane Toxisilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycid Xylpropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (Meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyltri-n-propoxysilane, 3- (meth) acryloyloxypropyltriisopropoxysilane, 3-ureidopropylto Trialkoxysilanes such as limethoxysilane and 3-ureidopropyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldi Ethoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n- Hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n - Dialkoxysilanes such as cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane; trimethylmethoxysilane, trimethylethoxysilane, etc. And monoalkoxysilanes. These silicon alkoxides and silane coupling agents can be used alone or in admixture of two or more.

When the silicon alkoxide or silane coupling agent is used as a condensation product, the condensation product preferably has a polystyrene equivalent weight average molecular weight of 200 to 5,000, more preferably 300 to 1,000.
Among the silicon alkoxides, tetrafunctional silicon alkoxides are preferably used, and tetramethoxysilane and tetramethoxysilane having a high hydrolysis rate are more preferable.
Also, silicon alkoxides having a phenyl group, such as phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, etc. are very preferable because of excellent polymerization stability in the presence of water and an emulsifier.

Among the hydrolyzable silicon compounds (b1) that can be used in the present invention, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloyl Oxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltri-n-propoxysilane, 3- (meth) acryloyloxypropyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, 2- Silane coupling agents having a vinyl polymerizable group such as trimethoxysilylethyl vinyl ether, and silane coupling agents having a thiol group such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane will be described later. By copolymerization or chain transfer reaction with vinyl monomer (b2) or the like having a secondary and / or tertiary amide group it is possible to generate a chemical bond. For this reason, when a silane coupling agent having a vinyl polymerizable group or a thiol group is used alone or mixed with or complexed with the above-described silicon alkoxide, silane coupling agent, and their condensation products, the present invention. The polymer product of the hydrolyzable silicon compound (b1) constituting the polymer emulsion particles (B) and the polymer product such as the vinyl monomer (b2) having a secondary and / or tertiary amide group are hydrogen. In addition to bonds, they can be combined by chemical bonds. The organic / inorganic composite composition of the present invention containing such polymer emulsion particles (B) can form an organic / inorganic composite having excellent weather resistance, chemical resistance, optical properties, strength, and the like. Therefore, it is very preferable.

In the present invention, it is particularly preferable from the viewpoint of weather resistance to use a silane coupling agent having a vinyl polymerizable group as the hydrolyzable silicon compound (b1), and the blending amount thereof is 100 parts by mass of the polymer emulsion particles (B). On the other hand, it is preferably from 0.01 to 20 parts by mass from the viewpoint of polymerization stability. More preferably, it is 0.1 to 10 parts by mass.
Moreover, the compounding quantity of the silane coupling agent which has a vinyl polymerizable group is 0.1-100 mass parts with respect to 100 mass parts of vinyl monomers (b2) which have a secondary and / or tertiary amide group. It is preferable from the viewpoint of polymerization stability, and more preferably 0.5 to 50 parts by mass.

In the present invention, a cyclic siloxane oligomer can be used in combination with the hydrolyzable silicon compound (b1) described above. By using the cyclic siloxane oligomer in combination, an organic / inorganic composite having excellent flexibility and the like can be formed from the organic / inorganic composite composition of the present invention.
As said cyclic siloxane oligomer, the compound represented by following formula (3) can be illustrated.
(R ′ ₂ SiO) _m (3)
(In the formula, R ′ is a hydrogen atom, a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, and an unsubstituted or substituted carbon atom having 1 to 30 carbon atoms. It represents at least one selected from an alkyl group having 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom, m is an integer, and 2 ≦ m ≦ 20 is there.)
Among the cyclic siloxane oligomers, cyclic dimethylsiloxane oligomers such as octamethylcyclotetrasiloxane are preferable from the viewpoint of reactivity.

In the present invention, titanium alkoxide, zirconium alkoxide, a condensation product thereof, or a chelated product thereof can be used in combination with the hydrolyzable silicon compound (b1) described above. By using these compounds in combination, an organic / inorganic composite excellent in water resistance, hardness and the like can be formed from the organic / inorganic composite composition of the present invention.
Specific examples of the titanium alkoxide include, for example, tetramethoxy titanium, tetraethoxy titanium, tetra-i-propoxy titanium, tetra-n-propoxy titanium, tetra-n-butoxy titanium, tetra-sec-butoxy titanium, tetra-tert. -Butoxy titanium etc. are mentioned.
When the titanium alkoxide is used as a condensation product, the weight average molecular weight in terms of polystyrene of the condensation product is preferably 200 to 5,000, more preferably 300 to 1,000.

Specific examples of the zirconium alkoxide include tetramethoxy zirconium, tetraethoxy zirconium, tetra-i-propoxy zirconium, tetra-n-propoxy zirconium, tetra-n-butoxy zirconium, tetra-sec-butoxy zirconium, tetra-tert. -Butoxyzirconium etc. are mentioned.
When the zirconium alkoxide is used as a condensation product, the weight average molecular weight in terms of polystyrene of the condensation product is preferably 200 to 5,000, more preferably 300 to 1,000.

  Further, as a preferable chelating agent for coordination with a free metal compound to form a chelate, alkanolamines such as diethanolamine and triethanolamine; glycols such as ethylene glycol, diethylene glycol and propylene glycol; acetylacetone; Examples thereof include ethyl acetoacetate having a molecular weight of 10,000 or less. By using these chelating agents, the polymerization rate of the hydrolyzable metal compound (b1) can be controlled, and this is very preferable in order to make the polymerization stability excellent in the presence of water and an emulsifier. In this case, the chelating agent is preferably used in a ratio of 0.1 mol to 2 mol per mol of the metal atom of the free metal compound that coordinates it.

  As a preferable production method of the polymer emulsion particles (B), a hydrolyzable silicon metal compound (b1) and a vinyl monomer (b2) having a secondary and / or tertiary amide group in the presence of water and an emulsifier. The method of polymerizing is exemplified. When such polymer emulsion particles (B) are used, the mechanical strength of the resulting organic / inorganic composite is further increased by hydrogen bonds formed between the amide groups and the hydroxyl groups of the inorganic oxide particles (A). It will be excellent. In addition, the amide group has high hydrophilicity and has an effect of lowering the water contact angle of the organic / inorganic composite.

At this time, the mass ratio (b2) / (b1) of the vinyl monomer (b2) having a secondary and / or tertiary amide group to the hydrolyzable silicon compound (b1) is 5/95 to 95/5, Preferably it is 10 / 90-90 / 10.
The polymer emulsion particles (B) thus obtained have a vinyl monomer (b2) having a silanol group and a secondary and / or tertiary amide group that the polymerization product of the hydrolyzable silicon compound (b1) has. ) Polymerization products are combined by hydrogen bonding.

  As the vinyl monomer (b2) having a secondary and / or tertiary amide group used for producing the polymer emulsion particles (B) of the present invention, N-alkyl or N-alkylene-substituted (meth) acrylamide is used. Specifically, for example, N-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N-ethylmethacrylamide, N-methyl-N-ethylacrylamide, N-methyl-N-ethylmethacrylamide, N-isopropylacrylamide, Nn-propylacrylamide, N-isopropylmethacrylamide, Nn-propylmethacrylamide N-methyl-Nn-propyl Pyracrylamide, N-methyl-N-isopropylacrylamide, N-acryloylpyrrolidine, N-methacryloylpyrrolidine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylhexahydroazepine, N-acryloylmorpholine, N-methacryloylmorpholine, N -Vinylpyrrolidone, N-vinylcaprolactam, N, N'-methylenebisacrylamide, N, N'-methylenebismethacrylamide, N-vinylacetamide, diacetone acrylamide, diacetone methacrylamide, N-methylol acrylamide, N-methylol And methacrylamide.

A vinyl monomer (b2) having a secondary and / or tertiary amide group is used to produce the polymer emulsion particles (B) of the present invention. Among them, a vinyl monomer having a tertiary amide group is used. And hydrogen bondability is preferred.
Among the vinyl monomers (b2) having the secondary and / or tertiary amide groups, N, N-diethylacrylamide is particularly excellent in polymerization stability in the presence of water and an emulsifier, and has been described above. Since it is possible to form a strong hydrogen bond with the hydroxyl group of the polymerization product of the hydrolyzable silicon compound (b1) and the hydroxyl group of the inorganic oxide particles (A), it is very preferable.
The amount of the vinyl monomer (b2) having a secondary and / or tertiary amide group is 0.1 or more as a mass ratio [(b2) / (B)] to the resulting polymer emulsion particles (B). It is preferable that it is 0.5 or less, and it is preferable that mass ratio (b2) / (A) with the inorganic oxide particle (A) mentioned above is 0.1 or more and 1.0 or less. When (b2) is present in this range, the hydrogen bonding force and the blending stability of the inorganic oxide particles (A) are preferably compatible.

Further, in the present invention, when the polymerization of the vinyl monomer (b2) having the secondary and / or tertiary amide group is carried out together with another vinyl monomer (b3) copolymerizable therewith, it is generated. It is possible to control the properties of the polymerized product (glass transition temperature, molecular weight, hydrogen bond strength, polarity, dispersion stability, weather resistance, compatibility with the polymerized product of hydrolyzable silicon compound (b1), etc.) preferable.
As the vinyl monomer (b3), in addition to acrylic acid ester, methacrylic acid ester, aromatic vinyl compound, vinyl cyanide, carboxyl group-containing vinyl monomer, hydroxyl group-containing vinyl monomer, epoxy group-containing Examples thereof include a monomer containing a functional group such as a vinyl monomer, a carbonyl group-containing vinyl monomer, and an anionic vinyl monomer.

Examples of the (meth) acrylic acid ester include (meth) acrylic acid alkyl ester having 1 to 50 carbon atoms in the alkyl portion, and (poly) oxyethylene di (meth) acrylate having 1 to 100 ethylene oxide groups. Etc. Specific examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and methyl (meth) acrylate. Examples include cyclohexyl, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, and the like. Specific examples of (poly) oxyethylene di (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, diethylene glycol methoxy (meth) acrylate, tetraethylene glycol di (meth) acrylate Etc.
In the present specification, (meth) acrylic is a simple description of methacrylic or acrylic.
The amount of the (meth) acrylic acid ester is preferably 0 to 99.9% by mass, more preferably 5 to 80% by mass in the total vinyl monomer as one or a mixture of two or more.

Examples of the carboxyl group-containing vinyl monomer include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, or half of a dibasic acid such as itaconic acid, maleic acid, and fumaric acid. Esters and the like. By using a carboxylic acid group-containing vinyl monomer, a carboxyl group can be introduced into the polymer emulsion particles (B), improving the stability as an emulsion, and having a resistance to dispersion and destruction from the outside. It is possible to have it. At this time, part or all of the introduced carboxyl group can be neutralized with an amine such as ammonia, triethylamine or dimethylethanolamine, or a base such as NaOH or KOH.
It is preferable from the surface of water resistance that the usage-amount of a carboxyl group-containing vinyl monomer is 0-50 mass% in all vinyl monomers as a 1 type, or 2 or more types of mixture. More preferably, it is 0.1-10 mass%, More preferably, it is 0.1-5 mass%.

Examples of the hydroxyl group-containing vinyl monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. Hydroxyalkyl esters of (meth) acrylic acid such as 3-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate, di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl monobutyl fumarate , (Poly) oxyethylene mono (meth) acrylate having 1 to 100 allyl alcohol or ethylene oxide groups, (poly) oxypropylene mono (meth) acrylate having 1 to 100 propylene oxide groups, "Placcel FM, FA Nomar "(manufactured by Daicel Chemical Industries, Ltd., trade name of caprolactone addition monomer) and other alpha, and the like hydroxyalkyl esters of β- ethylenically unsaturated carboxylic acid. Specific examples of the (poly) oxyethylene (meth) acrylate include ethylene glycol (meth) acrylate, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, diethylene glycol methoxy (meth) acrylate, (meth ) Tetraethylene glycol acrylate, tetraethylene glycol methoxy (meth) acrylate, and the like. Specific examples of (poly) oxypropylene (meth) acrylate include propylene glycol (meth) acrylate, propylene glycol methoxy (meth) acrylate, dipropylene glycol (meth) acrylate, dimethoxy meth (meth) acrylate. Examples include propylene glycol, tetrapropylene glycol (meth) acrylate, and tetrapropylene glycol methoxy (meth) acrylate. By using a hydroxyl group-containing vinyl monomer, it becomes possible to control the hydrogen bonding force of the polymerization product with the vinyl monomer (b2) having a secondary and / or tertiary amide group, and a polymer. It becomes possible to improve the water dispersion stability of the emulsion particles (B).
The use amount of the hydroxyl group-containing vinyl monomer described above is preferably 0 to 80% by mass, more preferably 0.1 to 50% by mass, and more preferably 0.1 to 50% by mass in the total vinyl monomer as one or a mixture of two or more. Preferably it is 0.1-10 mass%.

Examples of the glycidyl group-containing vinyl monomer include glycidyl (meth) acrylate, allyl glycidyl ether, and allyl dimethyl glycidyl ether.
When a glycidyl group-containing vinyl monomer or a carbonyl group-containing vinyl monomer is used, the polymer emulsion particles (B) are reactive and crosslinked with hydrazine derivatives, carboxylic acid derivatives, isocyanate derivatives, etc. It is possible to form an organic / inorganic composite having excellent properties. The amount of the glycidyl group-containing vinyl monomer or the carbonyl group-containing vinyl monomer used is preferably 0 to 50% by mass in the total vinyl monomers.

Specific examples of the vinyl monomer (b3) other than the above include, for example, (meth) acrylamide, olefins such as ethylene, propylene and isobutylene, dienes such as butadiene, vinyl chloride, vinylidene chloride vinyl chloride, tetra Haloolefins such as fluoroethylene and chlorotrifluoroethylene, vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl benzoate, vinyl pt-butylbenzoate, vinyl pivalate, vinyl 2-ethylhexanoate, versatic Carboxylic acid vinyl esters such as vinyl acid and vinyl laurate, isopropenyl acetate, isopropenyl carboxylic acid such as isopropenyl propionate, vinyl ethers such as ethyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, Aromatic vinyl compounds such as tylene and vinyltoluene, allyl esters such as allyl acetate and allyl benzoate, allyl ethers such as allyl ethyl ether and allyl phenyl ether, and 4- (meth) acryloyloxy-2,2,6 , 6, -tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6, -pentamethylpiperidine, perfluoromethyl (meth) acrylate, perfluoropropyl (meth) acrylate, perfluoropro Examples thereof include pyromethyl (meth) acrylate, vinyl pyrrolidone, trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate, and the like and combinations thereof.

In the present invention, polymerization of a vinyl monomer (b2) having a secondary and / or tertiary amide group (the vinyl monomer (b3) copolymerizable therewith may be used if necessary). A chain transfer agent may be used for the purpose of controlling the molecular weight of the product.
Examples of such chain transfer agents include alkyl mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan; aromatic mercaptans such as benzyl mercaptan and dodecyl benzyl mercaptan; thiocarboxylic acids such as thiomalic acid. Examples include acids or salts thereof or alkyl esters thereof, or polythiols, diisopropylxanthogen disulfide, di (methylenetrimethylolpropane) xanthogen disulfide and thioglycol, and allyl compounds such as dimers of α-methylstyrene. it can.
The amount of these chain transfer agents used is preferably 0.001 to 30% by mass, more preferably 0.05 to 10% by mass, based on the total vinyl monomer.

In the present invention, examples of the emulsifier that can be used for the synthesis of the polymer emulsion particles (B) include alkylbenzene sulfonic acid, alkyl sulfonic acid, alkyl sulfosuccinic acid, polyoxyethylene alkyl sulfuric acid, polyoxyethylene alkyl aryl sulfuric acid, poly Acidic emulsifiers such as oxyethylene distyryl phenyl ether sulfonic acid, alkali metal (Li, Na, K, etc.) salts of acidic emulsifiers, ammonium salts of acidic emulsifiers, anionic surfactants such as fatty acid soaps, and alkyltrimethylammonium bromides , Quaternary ammonium salts such as alkylpyridinium bromides and imidazolinium laurates, pyridinium salts, imidazolinium salt type cationic surfactants, polyoxyethylene alkylaryl ethers, polyoxyethylenes Nsorubitan fatty acid esters, polyoxyethylene polyoxypropylene block copolymers can be exemplified reactive emulsifier or the like having a nonionic surface active agent and a radical polymerizable double bond polyoxyethylene distyryl phenyl ether.
Among these emulsifiers, when a reactive emulsifier having a radical polymerizable double bond is selected, the water dispersion stability of the polymer emulsion particles (B) of the present invention becomes very good, and the polymer emulsion From the organic / inorganic composite composition of the present invention containing the particles (B), an organic / inorganic composite having excellent water resistance, chemical resistance, optical properties, strength, and the like can be formed. .

Examples of the reactive emulsifier having a radical polymerizable double bond include a vinyl monomer having a sulfonic acid group or a sulfonate group, a vinyl monomer having a sulfate ester group, an alkali metal salt thereof, an ammonium salt, Examples include vinyl monomers having a nonionic group such as oxyethylene, and vinyl monomers having a quaternary ammonium salt.
As a specific example of the reactive emulsifier, taking a vinyl monomer salt having a sulfonic acid group or a sulfonate group as an example, it has a radical polymerizable double bond, and is an ammonium salt or sodium salt of a sulfonic acid group. Or an alkyl group having 1 to 20 carbon atoms, an alkyl ether group having 2 to 4 carbon atoms, a polyalkyl ether group having 2 to 4 carbon atoms, a 6 or 10 carbon atom, partially substituted with a group that is a potassium salt It is a compound having a substituent selected from the group consisting of an aryl group and a succinic acid group, or a vinyl sulfonate compound having a vinyl group to which a group which is an ammonium salt, sodium salt or potassium salt of a sulfonic acid group is bonded. . The vinyl monomer having a sulfate ester group has a radically polymerizable double bond and is partially substituted with a group that is an ammonium salt, sodium salt or potassium salt of a sulfate ester group, having 1 to 1 carbon atoms. It is a compound having a substituent selected from the group consisting of 20 alkyl groups, alkyl ether groups having 2 to 4 carbon atoms, polyalkyl ether groups having 2 to 4 carbon atoms, and aryl groups having 6 or 10 carbon atoms.

Specific examples of the compound having a succinic acid group partially substituted with a group which is an ammonium salt, sodium salt or potassium salt of the sulfonic acid group include allylsulfosuccinate. Specific examples thereof include, for example, Eleminol JS-2 (trade name) (manufactured by Sanyo Kasei Co., Ltd.), Latemul S-120, S-180A or S-180 (trade name) (manufactured by Kao Corporation), and the like. Can be mentioned.
Further, a compound having an alkyl ether group having 2 to 4 carbon atoms or a polyalkyl ether group having 2 to 4 carbon atoms, which is partially substituted by a group which is an ammonium salt, sodium salt or potassium salt of the sulfonic acid group. As specific examples, for example, Aqualon HS-10 or KH-1025 (trade name) (Daiichi Kogyo Seiyaku Co., Ltd.), Adekaria Soap SE-1025N or SR-1025 (trade name) (Asahi Denka Kogyo Co., Ltd.) And the like.
Other specific examples of the compound having an aryl group partially substituted with a sulfonate group include ammonium salt, sodium salt and potassium salt of p-styrenesulfonic acid.

Examples of the vinyl sulfonate compound having a vinyl group to which a group of ammonium salt, sodium salt or potassium salt of the sulfonic acid group is bonded include, for example, alkyl sulfonic acid (meth) acrylate such as 2-sulfoethyl acrylate, and methylpropane sulfonic acid. Examples thereof include ammonium salts such as (meth) acrylamide and allyl sulfonic acid, sodium salts, and potassium salts.
Examples of the compound having an alkyl ether group having 2 to 4 carbon atoms or a polyalkyl ether group having 2 to 4 carbon atoms partially substituted with the ammonium salt, sodium salt or potassium salt of the sulfate ester group include, for example, Examples include compounds having an alkyl ether group partially substituted with a sulfonate group.

In addition, specific examples of vinyl monomers having a nonionic group include α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-hydroxypolyoxyethylene (trade name: ADEKA rear soap). NE-20, NE-30, NE-40, etc., manufactured by Asahi Denka Kogyo Co., Ltd.), polyoxyethylene alkylpropenyl phenyl ether (trade names: Aqualon RN-10, RN-20, RN-30, RN-50, etc.) , Manufactured by Daiichi Pharmaceutical Co., Ltd.).
As the usage-amount of the said emulsifier, the inside of the range used as 10 mass parts or less is suitable with respect to 100 mass parts of polymer emulsion particle | grains (B), Especially, within the range used as 0.001-5 mass parts. preferable.

In addition to the above emulsifiers, a dispersion stabilizer can also be used for the purpose of improving the water dispersion stability of the polymer emulsion particles (B) of the present invention. Examples of the dispersion stabilizer include various water-soluble oligomers selected from the group consisting of polycarboxylic acids and sulfonates, polyvinyl alcohol, hydroxyethyl cellulose, starch, maleated polybutadiene, maleated alkyd resin, polyacrylic acid (salt ), Synthetic or natural water-soluble or water-dispersible water-soluble polymer substances such as polyacrylamide, water-soluble or water-dispersible acrylic resin, etc., and one or a mixture of two or more of these are used. be able to.
When these dispersion stabilizers are used, the amount used is suitably within a range of 10 parts by mass or less with respect to 100 parts by mass of the polymer emulsion particles (B). The range of 5 parts by mass is preferable.

In the present invention, the polymerization of the hydrolyzable silicon compound (b1) and the vinyl monomer (b2) having a secondary and / or tertiary amide group is preferably carried out in the presence of a polymerization catalyst.
Here, as a polymerization catalyst for the hydrolyzable silicon compound (b1), hydrogen halides such as hydrochloric acid and hydrofluoric acid, carboxylic acids such as acetic acid, trichloroacetic acid, trifluoroacetic acid and lactic acid, sulfuric acid,
Sulfonic acids such as p-toluenesulfonic acid, acidic emulsifiers such as alkylbenzene sulfonic acid, alkyl sulfonic acid, alkyl sulfosuccinic acid, polyoxyethylene alkyl sulfuric acid, polyoxyethylene alkyl aryl sulfuric acid, polyoxyethylene distyryl phenyl ether sulfonic acid, Acidic or weakly acidic inorganic salts, acidic compounds such as phthalic acid, phosphoric acid, nitric acid; sodium hydroxide, potassium hydroxide, sodium methylate, sodium acetate, tetramethylammonium chloride, tetramethylammonium hydroxide, tributylamine , Diazabicycloundecene, ethylenediamine, diethylenetriamine, ethanolamines, γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane And basic compounds such as: Tin compounds such as dibutyltin octylate and dibutyltin dilaurate.
Among these, as a polymerization catalyst for the hydrolyzable silicon compound (b1), acidic emulsifiers having an action as an emulsifier as well as a polymerization catalyst, particularly alkylbenzenesulfonic acid (dodecylbenzenesulfonic acid having 5 to 30 carbon atoms). Etc.) is highly preferred.

  On the other hand, as a polymerization catalyst for the vinyl monomer (b2) having a secondary and / or tertiary amide group, a radical polymerization catalyst that causes radical polymerization by heat or a reducing substance to cause addition polymerization of the vinyl monomer And water-soluble or oil-soluble persulfates, peroxides, azobis compounds and the like are used. Examples include potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, 2,2-azobisisobutyronitrile, 2,2-azobis. (2-diaminopropane) hydrochloride, 2,2-azobis (2,4-dimethylvaleronitrile), etc., and the amount thereof is 0.001 to 5 parts by mass with respect to 100 parts by mass of the total vinyl monomer. Is preferable. When acceleration of the polymerization rate and polymerization at a low temperature of 70 ° C. or lower are desired, it is advantageous to use a reducing agent such as sodium bisulfite, ferrous chloride, ascorbate, or longalite in combination with the radical polymerization catalyst. is there.

As described above, the polymer emulsion particles (B) used in the organic / inorganic composite composition of the present invention are hydrolyzable silicon compound (b1) and secondary and / or tertiary amide groups in the presence of water and an emulsifier. A vinyl monomer (b2) having a hydrogen atom (other vinyl monomer (b3) copolymerizable therewith may be used if necessary), preferably by polymerizing in the presence of a polymerization catalyst. Can do.
Here, the polymerization of the hydrolyzable silicon compound (b1) and the vinyl monomer (b2) having a secondary and / or tertiary amide group can be carried out separately, but by carrying out at the same time. This is preferable because a micro organic / inorganic composite by hydrogen bonding or the like can be achieved.

In the present invention, it is important that the particle diameter of the polymer emulsion particles (B) is 10 to 800 nm. By adjusting to such a particle size range and combining with inorganic oxide particles (A) having a particle size of 1 to 400 nm to form an organic / inorganic composite composition, weather resistance, chemical resistance, optical properties, Furthermore, it becomes possible to form an organic / inorganic composite having excellent antifouling properties, antifogging properties, antistatic properties and the like. Moreover, it is more preferable that the particle diameter of the polymer emulsion particles (B) is 50 to 300 nm because the transparency of the obtained coating film is improved.
As a method for obtaining the polymer emulsion particles (B) having such a particle size, the hydrolyzable metal compound (b1) and the secondary and / or 3 in the presence of a sufficient amount of water for the emulsifier to form micelles. So-called emulsion polymerization in which the vinyl monomer (b2) having a secondary amide group is polymerized is the most suitable method.

Examples of the emulsion polymerization include hydrolyzable silicon compound (b1) and vinyl monomer (b2) having a secondary and / or tertiary amide group (other vinyls copolymerizable therewith if necessary). The monomer (b3)) is dropped into the reaction vessel as it is or in an emulsified state, all at once, in a divided manner or continuously, and in the presence of the polymerization catalyst, preferably from atmospheric pressure to 1 if necessary.
What is necessary is just to superpose | polymerize at the reaction temperature of about 30-150 degreeC under the pressure of 0 Mpa. In some cases, the polymerization may be carried out at a higher pressure or lower temperature. The ratio of the total amount of hydrolyzable silicon compound (b1) and all vinyl monomers to water is set so that the final solid content is in the range of 0.1 to 70% by mass, preferably 1 to 55% by mass. Is preferred. Further, in order to grow or control the particle diameter in carrying out emulsion polymerization, a seed polymerization method in which emulsion particles are preliminarily present in an aqueous phase may be used. The polymerization reaction may be allowed to proceed in the range of pH in the system of preferably 1.0 to 10.0, more preferably 1.0 to 6.0. The pH can be adjusted using a pH buffer such as disodium phosphate, borax, sodium hydrogen carbonate, or ammonia.

  As a method for obtaining the polymer emulsion particles (B) of the present invention, the hydrolyzable metal compounds (b1) and 2 in the presence of water and an emulsifier necessary for polymerizing the hydrolyzable silicon compound (b1). Although the vinyl monomer (b2) having a tertiary and / or tertiary amide group is polymerized in the presence of a solvent, if necessary, water may be added until the polymerization product becomes an emulsion. Compared with the polymerization method, it is difficult to control the particle diameter of the resulting polymer emulsion particles (B).

  In the present invention, when the polymer emulsion particles (B) have a core / shell structure formed of two or more layers, the organic / inorganic composite composition containing the polymer emulsion particles (B) An organic / inorganic composite having excellent physical properties (balance of strength and flexibility, etc.) can be formed, which is preferable. In particular, the mass ratio (b2) / (b1) of the vinyl monomer (b2) having a secondary and / or tertiary amide group to the hydrolyzable silicon compound (b1) forming the innermost layer is 1.0 or less. When the mass ratio (b2) / (b1) between (b2) and (b1) forming the outermost layer is 0.1 or more and 5.0 or less, the resulting composite has weather resistance and mechanical properties. Are particularly good and preferred.

Multi-stage emulsion polymerization is very useful as a method for producing the core / shell structured polymer emulsion particles (B).
Here, the multi-stage emulsion polymerization means two or more different hydrolyzable silicon compounds (b1) and vinyl monomers (b2) having secondary and / or tertiary amide groups (if necessary, this It is meant that other vinyl monomers (b3)) that can be copolymerized with are prepared and polymerized in separate stages.

Hereinafter, the synthesis of the polymer emulsion particles (B) by the multistage emulsion polymerization of the present invention will be described by taking the synthesis of the polymer emulsion particles (B) by the simplest and useful two-stage emulsion polymerization as an example. To do.
In the present invention, as the synthesis of the polymer emulsion particles (B) by two-stage emulsion polymerization, for example, the vinyl monomer (C) and / or the hydrolyzable silicon compound (b1) is polymerized in the presence of water and an emulsifier. Examples thereof include a method of polymerizing the hydrolyzable silicon compound (b1) and the vinyl monomer (b2) having a secondary and / or tertiary amide group in the presence of the obtained seed particles.
Here, the vinyl monomer (C) means a vinyl monomer (b2) having a secondary and / or tertiary amide group and / or the other vinyl monomer (b3) described above.

The synthesis of the polymer emulsion particles (B) by the above two-stage emulsion polymerization is the first stage in which emulsion polymerization is performed by supplying the first series (vinyl monomer (C) and / or hydrolyzable metal compound (b1)). And the second series (hydrolyzable metal compound (b1) and vinyl monomer (b2) having secondary and / or tertiary amide group (copolymerized with this if necessary) The other possible vinyl monomer (b3))) is supplied, and this is carried out by a two-stage polymerization process comprising a second stage polymerization in which emulsion polymerization is carried out in an aqueous medium. At this time, the mass ratio of the solid content mass (M1) in the first series and the solid content mass (M2) in the second series is preferably (M1) / (M2) = 9/1 to 1/9.
More preferably, it is 8/2 to 2/8.

In the present invention, the preferred core / shell structure polymer is characterized in that the particle size of the seed particles obtained by the first stage polymerization is not greatly changed in the particle size distribution (volume average particle size / number average particle size). (Preferably in a monodispersed state) can be increased by the second stage polymerization (increase in particle diameter).
The core / shell structure can be confirmed by, for example, morphological observation with a transmission electron microscope, analysis by viscoelasticity measurement, or the like.

In the presence of seed particles obtained by polymerizing the polymer emulsion particles (B) with the hydrolyzable silicon compound (b1) in the presence of water and an emulsifier, the hydrolyzable silicon compound (b1) and the secondary and / or Polymerization of the vinyl monomer (b2) having a tertiary amide group is preferred because of excellent polymerization stability.
In the above-described polymer emulsion particles (B) having a core / shell structure, the glass transition temperature (Tg) of the core phase is 0 ° C. or lower, that is, the glass transition temperature of the seed particles is 0 ° C. or lower. From the organic / inorganic composite composition to be contained, it is possible to form an organic / inorganic composite that is excellent in flexibility at room temperature and hardly cracks.
In the present invention, when carrying out multi-stage emulsion polymerization of three or more stages, the number of series to be polymerized may be increased with reference to the synthesis example of the polymer emulsion particles (B) by the two-stage polymerization described above.
A vinyl monomer having an amide group can also be obtained by using a vinyl monomer capable of forming a hydrogen bond with the inorganic oxide particles (A), such as a hydroxyl group-containing vinyl monomer or a carboxyl group-containing vinyl monomer. The same effect as when the monomer (b1) is used can be obtained.

The polyfunctional silane (C) in the present invention is characterized by having 3 to 20 atomic groups (c1) represented by the following formula (4) in one molecule.
R ¹ _n SiX _3-n A- (4)
{Wherein R ¹ represents hydrogen or an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, or an aryl group. Moreover, you may have functional groups, such as a halogen group, a hydroxy group, a mercapto group, an amino group, a (meth) acryloyl group, an epoxy group, on these substituents. X represents a hydrolyzable group, and n is an integer of 0-2. A is a site containing 2 to 20 methylene groups and may have a substituent. }

When there are three or more atomic groups (c1) in one molecule, the hydrophilicity of the organic / inorganic composite formed from the organic / inorganic composite composition of the present invention is increased, and the antifouling property is improved. Moreover, when the atomic group (c1) is 20 or less, the mixing stability with the inorganic oxide particles (A) and the polymer emulsion particles (B) becomes good. The number of atomic groups (c1) is more preferably 3 to 10, more preferably 3 to 5, and most preferably 3 to 4.
The larger the number of hydrolyzable groups X bonded to the silicon atom of the atomic group (c1), the higher the hydrophilicity of the organic / inorganic composite formed from the organic / inorganic composite composition, and the antifouling property is improved. . Further, the smaller the number of X, that is, the larger the number of R ¹ , the more flexible the organic / inorganic composite.

The hydrolyzable group is not particularly limited as long as it is a conventionally known hydrolyzable group. Specific examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable. Particularly preferred.
More specific examples of the alkoxy group include a methoxy group, an ethoxy group, and an isopropoxy group. A methoxy group and an ethoxy group are more preferable, and a methoxy group is particularly preferable because of high activity and good curability.

Here, the atomic group (c1) has a portion A containing 2 to 20 methylene groups in order to control flexibility in the organic / inorganic composite composition. The site A may have a substituent, and a hetero atom other than silicon (for example, nitrogen, oxygen, and sulfur) may be included between the methylene groups. By including a methylene group, flexibility is imparted. From the viewpoint of flexibility, it is preferable that the methylene groups are directly bonded and the number thereof is larger, and the substituents of the methylene group are preferably smaller. Examples of the site A include an ethylene group, a propylene group, a butylene group, and an isobutylene group.
If the number of methylene groups at site A is 2 or more, the flexibility of the organic / inorganic composite is good, and if it is 20 or less, inorganic oxide particles (A) and polymer emulsion particles (B) The mixing stability of is improved. More preferably, the number of methylene groups is 3-10, more preferably 3-5, and most preferably 3.

Sites other than the atomic group (c1) of the polyfunctional silane (C) are not particularly limited, and examples include isocyanurate groups, biuret groups, urethane groups, and urea groups. An isocyanurate group is preferable because the resulting organic / inorganic composite has high hardness.
Examples of the polyfunctional silane (C) having an isocyanurate group include tris- (3-trialkoxysilylpropyl) isocyanurate, specifically, tris- (3-trimethoxysilylpropyl) isocyanurate, tris- (3-triethoxysilylpropyl) isocyanurate and the like.
Examples of other polyfunctional silanes (C) include compounds obtained by reacting aminosilane and isocyanate silane, compounds obtained by reacting polyamine and isocyanate silane, and compounds obtained by reacting polyol and isocyanate silane. It can be produced by reacting in the same manner as in ordinary polyurethane production.

When the polyfunctional silane (C) of the present invention has a urea group and / or a urethane group, the interaction with the inorganic oxide particles (A) and the polymer emulsion particles (B) is strengthened, and the organic / inorganic composite composition The film formability is improved. Moreover, the dispersibility of polyfunctional silane (C) and its hydrolyzate or hydrolysis condensate is also improved.
When manufacturing polyfunctional silane (C) from aminosilane and isocyanate silane, it can carry out by stirring at 20-40 degreeC, for example, 30 degreeC. Further, if necessary, a urethanization catalyst such as an organic tin compound, organic bismuth, or amine can be used.

  The aminosilane is preferably an aminoalkoxysilane having a primary or secondary amino group. For example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ -Aminopropylmethyldiethoxysilane, aminophenyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropylmethyldimethoxysilane, N- (n-butyl) -γ-aminopropyl Trimethoxysilane, N- (n-butyl) -γ-aminopropylmethyldimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, N-methylaminopropylmethyldimethoxysilane, N-methylaminopropyltrimethoxysilane, bis (to Rimethoxysilylpropyl) amine, bis (triethoxysilylpropyl) amine, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, Examples thereof include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, and the like.

Examples of the isocyanate silane include isocyanate propyl trimethoxy silane, isocyanate propyl triethoxy silane, isocyanate methyl trimethoxy silane, and isocyanate methyl triethoxy silane.
The polyamine is preferably a triamine or higher polyamine, and examples thereof include melamine, diethylenetriamine, triethylenetetramine, and tri (aminomethyl) propane.
As the polyol, a tri- or higher functional polyol is preferable, and examples thereof include trimethylolpropane, glycerin, pentaerythritol, ditrimethylolpropane, and the like.
For example, when polyfunctional silane (C) is produced from bis (trimethoxysilylpropyl) amine and isocyanatepropyltriethoxysilane, polyfunctional silane (C) of the following formula (5) is obtained.

The polyfunctional silane (C) of this invention can be used individually or in mixture of 2 or more types.
The content of the polyfunctional silane (C) in the present invention (completely hydrolyzed reduced weight, the same applies hereinafter) is preferably 1 to 99 parts by weight among the organic / inorganic composite composition and the total amount of 100 parts by weight. . If it is 1 part by weight or more, the hardness and solvent resistance of the formed organic / inorganic composite will be good, and if it is 99 parts by weight or less, cracks will occur when the organic / inorganic composite is formed on the resin substrate. Is less likely to occur. More preferable content is 2-50, More preferably, it is 5-30, Most preferably, it is 8-20. Here, the complete hydrolysis-condensation reduced weight means the weight when the hydrolyzable group of the polyfunctional silane (C) is hydrolyzed to 100% to be a SiOH group, and is further completely condensed to a siloxane.

When forming an organic / inorganic composite having a film thickness of 0.3 to 1.5 μm on the substrate from the inorganic oxide particles (A) and the polymer emulsion particles (B) without using the polyfunctional silane (C), Interference patterns are conspicuous and tend to be poor in appearance. This is presumably because voids are formed between the inorganic oxide particles of the organic / inorganic composite and the refractive index is lower than that of the substrate. Therefore, interference patterns can be made inconspicuous by using polyfunctional silane (C) and filling the gaps between the inorganic oxide particles. By changing the content ratio (C) / (A) of the inorganic oxide particles (A) and the polyfunctional silane (C) according to the refractive index of the substrate, it is possible to suppress the interference pattern.
When the organic / inorganic composite is formed on the resin substrate, the preferable range of (C) / (A) is 10/100 to 200/100, more preferably 20/100 to 100/100, and still more preferably. Is 30 / 100-60 / 100.

In the organic / inorganic composite composition of the present invention, the inorganic oxide particles (A) and / or polymer emulsion particles (B) and the polyfunctional silane (C) are dispersed and dissolved in a dispersion medium to cause a hydrolysis reaction. It is preferable to perform a condensation reaction. Here, the dispersion medium to be used is one in which the inorganic oxide particles (A) and / or the polymer emulsion particles (B) are substantially stably dispersed, and the polyfunctional silane (C) and other additives described later are dissolved. If it is, it will not be specifically limited. Moreover, even when polyfunctional silane (C) does not melt | dissolve, what is necessary is just a dispersion medium in which the hydrolyzate and / or hydrolysis condensate of polyfunctional silane (C) melt | dissolve.

Specifically, water, monohydric alcohol having 1 to 6 carbon atoms, dihydric alcohol having 1 to 6 carbon atoms, alcohols such as glycerin, formamide, N-methylformamide, N-ethylformamide, N, N -Amides such as dimethylformamide, N, N-diethylformamide, N-methylacetamide, N-ethylacetamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methylpyrrolidone, tetrahydrofuran, diethyl ether, di (N-propyl) ether, diisopropyl ether, diglyme, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol Ethers such as dimethyl ether, ethyl formate, methyl acetate, ethyl acetate, ethyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol diacetate, propylene glycol monomethyl ether acetate, esters such as diethyl carbonate, ethylene carbonate, propylene carbonate, acetone, Ketones such as methyl ethyl ketone, methyl propyl ketone, methyl (n-butyl) ketone, methyl isobutyl ketone, methyl amyl ketone, cyclopentanone and cyclohexanone, and nitriles such as acetonitrile, propionitrile, n-butyronitrile and isobutyronitrile , Dimethyl sulfoxide, dimethyl sulfone, sulfolane and the like are preferably used. These dispersion media may be mixed or mixed with other arbitrary dispersion media or additives as long as the object of the present invention is not impaired.
More preferable dispersion media are water, monohydric alcohols having 1 to 6 carbon atoms, or alkanol ethers such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether, and mixtures thereof.

The coating composition of the present invention preferably contains a catalyst for the purpose of promoting the hydrolysis / dehydration condensation reaction of the polyfunctional silane (C). Examples of the catalyst include an acidic catalyst, an alkaline catalyst, and an organic tin compound. In particular, acidic catalysts are preferable, and examples thereof include mineral acids such as nitric acid and hydrochloric acid, and organic acids such as oxalic acid and acetic acid.
The amount of the acid as the catalyst is preferably contained in the organic / inorganic composite composition at a concentration of 0.0008 mol / liter or more, and more preferably at a concentration of 0.0008 to 1 mol / liter or more. If it is 0.0008 mol / liter or more, the hydrolysis / dehydration condensation reaction of the polyfunctional silane (C) proceeds sufficiently, and the hardness and solvent resistance are improved. On the other hand, by making 1 mol / liter or less, the stability of the inorganic oxide particles (A) and / or the polymer emulsion particles (B) becomes good.

When the organic / inorganic composite composition of the present invention contains an alkaline earth metal salt, the coating performance on various substrates can be improved, and the strength of the organic / inorganic composite can be further increased. It is preferable because it is possible. As the alkaline earth metal salt, for example, chlorides such as magnesium, calcium, strontium and barium, inorganic acid salts such as nitrates, sulfates, formates and acetates, and organic acid salts are preferable. Of these, inorganic salts and organic acid salts of magnesium and calcium are particularly preferable. Moreover, the said alkaline-earth metal salt can be used individually or in mixture of 2 or more types.
The alkaline earth metal salt is preferably in the range of 0.001 to 0.1, more preferably 0.005 to 0.05, in terms of molar ratio to the silicon atoms contained in the organic / inorganic composite composition. It is.

  Regarding the mixing method of the polyfunctional silane (C), after the hydrolysis / dehydration condensation reaction of the polyfunctional silane (C) is performed in advance, the polyfunctional silane (C) is mixed with the inorganic oxide particles (A) and / or the polymer emulsion particles (B). However, it is preferable to conduct the hydrolysis / dehydration condensation reaction in a state where the inorganic oxide particles (A) and / or the polymer emulsion particles (B) and the polyfunctional silane (C) coexist. More preferably, the polyfunctional silane (C) is added to the mixture of the inorganic oxide particles (A) and the polymer emulsion particles (B) to perform a hydrolysis / condensation reaction.

Specifically, the inorganic oxide particles (A) and / or polymer emulsion particles (B) and the polyfunctional silane (C) are mixed, and additives such as water and catalyst are added as necessary. Silane (C) is hydrolyzed and dehydrated.
The higher the reaction temperature at which hydrolysis and dehydration condensation is performed, the faster the reaction proceeds, which is preferable in terms of productivity.However, if the reaction is too early, dehydration condensation proceeds too much and the viscosity of the coating composition increases and the substrate in the coating process increases. The temperature at which the hydrolysis / dehydration condensation is usually performed is a temperature at which the viscosity of the coating composition can be easily controlled, specifically 20 to 100 ° C., preferably 20 to 60 ° C., more preferably 20 to 40 ° C. When the hydrolysis / dehydration condensation is performed at the above temperature, the time required is at least 1 hour at 20 ° C., and at least 20 minutes at 60 ° C.
When performing the hydrolysis / dehydration condensation reaction as described above, it is preferable that the catalyst and water further coexist. The kind of catalyst used and the amount of catalyst and water are as described above.

In the present invention, the polyfunctional silane (C) is hydrolyzed and dehydrated in the presence of the inorganic oxide particles (A) and / or the polymer emulsion particles (B), whereby the inorganic oxide particles (A) and Alternatively, the surface of the polymer emulsion particles (B) is modified with the polyfunctional silane (C). The inorganic oxide particles (A), the polymer emulsion particles (B), and the inorganic oxide particles (A) and the polymer are formed by condensation of silanol derived from the polyfunctional silane (C) during the formation of the organic / inorganic composite. Since the emulsion particles (B) are combined, it is considered that the hardness and solvent resistance can be improved. Therefore, compared with the case where the polyfunctional silane (C) is previously hydrolyzed and dehydrated and condensed with the inorganic oxide particles (A) and / or the polymer emulsion particles (B), the organic An inorganic composite can be formed.
Furthermore, an alkaline earth metal salt as described above and various additives are added as necessary to obtain an organic / inorganic composite composition. These alkaline earth metal salts and additives may be added before the hydrolysis / dehydration condensation reaction, or may be added later.

As long as the characteristics of the present invention are not impaired, hydrolyzable silicon compounds represented by the following general formulas (6) to (8) can be used together with the polyfunctional silane (C).
R ¹ _n SiX _4-n (6)
(Wherein R ¹ represents hydrogen or an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group or an aryl group. Further, a halogen group, a hydroxy group, a mercapto group, an amino group, ( It may have a functional group such as a (meth) acryloyl group, an epoxy group, etc. X represents a hydrolyzable group, n is an integer of 0 to 3. The hydrolyzable group is a group that generates a hydroxyl group by hydrolysis. And may be any halogen atom, alkoxy group, acyloxy group, amino group, phenoxy group, oxime group, etc.)
_{^{X 3 Si-R 2 n -SiX}} 3 (7)
(Wherein X represents a hydrolyzable group, R ² represents an alkylene group having 1 to 6 carbon atoms or a phenylene group, and n is 0 or 1)
R ³ — (O—Si (OR ³ ) ₂ ) _n —OR ³ (8)
(In the formula, ^{R 3} .n represents an alkyl group having 1 to 6 carbon atoms is an integer of 2-8.)

Specific examples of hydrolyzable silicon compounds include tetramethoxysilane, tetraethoxysilane, tetra (n-propoxy) silane, tetra (i-propoxy) silane, tetra (n-butoxy) silane, tetra (i- Butoxy) silane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane , Propyltriethoxysilane, isobutyltriethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxysilane, diethoxysilane, methyldimethoxysilane, Tildiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (triphenoxysilyl) methane, bis (trimethoxysilyl) ethane, bis (triethoxy Silyl) ethane, bis (triphenoxysilyl) ethane, 1,3-bis (trimethoxysilyl) propane, 1,3-bis (triethoxysilyl) propane, 1,3-bis (triphenoxysilyl) propane, 1, 4-bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyl Triethoxysilane, -Mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltri Ethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, tetraacetoxysilane, tetrakis (trichloroacetoxy) silane, tetrakis (trifluoroacetoxy) silane, triacetoxysilane, tris (trichloroacetoxy) silane , Tris (trifluoroacetoxy) silane, methyltriacetoxysilane, methyltris (trichloroacetoxy) silane, tetrachlorosilane, tetrabromosilane Lan, tetrafluorosilane, trichlorosilane, tribromosilane, trifluorosilane, methyltrichlorosilane, methyltribromosilane, methyltrifluorosilane, tetrakis (methylethylketoxime) silane, tris (methylethylketoxime) silane, methyltris (methylethylketoxime) Silane, phenyltris (methylethylketoxime) silane, bis (methylethylketoxime) silane, methylbis (methylethylketoxime) silane, hexamethyldisilazane, hexamethylcyclotrisilazane, bis (dimethylamino) dimethylsilane, bis (diethylamino) dimethylsilane, Examples thereof include bis (dimethylamino) methylsilane and bis (diethylamino) methylsilane.

  Moreover, as a specific example of the hydrolyzable silicon compound represented by the general formula (7), a partial hydrolysis condensate of tetramethoxysilane (trade name “M silicate 51” manufactured by Tama Chemical Industry Co., Ltd. Name "MSI51" manufactured by Colcoat Co., Ltd.), trade names "MS51", "MS56" manufactured by Mitsubishi Chemical Corporation), partially hydrolyzed condensate of tetoethoxysilane (trade names "silicate 35", "silicate 45" Tama Manufactured by Chemical Industry Co., Ltd., trade names "ESI40", "ESI48" manufactured by Colcoat Co., Ltd.), co-hydrolyzed condensate of tetramethoxysilane and tetraethoxysilane (trade name "FR-3" Tama Chemical Industries ( Co., Ltd., trade name “EMSi48” manufactured by Colcoat Co., Ltd.) and the like.

As long as the characteristics of the present invention are not impaired, a metal oxide (D) other than the inorganic oxide particles (A) may be added. Examples of the metal oxide (D) include aluminum oxide, antimony oxide, titanium oxide, indium oxide, tin oxide, zirconium oxide, lead oxide, iron oxide, calcium silicate, magnesium oxide, niobium oxide, cerium oxide, zinc oxide and the like. Examples of the composite oxides can be given.
When a photocatalyst is selected as the metal oxide (D), the organic / inorganic composite formed from the organic / inorganic composite composition of the present invention is highly preferable because it exhibits photocatalytic activity and / or hydrophilicity upon light irradiation.

  Here, the photocatalyst refers to a substance that causes an oxidation or reduction reaction by light irradiation. That is, when light (excitation light) with an energy larger than the energy gap between the conduction band and the valence band (ie, a short wavelength) is irradiated, excitation (photoexcitation) of electrons in the valence band occurs, resulting in conduction. It is a substance that can generate electrons and holes. At this time, various chemical reactions are performed using the reducing power of electrons generated in the conduction band and / or the oxidizing power of holes generated in the valence band. Can do.

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.
Furthermore, in the present invention, the hydrophilicity preferably means a case where the contact angle of water at 20 ° C. is 60 ° or less, and the surface having a hydrophilicity with a contact angle of water of 30 ° or less is particularly suitable for rain or the like. It is preferable because it exhibits stain resistance due to its self-purifying ability (self-cleaning). Further, from the viewpoint of excellent stain resistance and antifogging properties, the contact angle of water on the surface is preferably 20 ° or less, more preferably 10 ° or less, and even more preferably 5 ° or less. .

  As a photocatalyst that can be usefully used as the metal oxide (D) of the present invention, a semiconductor compound having a band gap energy of preferably 1.2 to 5.0 eV, more preferably 1.5 to 4.1 eV can be exemplified. . If the band gap energy is less than 1.2 eV, the ability to cause oxidation and reduction reaction by light irradiation is very weak, which is not preferable. If the band gap energy is larger than 5.0 eV, the energy of light necessary for generating holes and electrons becomes very large, which is not preferable.

Examples of the photocatalyst include, for example, TiO ₂ , ZnO, SrTiO ₃ , BaTiO ₃ , BaTiO ₄ , BaTi ₄ O ₉ , K ₂ NbO ₃ , Nb ₂ O ₅ , Fe ₂ O ₃ , Ta ₂ O ₅ , K _3. Ta ₃ Si ₂ O ₃ , WO ₃ , SnO ₂ , Bi ₂ O ₃ , BiVO ₄ , NiO, Cu ₂ O, RuO ₂ , CeO _2, etc., and at least one selected from Ti, Nb, Ta, V Layered oxides having these elements (for example, JP-A-62-274452, JP-A-2-172535, JP-A-7-24329, JP-A-8-89799, JP-A-8-89800, JP-A-8-89804, JP-A-8-198061, JP-A-9-248465, JP-A-10-99694, JP-A-10-24416 No. See Publication) can be exemplified.
Among these photocatalysts, TiO ₂ (titanium oxide) is preferable because it is harmless and has excellent chemical stability. Any of anatase, rutile, and brookite can be used as titanium oxide.

  Moreover, as a photocatalyst used for the metal oxide (D) of the present invention, a visible light responsive photocatalyst capable of expressing photocatalytic activity and / or hydrophilicity by irradiation with visible light (for example, a wavelength of about 400 to 800 nm) is used. When selected, the photocatalyst member treated with the photocatalyst composition of the present invention is preferable because the environmental purification effect and the antifouling effect in a place where ultraviolet rays such as a room are not sufficiently irradiated are very large. The bandgap energy of these visible light responsive photocatalysts is preferably 1.2 to 3.1 eV, more preferably 1.5 to 2.9 eV, and still more preferably 1.5 to 2.8 eV.

Any visible light responsive photocatalyst can be used as long as it exhibits photocatalytic activity and / or hydrophilicity with visible light. For example, TaON, LaTiO ₂ N, CaNbO ₂ N, LaTaON ₂ , and CaTaO ₂ N can be used. Such as oxysulfide compounds such as Sm ₂ Ti ₂ S ₂ O ₇ (see, for example, JP 2002-233770 A), CaIn ₂ O ₄ , and SrIn _2. O ₄ , ZnGa
_{2 O 4, Na 2 Sb 2} O 6 such as an oxide containing a ^{d 10} of electronic state metal ion (for example, Japanese see JP 2002-59008), titanium oxide precursor in the presence of a nitrogen-containing compound such as ammonia or urea Nitrogen-doped titanium oxide (for example, JP 2002-29750 A, JP 2002-87818 A, JP 2002-2002 A) obtained by firing a body (titanium oxysulfate, titanium chloride, alkoxy titanium, etc.) or high surface titanium oxide. 154823, JP-A-2001-207082), sulfur-doped titanium oxide obtained by firing a titanium oxide precursor (titanium oxysulfate, titanium chloride, alkoxytitanium, etc.) in the presence of a sulfur compound such as thiourea. , Oxygen-deficient acid obtained by hydrogen plasma treatment of titanium oxide or heat treatment under vacuum Titanium (see, for example, JP-A-2001-98219), photocatalyst particles are treated with a halogenated platinum compound (see, for example, JP-A-2002-239353), or treatment with tungsten alkoxide (JP-A-2001-286755). The surface-treated photocatalyst obtained by (see) can be preferably mentioned.
Among the visible light responsive photocatalysts, oxynitride compounds and oxysulfide compounds have a large photocatalytic activity by visible light and can be used particularly preferably.

  The oxynitride compound that can be particularly preferably used in the present invention is an oxynitride containing a transition metal, and preferably has a high photocatalytic activity, and the transition metal is preferably selected from the group consisting of Ta, Nb, Ti, Zr, and W. The oxynitride is characterized in that it further comprises at least one element selected from the group consisting of alkali, alkaline earth and group IIIB metals. The oxynitride further includes at least one metal element selected from the group consisting of Ca, Sr, Ba, Rb, La, and Nd.

Examples of oxynitride containing the transition _{metal, LaTiO 2 N, La v Ca} w TiO 2 N (v + w = 3), La v Ca w TaO 2 N (v + w = 3), LaTaON 2, CaTaO 2 N, General formula AMOxNy such as SrTaO ₂ N, BaTaO ₂ N, CaNbO ₂ N, CaWO ₂ N, SrWO ₂ N, etc. (A = alkali metal, alkaline earth metal, group IIIB metal; M = Ta, Nb, Ti, Zr, W X + y = 3), TaON, NbON, WON, Li ₂ LaTa ₂ O ₆ N and the like. Among these, LaTiO ₂ N, LavCawTiO ₂ N (v + w = 3), LavCawTaO ₂ N (v + w = 3), and TaON are preferable because the photocatalytic activity in visible light is very large.

The oxysulfide compound that can be used particularly preferably in the present invention is an oxysulfide containing a transition metal, and has a high photocatalytic activity, and the transition metal is preferably selected from the group consisting of Ta, Nb, Ti, Zr, and W. Oxysulfide, characterized in that it is at least one, more preferably at least one element selected from the group consisting of alkali, alkaline earth and Group IIIB metals More preferably, the oxysulfide is characterized by further containing a rare earth element.
Examples of the oxysulfide containing the transition metal include Sm ₂ Ti ₂ S ₂ O ₅ , Nd ₂ Ti ₂ S ₂ O ₅ , La ₆ Ti ₂ S ₈ O ₅ , Pr ₂ Ti ₂ S ₂ O ₅ , and Sm _3. NbS ₃ O _{4 and the} like can be mentioned. Among these, Sm ₂ Ti ₂ S ₂ O ₅ and Nd ₂ Ti ₂ S ₂ O ₅ are very preferable because of their very high photocatalytic activity under visible light.

Further, the above-mentioned photocatalyst is preferably added or fixed with a metal such as Pt, Rh, Ru, Nb, Cu, Sn, Ni, Fe and / or an oxide thereof, or coated with silica or porous calcium phosphate. (See, for example, JP-A-10-244166).
The photocatalyst used in the present invention has a particle shape in which the ratio (l / d) of the particle length (l) to the particle diameter (d) is 1 from the viewpoint of the specific surface area of the photocatalyst particles and the effect of particle orientation. / 1 to 20/1 is preferable. More preferred (l / d) is in the range of 1/1 to 15/1, and even more preferred (l / d) is in the range of 1/1 to 10/1.
In the present invention, when a metal oxide having conductivity is selected as the metal oxide (D), the organic / inorganic composite formed from the organic / inorganic composite composition of the present invention has a conductive performance and an antistatic property. This is very preferable because it exhibits performance, electromagnetic wave shielding performance, and surface heat generation performance.

Examples of the metal oxide having conductivity that can be usefully used as the metal oxide (D) of the present invention include tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), tin oxide, and zinc oxide. Etc.
In the organic / inorganic composite composition of the present invention, in order to form an organic / inorganic composite excellent in transparency, strength, weather resistance, etc., the particle diameter of the metal oxide (D) is 1 to 400 nm. Necessary, preferably 1 to 100 nm, more preferably 5 to 50 nm.
As the form of the metal oxide (D) used in the present invention, any of powder, dispersion, and sol can be used. Here, the metal oxide (D) sol and the metal oxide (D) dispersion used in the present invention are 0.01 to 80% by mass, preferably 0, of photocatalyst particles in water and / or a hydrophilic organic solvent. 0.1 to 50% by mass and dispersed as primary particles and / or secondary particles.

  Here, examples of the hydrophilic organic solvent used in the metal oxide (D) sol or the metal oxide (D) dispersion include ethylene glycol, butyl cellosolve, n-propanol, isopropanol, n-butanol, ethanol, Alcohols such as methanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethers such as tetrahydrofuran and dioxane, amides such as dimethylacetamide and dimethylformamide, dimethyl sulfoxide, nitrobenzene and the like, and two or more of these A mixture is mentioned.

  In the present invention, the form of the metal oxide (D) to be used is an important factor for the expression of functions such as optical characteristics of the organic / inorganic composite. The metal oxide (D) preferably used in the present invention has a number average dispersed particle size of a mixture of primary particles and secondary particles (either primary particles or only secondary particles may be 1 to 1). A 400 nm metal oxide (D) sol or metal oxide (D) dispersion is desirable. In particular, when a metal oxide (D) sol or metal oxide (D) dispersion having a number average dispersed particle size of 1 to 100 nm is used, the organic / inorganic composite composition of the present invention has excellent transparency. It is very preferable because an inorganic composite can be obtained. More preferably, a metal oxide (D) sol or metal oxide (D) dispersion having a number average dispersed particle size of 3 to 80 nm, more preferably 5 to 50 nm is suitably selected.

In the present invention, a triorganosilane unit represented by the following formula (9), a monooxydiorganosilane unit represented by the following formula (10), a dioxyorganosilane unit represented by the following formula (11), a formula (12) The metal oxide comprising at least one modifier compound selected from the group consisting of compounds having at least one structural unit selected from the group consisting of a trioxysilane unit represented by (12) and a difluoromethylene unit. By modifying (D), a modified metal oxide (D ′) that is very excellent in dispersion stability, chemical stability, durability and the like in a solvent can be obtained.
R ₃ Si- (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.)
_{- (R 2 SiO) - (} 10)
(In the formula, R is as defined in formula (1).)

（式中、Ｒは式（１）で定義した通りである。）

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

In addition, as the modifier compound, a compound having a small surface energy {for example, the R group in the above formulas ( 9) to (11) is a linear or branched alkyl group having 1 to 30 carbon atoms, linear or A compound having at least one kind selected from a branched fluoroalkyl group having 1 to 30 carbon atoms, a linear or branched alkenyl group having 2 to 30 carbon atoms, and / or a compound having a difluoromethylene unit} When is selected, the surface energy of the resulting modified metal oxide (D ′) is reduced, and it is possible to have a self-gradient function.
Here, the self-gradient is an organic / inorganic composite described later from an organic / inorganic composite composition containing the modified metal oxide (D ′), polymer emulsion particles (B), and metal oxide (D). When a functional composite is produced by forming on a substrate, the modified metal oxide (D ′) corresponds to the property (particularly hydrophilic / hydrophobic) of the interface with which the organic / inorganic composite contacts in the formation process. This means that a structure having a concentration gradient of the modified metal oxide (D ′) is autonomously formed.

In the present invention, when the photocatalyst is selected as the metal oxide (D), the organic / inorganic composite of the present invention containing the modified photocatalyst (D) modified with the above-described modifier compound having a structure having a small surface energy. From the composition, a large amount of the modified photocatalyst (D) is present on the surface of the organic / inorganic composite in contact with air, and the amount of the modified photocatalyst (D) present at the interface between the substrate and the organic / inorganic composite is reduced. Therefore, it is very preferable because a functional complex having an excellent photocatalytic function that exhibits high photocatalytic activity and does not decompose the substrate can be obtained.
In the present invention, the modification treatment means immobilizing the modifier compound on the surface of the metal oxide (D). The immobilization of the modifier compound on the surface of the metal oxide (D) is considered to be due to van der Waals force (physical adsorption) or chemical bonding. In particular, modification using a chemical bond is preferable because the interaction between the modifier compound and the metal oxide (D) is strong, and the modifier compound is firmly fixed on the surface of the metal oxide (D) particles.

  In the present invention, the modification treatment of the metal oxide (D) with the modifier compound (d1) is the same as the above-described metal oxide (D) in the presence or absence of water and / or an organic solvent. The modifier compound (d1) is preferably a mass ratio (D) / (d1) = 1/99 to 99.99 / 0.01, more preferably (D) / (d1) = 10/90 to 99.5 /. By mixing at a ratio of 0.5, preferably by heating at 0 to 200 ° C., more preferably at 10 to 80 ° C., or by changing the solvent composition of the mixture by (reduced pressure) distillation or the like. Can be obtained.

  Here, when performing the above modification treatment, examples of organic solvents that can be 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, cyclohexanone, ethers such as tetrahydrofuran, dioxane, dimethylacetamide, dimethylformamide Amides such as chloroform, halogen compounds such as chloroform, methylene chloride, carbon tetrachloride, dimethyl sulfoxide, nitrobenzene, and a mixture of two or more thereof.

  Examples of the modifier compound suitably used for modifying the metal oxide (D) of the present invention include Si—H groups, hydrolyzable silyl groups (alkoxysilyl groups, hydroxysilyl groups, silyl halides). Groups, acetoxysilyl groups, aminoxysilyl groups, etc.), epoxy compounds, acetoacetyl groups, thiol groups, acid anhydride groups and other photocatalytic particles and reactive silicon compounds, fluoroalkyl compounds, fluoroolefin polymers, etc. Can be mentioned. These compounds are more preferable because they can be chemically bonded to the metal oxide (D) and are firmly fixed on the surface of the metal oxide (D).

When the specific example of a fluoroalkyl compound is shown in the said modifier compound, the compound which can be represented by following formula (13) can be mentioned.
_{CF 3 (CF 2) g -Y-} (V) w (13)
{In the formula, g represents an integer of 0 to 29. Y represents a w-valent organic group having a molecular weight of 14 to 50,000. w is an integer of 1-20. V is composed of an epoxy group, a hydroxyl group, an acetoacetyl group, a thiol group, a cyclic acid anhydride group, a carboxyl group, a sulfonic acid group, a polyoxyalkylene group, a phosphoric acid group, and a group represented by the following formula (14). It represents at least one functional group selected from the group.
-SiW _x R _y (14)
(In the formula, W represents an alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, an acetoxy group having 1 to 20 carbon atoms, a halogen atom, a hydrogen atom, an oxime group having 1 to 20 carbon atoms, an enoxy group, an aminoxy group, and an amide group. Represents at least one selected group, wherein R is a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, and an unsubstituted or carbon atom. It represents at least one hydrocarbon group selected from an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom, where x is 1 or more. Is an integer of 3 or less, and y is an integer of 0 or more and 2 or less, and x + y = 3.)}

The organic / inorganic composite composition of the present invention may be in a solvent-free state or in a state dispersed in water, and is not particularly limited, but when used as a coating agent, A dispersed state is preferred. At this time, the solid content of the organic / inorganic composite composition is preferably 0.01 to 60% by mass, more preferably 1 to 40% by mass. The viscosity at that time is preferably 0.1 to 100,000 mPa · s, preferably 1 to 10000 mPa · s at 20 ° C.
In addition, alcohols can be added to the organic / inorganic composite composition of the present invention for the purpose of controlling the interaction between the inorganic oxide particles (A) and the polymer emulsion particles (B) due to hydrogen bonding or the like. . Addition of alcohol greatly improves storage stability and the like.

Examples of the alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, modified ethanol, glycerin, monoalkyl monoglyceryl ether having 3 to 8 carbon atoms in the alkyl chain, and propylene glycol monomethyl. Ether, diethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether or di to tetraethylene glycol monophenyl ether are preferred. Of these, ethanol is most preferable from the environmental viewpoint.

In the organic / inorganic composite composition of the present invention, as a UV absorber, at least one selected from the group consisting of a benzophenone UV absorber, a benzotriazole UV absorber, and a triazine UV absorber, as a light stabilizer, At least one selected from the group consisting of hindered amine light stabilizers can be used. It is preferable to use 0.1 mass%-5 mass% of a ultraviolet absorber and / or a light stabilizer with respect to the mass of a polymer emulsion particle (B). Moreover, a radical polymerizable ultraviolet absorber having a radical polymerizable double bond in the molecule as an ultraviolet absorber, and a radical polymerizable light stabilizer having a radical polymerizable double bond in the molecule as a light stabilizer. It can also be used. In addition, it is preferable to use an ultraviolet absorber and a light stabilizer in combination since the weather resistance is excellent when a composite is formed using the obtained organic / inorganic composite composition.
These ultraviolet absorbers and light stabilizers can be simply blended with the inorganic oxide particles (A) and the polymer emulsion particles (B), and coexist when synthesizing the polymer emulsion particles (B). It is also possible to make it.

  Specific examples of the benzophenone-based ultraviolet absorber that can be used in the present invention include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2- Hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2, -Hydroxy-4 Methoxy-2'-carboxy benzophenone, and the like 2-hydroxy-4-stearyloxy benzophenone. Specific examples of the radical polymerizable benzophenone ultraviolet absorber include 2-hydroxy-4-acryloxybenzophenone, 2-hydroxy-4-methacryloxybenzophenone, 2-hydroxy-5-acryloxybenzophenone, 2-hydroxy-5- Methacryloxybenzophenone, 2-hydroxy-4- (acryloxy-ethoxy) benzophenone, 2-hydroxy-4- (methacryloxy-ethoxy) benzophenone, 2-hydroxy-4- (methacryloxy-diethoxy) benzophenone, 2-hydroxy-4- ( Acryloxy-triethoxy) benzophenone.

Specific examples of the benzotriazole-based UV absorber that can be used in the present invention include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-5′-tert-butylphenyl). Benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy −3,5-di-tert-octylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α′-dimethylbenzyl) phenyl] benzotriazole), methyl-3- [ 3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate Condensate with ethylene glycol (molecular weight 300) (product name: TINUVIN 1130, manufactured by Ciba-Geigy Corporation), isooctyl-3- [3- (2H-benzotriazol-2-yl) -5-tert-butyl-4- Hydroxyphenyl] propionate (manufactured by Ciba Geigy Japan, trade name: TINUVIN 384), 2- (3-dodecyl-5-methyl-2-hydroxyphenyl) benzotriazole (manufactured by Ciba Geigy Japan, trade name: TINUVIN 571), 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) benzo Triazole, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazo 2- [2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl] benzotriazole, 2,2-methylenebis [4- ( 1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl) -1-phenylethyl) phenol (Nippon Ciba-Geigy Co., Ltd., trade name: TINUVIN900). Specifically, 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole (manufactured by Otsuka Chemical Co., Ltd., trade name: RUVA-93) as a radical polymerizable benzotriazole-based ultraviolet absorber. ), 2- (2′-hydroxy-5′-methacryloxyethyl-3-tert-butylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5′-methacrylyloxypropyl-3-tert- Butylphenyl) -5-chloro-2H-benzotriazole, 3-methacryloyl-2-hydroxypropyl-3- [3 ′-(2 ″ -benzotriazolyl) -4-hydroxy-5-tert-butyl] phenylpropi Honate (Nippon Ciba-Geigy Co., Ltd., trade name: CGL-104).

Specific examples of triazine-based ultraviolet absorbers that can be used in the present invention include TINUVIN400 (trade name, manufactured by Nippon Ciba-Geigy Co., Ltd.).
As the UV absorber that can be used in the present invention, a benzotriazole UV absorber and a triazine UV absorber having high UV absorbing ability are preferable.
Specific examples of hindered amine light stabilizers that can be used in the present invention include bis (2,2,6,6-tetramethyl-4-piperidyl) succinate and bis (2,2,6,6-tetramethylpiperidyl) sebacate. Bis (1,2,2,6,6-pentamethyl-4-piperidyl) 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2-butylmalonate, 1- [2- [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propynyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propynyloxy] -2 , 2,6,6-tetramethylpiperidine, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl-1,2,2,6,6-pentamethyl Mixture of 4-piperidyl-sebacate (manufactured by Ciba Geigy Japan, trade name: TINUVIN292), bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, TINUVIN123 (trade name, Japan Ciba Gaigi Co., Ltd.). Specific examples of the radical polymerizable hindered amine light stabilizer include 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidyl acrylate, 2, 2,6,6-tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 1,2,2,6,6-pentamethyl-4-iminopiperidyl methacrylate, 2, 2,6,6, -tetramethyl-4-iminopiperidyl methacrylate, 4-cyano-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4-cyano-1,2,2,6,6- Examples include pentamethyl-4-piperidyl methacrylate.
As the hindered amine light stabilizer that can be used in the present invention, those having a low basicity are preferable, and specifically, those having a base constant (pKb) of 8 or more are preferable.

In addition, the organic / inorganic composite composition of the present invention usually includes components added to and blended with paints and molding resins, for example, thickeners, leveling agents, thixotropic agents, depending on the application and method of use. , Antifoaming agent, Freezing stabilizer, Matting agent, Crosslinking reaction catalyst, Pigment, Curing catalyst, Crosslinking agent, Filler, Anti-skinning agent, Dispersant, Wetting agent, Light stabilizer, Antioxidant, UV absorber , Rheology control agent, antifoaming agent, film forming aid, rust preventive agent, dye, plasticizer, lubricant, reducing agent, preservative, antifungal agent, deodorant, anti-yellowing agent, antistatic agent or A charge adjusting agent or the like can be selected and combined in accordance with each purpose.

The organic / inorganic composite composition of the present invention comprises a paint, a finishing material for building materials, an adhesive, an adhesive, a paper processing agent or a woven fabric, a non-woven fabric, a sealing agent, an adhesive, an ink, a coating material, It can be used in a wide range such as mold materials, elastomers, foams and plastic raw materials, and fiber treatment agents.
From the organic / inorganic composite composition of the present invention, an organic / inorganic composite in the form of a film, a sheet, a fiber, or a molded body can be formed.

In the present invention, when a metal oxide (photocatalyst) having photocatalytic activity is used as the metal oxide (D), the water contact angle of the obtained organic / inorganic composite can be kept low for a long period of time. Here, the range of the mass ratio (A) / (D) of the inorganic oxide particles (A) and the metal oxide (D) having photocatalytic activity is preferably 50/50 to 99/1, more preferably. 80/20 to 97/3, most preferably 85/15 to 95/5.
On the other hand, if the mass ratio (D) / (B) of the metal oxide (D) having photocatalytic activity to the polymer emulsion particles (B) is too high, light irradiation of the organic / inorganic composite formed on the substrate is performed. Deterioration due to is remarkable, which is not preferable. Therefore, the range of the mass ratio (D) / (B) is preferably 1/99 to 50/50, more preferably 3/97 to 20/80, and most preferably 5/95 to 15/85. It is.

In addition, the organic / inorganic composite in the case of using a photocatalyst as the metal oxide (D) has excellent decomposition activity of contaminating organic substances by irradiating light with energy higher than the band gap energy of the photocatalyst contained therein. It shows contamination resistance and further photoelectric conversion function.
Here, as a light source of light having energy higher than the band gap energy of the photocatalyst, light such as sunlight, indoor lighting, and light obtained in a general residential environment, light such as black light, xenon lamp, mercury lamp, LED, etc. Is available.
Further, the organic / inorganic composite in the case where a conductive metal oxide is used as the metal oxide (D) exhibits excellent conductive performance, antistatic performance, electromagnetic wave shielding performance, and surface heat generation performance.

  In the present invention, it is preferable that the organic / inorganic composite is formed in a state in which the inorganic oxide particles (A) effectively act as a curing agent for the polymer emulsion particles (B). As an example of such a preferable organic / inorganic composite, the inorganic oxide particles (A) interact with the polymer emulsion particles (B) to form a continuous layer between the particles of the polymer emulsion particles (B). Can be mentioned. The organic / inorganic composite in such a form is particularly excellent in chemical resistance, optical characteristics, and the like.

  In order to form the organic / inorganic composite in the form as described above, the mass ratio (A) / (B) of the inorganic oxide particles (A) and the polymer emulsion particles (B) in the organic / inorganic composite composition. It is most effective to set the value within the optimum range. The optimal range of the mass ratio (A) / (B) is, for example, measuring the transparency of the organic / inorganic composite produced from the organic / inorganic composite composition with the mass ratio (A) / (B) changed, It can be determined as a range of the mass ratio (A) / (B) having relatively good transparency. Here, the range of the optimum mass ratio (A) / (B) between the inorganic oxide particles (A) and the polymer emulsion particles (B) to be used is the surface area (SA) and the weight of the inorganic oxide particles (A). The difference in the number of surface areas (SB) of the combined emulsion particles (B) is preferably within 3 digits. The surface area can be calculated from the particle diameters of the inorganic oxide particles (A) and the polymer emulsion particles (B) and the blending mass numbers.

In the present invention, the most preferable form of the organic / inorganic composite is that the polymer emulsion particles (B) have a core / shell structure, and the continuous phase is formed with the shell phase interacting with the inorganic oxide particles (A). A particulate core phase formed and present in the continuous layer. The organic / inorganic composite having such a form is excellent not only in chemical resistance and optical properties but also in mechanical properties (balance of strength and flexibility, etc.) (see FIG. 1).
In another aspect of the present invention, a functional composite having an organic / inorganic composite on a substrate is provided.
The substrate used for obtaining the functional composite of the present invention is not particularly limited, and for example, all substrates used for the applications disclosed in the present invention can be used.
Specific examples of the base material used to obtain the functional composite of the present invention include organic base materials such as synthetic resins and natural resins, and inorganic base materials such as metals, ceramics, glass, stone, cement, and concrete. Or combinations thereof.

Examples of the organic base material include acrylic resins such as polymethyl methacrylate, styrene resins such as polystyrene and ABS resins, olefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, and 6-nylon. Polyamide resins such as 1,6-6-nylon, polyvinyl chloride resins, polyvinylidene chloride resins, polycarbonate resins, polyphenylene sulfide resins, polyphenylene ether resins, polyimide resins, polyetherimide resins, cellulose acetate Examples thereof include a base material made of a cellulose-based resin.
You may add various additives, such as a ultraviolet absorber, a hindered amine light stabilizer, and a plasticizer, to such an organic base material. If an additive having a relatively high molecular weight is used, it becomes difficult for the additive to bleed out on the surface of the organic / inorganic composite formed on the organic substrate, and the antifouling performance can be easily maintained. Moreover, the transition to the interface between the organic base material and the organic / inorganic composite is also suppressed, and the base material adhesion and chemical resistance of the organic / inorganic composite are improved.

  As an ultraviolet absorber used for an organic base material, a molecular weight of 300 or more is preferable. Examples of the ultraviolet absorber having a molecular weight of 300 or more include 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3). '-T-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy- 3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -4-methyl-6- (3,4,5,6-tetrahydrophthalimidylmethyl) Phenol, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2, -Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2H-benzotriazol-2-yl) -4,6 -Bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-di-t-pentylphenol, 2-hydroxy-4-methoxybenzophenone-5-sulfone Acid trihydrate, 2-hydroxy-4-octyloxybenzophenone, 4-n-dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2 ′, 4′-di-t-butylphenyl- 3,5-di-t-butyl-4-hydroxybenzoate, 2'-ethylhexyl 2-cyano-3,3-diphenyl acrylate , Bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, and the like. These can be used alone or in combination of two or more.

Among them, benzotriazole-based compounds are preferable because the resulting thermoplastic resin composition has excellent weather resistance, and particularly excellent in bleed-out resistance, so that the molecule has two or more benzotriazole skeletons. Benzotriazole compounds, specifically 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2H -Benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol and the like are preferable.

  As the hindered amine light stabilizer used for the organic substrate, those having a 2,2,6,6-tetraalkylpiperidine ring can be suitably used. These may be a low molecular weight type having a molecular weight of 1000 or less or a high molecular weight type having a molecular weight exceeding 1000.

Examples of the low molecular weight hindered amine light stabilizer include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2, 6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexanoyloxy-2,2,6,6-tetramethylpiperidine, 4- (o-chloro) Benzoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenoxyacetoxy) -2,2,6,6-tetramethylpiperidine, 1,3,8-triaza-7,7,9,9 Tetramethyl-2,4-dioxo-3-noctyl-spiro [4,5] decane, bis (2,2,6,6-tetramethyl-4-pipe Gil) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tris (2,2,6 , 6-Tetramethyl-4-piperidyl) benzene-1,3,5-tricarboxylate, Tris (2,2,6,6-tetramethyl-4-piperidyl) -2-acetoxypropane-1,2,3 Tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -2-hydroxypropane-1,2,3-tricarboxylate, tris (2,2,6,6-tetramethyl -4-piperidyl) triazine-2,4,6-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidine) phosphite, tris (2,2, , 6-Tetramethyl-4-piperidyl) butane-1,2,3-tricarboxylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) propane-1,1,2,3-tetra Examples thereof include carboxylate and tetrakis (2,2,6,6-tetramethyl-4-piperidyl) butane-1,2,3,4-tetracarboxylate. More specifically, those commercially available under trade names such as Sanol LS770, Tinuvin 144, Adekastab LA-57, Adekastab LA-62, Adekastab LA-67, Goodlight UV-3034 can be used.
Examples of the high molecular weight hindered amine light stabilizer include those represented by the following formulas (15) to (24).

More specifically, commercially available products such as Siasorb UV3346, Kimasorb 944LD, Tinuvin 622LD, and the like can be used.
In the above examples, the nitrogen of the 2,2,6,6-tetraalkylpiperidine ring is bonded to hydrogen or a hydrocarbon group, but the 2,2,6,6-tetramethylpiperidine ring of The NOR type in which the nitrogen atom is substituted by an RO group (R is a substituted or unsubstituted hydrocarbon group or acyl group) is used instead of the light stabilizer as described above or as described above. Can be used with light stabilizers. As the NOR type light stabilizer, in the low molecular weight type or high molecular weight type light stabilizer as described above, the nitrogen atom of the 2,2,6,6-tetramethylpiperidine ring is alkyloxy, alkenyloxy, Substituted with groups such as cycloalkyloxy, bicycloalkyloxy, phenyloxy, naphthyloxy, phenylalkoxy, alkyl group-substituted phenyloxy, hydroxyl group-substituted alkyloxy, acyloxy, alkyl group-substituted alkyloxy, thioalkoxy group-substituted alkyloxy Can be used.

More specifically, 1-cyclohexyloxy-4-stearoyloxy-2,2,6,6-tetramethylpiperidine, bis (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl Succinate, bis (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate, bis (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) ) Sebacate, 1-benzoyloxy-4- (Nn-butyl-N-benzoylamino) -2,2,6,6-tetramethylpiperidine, 1,4-di- (4-hydroxy-3,5-di) -T-butylbenzoyloxy) -2,2,6,6-tetramethylpiperidine, n-butyl- (1-benzoyloxy-2,2,6,6-teto Methylpiperidin-4-yl) carbonate, α, α ′-(di-1-ethoxy-2,2,6,6-tetramethylpiperidin-4-yloxy) -p-xylene, 1-ethoxy-4-benzyloxy -2,2,6,6-tetramethylpiperidine, 1,4-dibenzyloxy-2,2,6,6-tetramethylpiperidine, 1- (α-methylbenzyloxy) -4-benzoyloxy-2, 2,6,6-tetramethylpiperidine, bis (1-benzoyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1-benzoyloxy-2,2,6,6- Tetramethylpiperidin-4-yl) phthalate, bis (1-benzyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1-methoxy-) , 2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1-methoxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate, (1-cyclohexyloxy-2,2 , 6,6-tetramethylpiperidin-4-yl) -3,5-di-t-butyl-4-hydroxybenzoate, bis (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4- Yl) isophthalate, bis (1-cyclohexyloxy-2,2,6,6)
-Tetramethylpiperidin-4-yl) phthalate, bis (1-heptyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1- (α-methylbenzyloxy) -2, 2,6,6-tetramethylpiperidin-4-yl) terephthalate, bis (1- (α-methylbenzyloxy) -2,2,6,6-tetramethylpiperidin-4-yl) isophthalate, bis (1 -Ethoxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1-cumyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1-octadecyl) Oxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis [1- (bicyclo- [4,4,0] -decyl-1-oxy)- 2,2,6,6-tetramethylpiperidin-4-yl] sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1-octyloxy- 2,2,6,6-tetramethylpiperidin-4-yl) succinate, bis (1-n-butylcarbamoyloxy-2,2,6,6-tetramethylpiperidin-4-yl) 2,2-dimethylmalonate ), 2,4,4-trimethylhexane-1,6-dicarbamate bis (4-benzoyloxy-2,2,6,6-tetramethylpiperidin-1-yl), bis (1-n-butylcarbamoyloxy) -2,2,6,6-tetramethylpiperidin-4-yl) phthalate, bis (1-n-butylcarbamoyloxy-2,2,6,6-tetramethylpiperi N-4-yl) isophthalate, (3,5-di-t-butyl-4-hydroxybenzyl) n-butylmalonate bis (1-methoxy-2,2,6,6-tetramethylpiperidine-4- Yl), (3,5-di-t-butyl-4-hydroxybenzyl) n-butylmalonate bis (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl), 3, 15-di-α-methylbenzyloxy-2,2,4,4,14,14,16,16-octamethyl-7,11,18,21-tetraoxa-3,15-diazatrispiro [5,2,2,5 , 2,2] heneicosane, 3,15-di-dicyclohexyloxy-2,2,4,4,14,14,16,16-octamethyl-7,11,18,21-tetraoxa-3,15-diazato Rispiro [5,2,2,5,2,2] heneicosane, poly- [6-{(1,1,3,3-tetramethylbutyl) -imino} -1,3,5-triazine-2,4 -Diyl] [2- (1-acetoxy-2,2,6,6-tetramethylpiperidyl) -imino] -hexamethylene- [4- (1-acetoxy-2,2,6,6-tetramethylpiperidyl) -Imino], poly- [6-{(1,1,3,3-tetramethylbutyl) -imino} -1,3,5-triazine-2,4-diyl] [2- (1-acetoxy-2 , 2,6,6-tetramethylpiperidyl) -imino] -hexamethylene- [4- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidyl) -imino] etc. as a representative example Can do.

As these hindered amine light stabilizers, it is preferable to use a low molecular weight type and a high molecular weight type in combination, particularly considering weather resistance. In consideration of the antifouling property, substrate adhesion and chemical resistance of the organic / inorganic composite formed on the organic substrate, it is preferable to use only the high molecular weight type.
As the plasticizer used for the organic substrate, a polyester plasticizer is preferable. The polyester plasticizer is produced by condensing a polybasic acid component and a polyhydric alcohol component, if necessary, using a monohydric alcohol and / or a monobasic acid as a terminal terminating component.
As the polyhydric alcohol component, a compound having a specific branch represented by the following formula (25) is preferably used in an amount of 20% by weight or more, and more preferably 40% by weight or more.

  The polybasic acid component used for the production of the polyester plasticizer is mainly composed of an aliphatic dibasic acid such as malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, etc. In addition, a small percentage of aromatic polybasic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, butanetricarboxylic acid, tricarballylic acid, citric acid, etc. Aliphatic polybasic acids can also be used.

  Examples of the polyhydric alcohol component include 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2,2-diethyl-1,3-propanediol (di-ethylene). Methylolpentane), 2-ethyl-2-n-butyl-1,3-propanediol (dimethylolheptane), 3-methyl-1,5-pentanediol, and the like. In addition, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, , 5-hexanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl- , 5-pentane is mainly composed of glycol diol, other minor proportion of glycerol, trimethylol propane, trimethylol ethane, may also be used polyhydric alcohols such as pentaerythritol.

As end-stopping components, methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, isobutanol, hexanol, isohexanol, heptanol, isoheptanol, octanol, isooctanol, 2-ethylhexanol, isononyl alcohol, isodecanol, Aliphatic monohydric alcohols such as isoundecanol, isotridecyl alcohol, benzyl alcohol, and acetic acid, propionic acid, butyric acid, isobutyric acid, octylic acid, 2-ethylhexyl acid, lauric acid, myristic acid, palmitic acid, stearic acid, And aliphatic monobasic acids such as coconut oil fatty acid.
In addition, a part of the polybasic acid and / or polyhydric alcohol component can be replaced with 12-hydroxystearic acid, caprolactone, or the like.

The ratio of each of these components varies depending on the type of component used and the characteristics, molecular weight, etc. of the target polyester plasticizer. It is used in a ratio of 0% by weight and 0 to 50% by weight of the end-stopping component.
It is well known to produce a polyester plasticizer using these components, and for example, it can be easily produced by reacting in the presence of a catalyst such as dibutyltin oxide or tetraalkyl titanate.
The polyester plasticizer used for the organic base material preferably has a number average molecular weight of 600 to 5000, particularly 1000 to 3000, and preferably has an acid value of 1 or less and a hydroxyl value of 30 or less.

  The functional composite of the present invention is, for example, after applying the organic / inorganic composite composition to a substrate and drying it, and if desired, preferably 20 ° C. to 500 ° C., more preferably 40 ° C. to 250 ° C. It can be obtained by performing ultraviolet irradiation or the like to form an organic / inorganic composite film on the substrate. Examples of the coating method include spray spraying, flow coating, roll coating, brush coating, dip coating, spin coating, screen printing, casting, gravure printing, flexographic printing, and the like.

When the organic / inorganic composite of the present invention is formed as a film on a substrate, the thickness of the film is 0.05 to 100 μm, preferably 0.1 to 10 μm. The thickness is preferably 100 μm or less from the viewpoint of transparency, and is 0 for exhibiting functions such as antifouling properties, antifogging properties, antistatic properties, photocatalytic activity, electrical conductivity, electromagnetic wave shielding properties, and surface exothermic properties. The thickness is preferably 0.05 μm or more.
In the present specification, the expression “film” is used. However, the film is not necessarily a continuous film, and may be a discontinuous film, an island-shaped dispersion film, or the like.
The method for producing the functional composite of the present invention is not limited to the case where the organic / inorganic composite film of the present invention is formed on a substrate. The base material and the organic / inorganic composite of the present invention may be simultaneously molded, for example, integrally molded. Moreover, you may shape | mold a base material after shape | molding the organic-inorganic composite of this invention. Alternatively, the organic / inorganic composite of the present invention and the substrate may be individually molded and then formed into a functional composite by adhesion, fusion, or the like.

The functional composite of the present invention having an organic / inorganic composite formed from an organic / inorganic composite composition containing the above-described modified metal oxide (D ′) on the substrate -The density | concentration of the modified metal oxide (D ') in an inorganic composite has the characteristics that the other exposed surface is higher than the surface which contact | connects the base material of this organic-inorganic composite. At this time, when the modified metal oxide (D ′) is a modified photocatalyst, even when an organic base material that decomposes with a photocatalyst is used as the base material in the functional composite, the contact between the photocatalyst and the organic base material is small, so that it is durable. Therefore, a functional composite having a photocatalytic function having both excellent photocatalytic activity and durability can be obtained.
The organic / inorganic composite or functional composite of the present invention, which has a hydrophilic property (hydrophilic film, and the like) having a contact angle with water at 20 ° C. of 60 ° or less (preferably 30 ° or less) The substrate coated with a hydrophilic film can be applied to anti-fogging technology for preventing fogging of mirrors and glass, and further to antifouling technology and antistatic technology for building exteriors.

  Examples of the application of the organic / inorganic composite or functional composite of the present invention to the antifouling technology field include, for example, building materials, building exteriors, building interiors, window frames, window glass, structural members, residential building equipment, especially toilets. Tub, wash basin, lighting fixture, lighting cover, kitchenware, tableware, dishwasher, tableware dryer, sink, cooking range, kitchen hood, ventilation fan, etc. The organic / inorganic composite or functional composite of the present invention can also be used for the exterior and coating of vehicles, and the interior of some vehicles depending on the application, such as covers for vehicle lighting, window glass, instruments, display panels, etc. It is effective for use in members that are required, and it is effective for the exterior of machinery and articles, dust-proof covers and coatings, display devices, covers, traffic signs, various display devices, display objects such as advertising towers, for roads, Sound insulation walls for railways, bridges, guardrail exteriors and paintings, tunnel interiors and paintings, insulators, solar battery covers, solar water heater heat collection covers, etc., exterior parts of electronic and electrical equipment used outside, especially transparent materials, vinyl It can also be used for exteriors such as houses and greenhouses, especially transparent members, and in environments where there is a risk of contamination even inside, such as medical and physical education facilities and equipment.

Examples of the application of the organic / inorganic composite or functional composite of the present invention to the anti-fogging technology field include, for example, mirrors (vehicle rear-view mirrors, bathroom mirrors, toilet mirrors, dental mirrors, road mirrors, etc.) , Lenses (glass lenses, optical lenses, illumination lenses, semiconductor lenses, photocopier lenses, vehicle rear-view camera lenses, etc.), prisms, building and surveillance tower window glass, vehicle window glass (cars,
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, snow) Mobile, ropeway gondola, amusement park gondola, spacecraft, etc.), protective goggles, sports goggles, protective mask shield, sports mask shield, helmet shield, frozen food display case glass, insulated food Display case glass, measuring device cover, vehicle rear camera lens cover, focusing lens for laser dentistry, laser light detection sensor cover such as inter-vehicle distance sensor, infrared sensor cover, camera filter, etc. Can be mentioned.

  Examples of the application of the organic / inorganic composite or functional composite of the present invention to the antistatic technical field include, for example, cathode ray tubes, magnetic recording media, optical recording media, magneto-optical recording media, audio tapes, video tapes, analog records, Housing, parts, exterior and painting of household electrical products, housing, parts, exterior and painting of OA equipment products, building materials, building exteriors, building interiors, window frames, window glass, structural members, exterior and painting of vehicles, machinery And applications such as exteriors of articles, dust-proof covers and painting.

  The organic / inorganic composite or functional composite of the present invention can be applied to the antibacterial and antifungal technical fields by photocatalysis. For example, building materials, building exteriors, building interiors, window frames, structural members, housing and other building equipment, especially toilets, bathtubs, washstands, lighting fixtures, lighting covers, kitchenware, tableware, dishwashers, dish dryers, sinks, Cooking ranges, kitchen hoods, ventilation fans, cupboards, display cabinets, bathroom and toilet walls, ceilings, doorknobs, medical and public facilities, such as hospital parts, ambulance parts, food and pharmaceutical factories, schools・ For hygiene management in public facilities such as gymnasiums / stations, public baths, public toilets, inns, hotels, etc., mention the use of walls, floors and ceilings, fixtures, fixtures, door knobs, etc. it can. 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.

The organic / inorganic composite or functional composite of the present invention, which has photocatalytic activity such as organic matter decomposition, expresses various functions such as antibacterial, antifouling, deodorant, NOx decomposition, etc., air, water, etc. It can be used for applications such as environmental purification.
The organic / inorganic composite or functional composite of the present invention having a photoelectric conversion function can express functions such as power conversion of solar energy, and is used for (wet) solar cells and the like. It can be used for applications such as optical semiconductor electrodes.
The organic / inorganic composite or functional composite of the present invention having conductive performance is used for transparent conductive films such as solar cells, liquid crystal display materials, electronic paper, organic EL, and touch panels, and is anti-fogging / anti-proof. It can be used for surface heating applications such as frost heaters and heating panel heaters.

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. The following physical properties 2-6 are acrylic plates (trade name “Delagrass K” manufactured by Asahi Kasei Chemicals Co., Ltd., thickness 2 mm), and physical properties 7-7 below are polyvinyl chloride films (trade name “Scotch Cal XL- JS1000 ", manufactured by Sumitomo 3M Ltd.) was used for evaluation. In any test plate, a corona master manufactured by Shinko Electric Instrumentation Co., Ltd. was used, and a corona discharge treatment was performed under the conditions of a voltage of 14 V, an electrode / base material distance: 2 mm, and a sweep speed of 5 cm / sec. It was.

1. Number average particle diameter A sample was appropriately diluted by adding a solvent so that the solid content in the sample was 1 to 20% by mass, and measured using a wet particle size analyzer (Microtrac UPA-9230, manufactured by Nihon Koki Co., Ltd.).
2. Water contact angle A drop of deionized water was placed on the surface of the film, left at 20 ° C for 1 minute, and then measured using a CA-X150 contact angle meter manufactured by Kyowa Interface Science, Japan.
The smaller the contact angle of water with the film (hereinafter referred to as initial CA), the higher the hydrophilicity of the film surface.
3. Transparency The haze value was measured according to JIS-K7105, using a turbidimeter NDH2000 manufactured by Nippon Denshoku Industries, Japan.
4). Hardness It was determined as pencil hardness (scratch of film) according to JIS-K5400.

5. Alcohol resistance Ethanol was soaked in a cotton swab, a load of 100 g was applied, and the surface of the film was rubbed 10 times.
A: Good with no change in appearance. B: Part of the film is scratched, but good.
X: The film peels off and is bad.

6). Film appearance The surface of the film was visually observed, and the degree of interference pattern was evaluated in the following three stages.
(Double-circle): There is almost no interference pattern and it is favorable.
○: Some interference pattern is seen but good.
X: The interference pattern is conspicuous and bad.

7). Contamination resistance After the test plate was attached to a fence facing a general road (traffic volume of about 500 to 1000 units / day) for 3 months, the degree of contamination was visually evaluated.
A: Good with no dirt.
○: Good although there is some dirt.
X: Rain stains are seen and bad.

8). Crack resistance After the film was formed on the test plate and the stain resistance was evaluated (after 3 months), the surface of the film was visually observed and evaluated in the following three stages.
○: In all cases, there is no crack and it is good.
Δ: There are no cracks after the film is formed, but cracks are observed after the stain resistance test.
X: Cracks are observed after film formation, which is bad.

9. Photocatalytic activity After a 5% by mass ethanol solution of methylene blue was applied to the surface of the coating, the light of FL20S BLB type black light manufactured by Toshiba Lighting & Technology was irradiated for 3 days. At this time, the UV intensity measured by using a UVR-2 type UV intensity meter manufactured by Topcon, Japan (using a UD-36 type light receiving part manufactured by Topcon, Japan (corresponding to light having a wavelength of 310 to 400 nm) as the light receiving part). Was adjusted to 1 mW / cm ² .
Thereafter, the activity of the photocatalyst was evaluated in the following three stages based on the degree of decomposition of methylene blue (based on visual evaluation based on the degree of fading of the coating surface).
A: Methylene blue is completely decomposed.
○: Methylene blue slightly remains blue.
X: Methylene blue was hardly decomposed.

[Reference Example 1]
Synthesis of Polymer Emulsion Particles (B-1) Aqueous Dispersion 500 g of ion-exchanged water and 1 g of dodecylbenzenesulfonic acid were charged into a reactor having a reflux condenser, a dropping tank, a thermometer and a stirring device, and then stirred. The temperature was warmed to 80 ° C. To this, a mixed solution of 50 g of dimethyldimethoxysilane and 50 g of phenyltrimethoxysilane was dropped over about 2 hours with the temperature in the reaction vessel kept at 80 ° C., and then the temperature in the reaction vessel was 80 ° C. And stirring was continued for about 1 hour. Next, a mixed solution of 40 g of butyl acrylate, 50 g of phenyltrimethoxysilane, 130 g of tetraethoxysilane, 5 g of 3-methacryloxypropyltrimethoxysilane, 90 g of diethylacrylamide, 3 g of acrylic acid, a reactive emulsifier (trade name “ADEKA rear soap SR -1025 ", manufactured by Asahi Denka Co., Ltd., 25 g solid content aqueous solution), 2 g ammonium persulfate aqueous solution 40 g, and 1000 g of ion-exchanged water, with the temperature in the reaction vessel kept at 80 ° C. It was dripped simultaneously over about 2 hours. Further, stirring was continued for about 2 hours in a state where the temperature in the reaction vessel was 80 ° C., then cooled to room temperature, filtered through a 100-mesh wire mesh, and the solid content was adjusted to 10.0% by mass with ion-exchanged water. A polymer emulsion particle (B-1) aqueous dispersion having a number average particle diameter of 130 nm was obtained.

[Reference Example 2]
Synthesis of Polymer Emulsion Particle (B-2) Aqueous Dispersion 500 g of ion-exchanged water and 1 g of dodecylbenzenesulfonic acid were charged into a reactor having a reflux condenser, a dropping tank, a thermometer and a stirring device, and then stirred. The temperature was warmed to 80 ° C. To this, 40 g of butyl acrylate, 50 g of dimethyldimethoxysilane, 100 g of phenyltrimethoxysilane, 130 g of tetraethoxysilane, 5 g of 3-methacryloxypropyltrimethoxysilane, 90 g of diethylacrylamide, 3 g of acrylic acid, reactive emulsifier (product) Name “Adekaria Soap SR-1025”, manufactured by Asahi Denka Co., Ltd., 25 g solid content aqueous solution) 8 g, ammonium persulfate 2 mass% aqueous solution 40 g, and ion-exchanged water 1000 g. It was dripped simultaneously over about 2 hours in the state kept at ° C. Further, stirring was continued for about 2 hours in a state where the temperature in the reaction vessel was 80 ° C., then cooled to room temperature, filtered through a 100-mesh wire mesh, and the solid content was adjusted to 10.0% by mass with ion-exchanged water. A polymer emulsion particle (B-2) aqueous dispersion having a number average particle diameter of 130 nm was obtained.

[Reference Example 3]
Synthesis of polyfunctional silane (C-2) Bis (trimethoxysilylpropyl) amine (trade name “KBM-666P”, Shin-Etsu Chemical Co., Ltd.) was added to a reactor having a reflux condenser, a dropping tank, a thermometer and a stirring device. After 34.2 g was added, the temperature was raised to 40 ° C. under a nitrogen atmosphere and stirring. To this, 24.7 g of isocyanate propyltriethoxysilane (trade name “KBE-9007”, manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise over about 1 hour while maintaining the temperature of the reaction vessel at 80 ° C. Further, stirring was continued for about 30 minutes in a state where the temperature in the reaction vessel was 40 ° C., and then cooled to room temperature to obtain polyfunctional silane (C-2). This polyfunctional silane (C-2) was confirmed to be a polyfunctional silane represented by the above formula (5).

[Example 1]
Reference Example 1 was prepared by mixing 121 g of distilled water and 49 g of ethanol with 25 g of water-dispersed colloidal silica (trade name “Snowtex O”, manufactured by Nissan Chemical Industries, Ltd., solid content 20%) having a number average particle size of 12 nm. Polymer emulsion particles (B-1) dispersed in water (50 g), silica-coated titanium oxide hydrosol (trade name “TSK-5”, manufactured by Ishihara Sangyo Co., Ltd., solid content 30
%) 1.7 g, tris- (3-trimethoxysilylpropyl) isocyanurate (trade name “X-12-965”, manufactured by Shin-Etsu Chemical Co., Ltd.) 3.0 g (complete hydrolysis-condensation weight is 2.0 g) ) Were mixed and stirred at 23 ° C. for 1 hour to obtain an organic / inorganic composite composition (E-1).
The organic / inorganic composite composition (E-1) is bar-coated on a 6 cm × 6 cm acrylic plate so that the film thickness becomes 0.5 μm, dried at 70 ° C. for 10 minutes, and then cured at 23 ° C. for 1 week. As a result, a test plate (F-1) was obtained.
The organic / inorganic composite composition (E-1) is bar-coated on a 20 cm × 20 cm PVC film so that the film thickness is 0.5 μm, dried at 70 ° C. for 10 minutes, and then cured at 23 ° C. for 1 week. As a result, a test plate (G-1) was obtained.
The evaluation results of the test plates (F-1) and (G-1) are shown in Table 1.

[Example 2]
After mixing and stirring 114 g of distilled water and 48 g of ethanol in 25 g of water-dispersed colloidal silica (trade name “Snowtex O”, manufactured by Nissan Chemical Industries, Ltd., solid content 20%) having a number average particle size of 12 nm, Reference Example 1 Polymer emulsion particles (B-1) 50 g of an aqueous dispersion synthesized in the above, silica-coated titanium oxide hydrosol (trade name “TSK-5”, manufactured by Ishihara Sangyo Co., Ltd., solid content 30%) 1.7 g, Tris- 2.3 g of (3-trimethoxysilylpropyl) isocyanurate (trade name “X-12-965”, manufactured by Shin-Etsu Chemical Co., Ltd.) (total hydrolyzed and reduced weight is 1.5 g) is mixed at 23 ° C. The mixture was stirred for 1 hour to obtain an organic / inorganic composite composition (E-2).
The above organic / inorganic composite composition (E-2) is bar-coated on a 6 cm × 6 cm acrylic plate so that the film thickness becomes 0.5 μm, dried at 70 ° C. for 10 minutes, and then cured at 23 ° C. for 1 week. As a result, a test plate (F-2) was obtained.
The organic / inorganic composite composition (E-2) is bar-coated on a 20 cm × 20 cm PVC film so that the film thickness becomes 0.5 μm, dried at 70 ° C. for 10 minutes, and then cured at 23 ° C. for 1 week. As a result, a test plate (G-2) was obtained.
The evaluation results of the test plates (F-2) and (G-2) are shown in Table 1.

[Example 3]
After mixing and stirring 149 g of distilled water and 59 g of ethanol in 37.5 g of water-dispersed colloidal silica having a number average particle diameter of 12 nm (trade name “Snowtex O”, manufactured by Nissan Chemical Industries, Ltd., solid content 20%) 50 g of the polymer emulsion particles (B-1) aqueous dispersion synthesized in Example 1, 1.7 g of silica-coated titanium oxide hydrosol (trade name “TSK-5”, manufactured by Ishihara Sangyo Co., Ltd., solid content 30%), 3.0 g of tris- (3-trimethoxysilylpropyl) isocyanurate (trade name “X-12-965”, manufactured by Shin-Etsu Chemical Co., Ltd.) (total hydrolysis-condensation weight is 2.0 g) is mixed. Stirring was carried out at ° C for 1 hour to obtain an organic / inorganic composite composition (E-3).
The above organic / inorganic composite composition (E-3) is bar-coated on a 6 cm × 6 cm acrylic plate so that the film thickness is 0.5 μm, dried at 70 ° C. for 10 minutes, and then cured at 23 ° C. for 1 week. As a result, a test plate (F-3) was obtained.
The organic / inorganic composite composition (E-3) is bar-coated on a 20 cm × 20 cm PVC film so that the film thickness is 0.5 μm, dried at 70 ° C. for 10 minutes, and then cured at 23 ° C. for 1 week. As a result, a test plate (G-3) was obtained.
The evaluation results of the test plates (F-3) and (G-3) are shown in Table 1.

[Example 4]
Reference Example 1 was prepared by mixing 121 g of distilled water and 49 g of ethanol with 25 g of water-dispersed colloidal silica (trade name “Snowtex O”, manufactured by Nissan Chemical Industries, Ltd., solid content 20%) having a number average particle size of 12 nm. Polymer emulsion particles (B-1) synthesized in the above (B-1) 50 g of water dispersion, silica-coated titanium oxide hydrosol (trade name “TSK-5”, manufactured by Ishihara Sangyo Co., Ltd., solid content 30%) 1.7 g, Reference Example 3 is mixed with 3.5 g of the polyfunctional silane (C-2) synthesized in step 3 (2.0 g in terms of complete hydrolysis and contraction), and stirred at 23 ° C. for 1 hour to obtain an organic / inorganic composite composition (E-4). )
The organic / inorganic composite composition (E-4) is bar-coated on a 6 cm × 6 cm acrylic plate so that the film thickness becomes 0.5 μm, dried at 70 ° C. for 10 minutes, and then cured at 23 ° C. for 1 week. As a result, a test plate (F-4) was obtained.
The organic / inorganic composite composition (E-4) is bar-coated on a 20 cm × 20 cm PVC film so that the film thickness becomes 0.5 μm, dried at 70 ° C. for 10 minutes, and then cured at 23 ° C. for 1 week. As a result, a test plate (G-4) was obtained.
The evaluation results of the test plates (F-4) and (G-4) are shown in Table 1.

[Example 5]
Reference Example 1 was prepared by mixing 121 g of distilled water and 49 g of ethanol with 25 g of water-dispersed colloidal silica (trade name “Snowtex OS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20%) having a number average particle size of 9 nm. Polymer emulsion particles (B-1) 50 g of an aqueous dispersion synthesized in the above, silica-coated titanium oxide hydrosol (trade name “TSK-5”, manufactured by Ishihara Sangyo Co., Ltd., solid content 30%) 1.7 g, Tris- (3-trimethoxysilylpropyl) isocyanurate (trade name “X-12-965”, manufactured by Shin-Etsu Chemical Co., Ltd.) 3.0 g (complete hydrolysis-condensation weight is 2.0 g) is mixed at 23 ° C. The mixture was stirred for 1 hour to obtain an organic / inorganic composite composition (E-5).
The above organic / inorganic composite composition (E-5) is bar-coated on a 6 cm × 6 cm acrylic plate so that the film thickness becomes 0.5 μm, dried at 70 ° C. for 10 minutes, and then cured at 23 ° C. for 1 week. As a result, a test plate (F-5) was obtained.
The organic / inorganic composite composition (E-5) is bar-coated on a 20 cm × 20 cm PVC film so that the film thickness is 0.5 μm, dried at 70 ° C. for 10 minutes, and then cured at 23 ° C. for 1 week. As a result, a test plate (G-5) was obtained.
The evaluation results of the test plates (F-5) and (G-5) are shown in Table 1.

[Example 6]
Reference Example 2 was prepared by mixing 121 g of distilled water and 49 g of ethanol with 25 g of water-dispersed colloidal silica (trade name “Snowtex O”, manufactured by Nissan Chemical Industries, Ltd., solid content 20%) having a number average particle size of 12 nm. Polymer emulsion particles (B-2) 50 g of an aqueous dispersion synthesized in the above, silica-coated titanium oxide hydrosol (trade name “TSK-5”, manufactured by Ishihara Sangyo Co., Ltd., solid content 30%) 1.7 g, Tris- (3-trimethoxysilylpropyl) isocyanurate (trade name “X-12-965”, manufactured by Shin-Etsu Chemical Co., Ltd.) 3.0 g (complete hydrolysis-condensation weight is 2.0 g) is mixed at 23 ° C. The mixture was stirred for 1 hour to obtain an organic / inorganic composite composition (E-6).
The above organic / inorganic composite composition (E-6) is bar-coated on a 6 cm × 6 cm acrylic plate so that the film thickness becomes 0.5 μm, dried at 70 ° C. for 10 minutes, and then cured at 23 ° C. for 1 week. As a result, a test plate (F-6) was obtained.
The organic / inorganic composite composition (E-6) is bar-coated on a 20 cm × 20 cm PVC film so that the film thickness becomes 0.5 μm, dried at 70 ° C. for 10 minutes, and then cured at 23 ° C. for 1 week. As a result, a test plate (G-6) was obtained.
The evaluation results of the test plates (F-6) and (G-6) are shown in Table 1.

[Example 7]
After mixing and stirring 115 g of distilled water and 47 g of ethanol in 25 g of water-dispersed colloidal silica having a number average particle size of 12 nm (trade name “Snowtex O”, manufactured by Nissan Chemical Industries, Ltd., solid content 20%), Reference Example 1 Polymer emulsion particles (B-1) dispersed in water (50 g), tris- (3-trimethoxysilylpropyl) isocyanurate (trade name “X-12-965”, manufactured by Shin-Etsu Chemical Co., Ltd.) 3.0 g (The complete hydrolysis-condensation reduced weight is 2.0 g) and the mixture was stirred at 23 ° C. for 1 hour to obtain an organic / inorganic composite composition (E-7).
The organic / inorganic composite composition (E-7) is 0.5 μm thick on a 6 cm × 6 cm acrylic plate.
After being bar-coated to m, the sample was dried at 70 ° C. for 10 minutes and then cured at 23 ° C. for 1 week to obtain a test plate (F-7).
The organic / inorganic composite composition (E-7) is bar-coated on a 20 cm × 20 cm PVC film so that the film thickness becomes 0.5 μm, dried at 70 ° C. for 10 minutes, and then cured at 23 ° C. for 1 week. As a result, a test plate (G-7) was obtained.
The evaluation results of the test plates (F-7) and (G-7) are shown in Table 1.

[Example 8]
The organic / inorganic composite composition (E-2) obtained in Example 2 was bar-coated on a 6 cm × 6 cm acrylic plate so that the film thickness was 0.5 μm, and then dried at 70 ° C. for 10 minutes. A test plate (F-8) was obtained by curing at 0 ° C. for 1 week.
After bar coating the organic / inorganic composite composition (E-2) obtained in Example 2 on a 20 cm × 20 cm PVC film so that the film thickness becomes 0.5 μm, it is dried at 70 ° C. for 10 minutes, and 50 A test plate (G-8) was obtained by curing at 0 ° C. for 1 week.
Table 1 shows the evaluation results of the test plates (F-8) and (G-8).

[Comparative Example 1]
Reference Example 1 was prepared by mixing 91 g of distilled water and 42 g of ethanol with 25 g of water-dispersed colloidal silica (trade name “Snowtex O”, manufactured by Nissan Chemical Industries, Ltd., solid content 20%) having a number average particle size of 12 nm. 50 g of the polymer emulsion particles (B-1) synthesized in the above and 1.7 g of silica-coated titanium oxide hydrosol (trade name “TSK-5”, manufactured by Ishihara Sangyo Co., Ltd., solid content 30%) are mixed. The mixture was stirred at 23 ° C. for 1 hour to obtain an organic / inorganic composite composition (E-9).
The organic / inorganic composite composition (E-9) is bar-coated on a 6 cm × 6 cm acrylic plate so that the film thickness is 0.5 μm, dried at 70 ° C. for 10 minutes, and then cured at 23 ° C. for 1 week. As a result, a test plate (F-9) was obtained.
The organic / inorganic composite composition (E-9) is bar-coated on a 20 cm × 20 cm PVC film so that the film thickness is 0.5 μm, dried at 70 ° C. for 10 minutes, and then cured at 23 ° C. for 1 week. As a result, a test plate (G-9) was obtained.
The evaluation results of the test plates (F-9) and (G-9) are shown in Table 1. Although the stain resistance was good, the alcohol resistance and the film appearance were poor.

[Comparative Example 2]
After mixing and stirring 50 g of water-dispersed colloidal silica having a number average particle size of 12 nm (trade name “Snowtex O”, manufactured by Nissan Chemical Industries, Ltd., solid content 20%) with 153 g of distilled water and 51 g of ethanol, silica-coated oxidation Titanium hydrosol (trade name “TSK-5”, manufactured by Ishihara Sangyo Co., Ltd., solid content 30%) 3.3 g, tris- (3-trimethoxysilylpropyl) isocyanurate (trade name “X-12-965”) , Manufactured by Shin-Etsu Chemical Co., Ltd.) (total hydrolyzed and reduced weight is 2.0 g), and stirred at 23 ° C. for 1 hour to obtain an organic / inorganic composite composition (E-10). .
The organic / inorganic composite composition (E-10) is bar-coated on a 6 cm × 6 cm acrylic plate so that the film thickness becomes 0.5 μm, dried at 70 ° C. for 10 minutes, and then cured at 23 ° C. for 1 week. As a result, a test plate (F-10) was obtained.
The organic / inorganic composite composition (E-10) is bar-coated on a 20 cm × 20 cm PVC film so that the film thickness becomes 0.5 μm, dried at 70 ° C. for 10 minutes, and then cured at 23 ° C. for 1 week. As a result, a test plate (G-10) was obtained.
The evaluation results of the test plates (F-10) and (G-10) are shown in Table 1. Although the alcohol resistance and stain resistance were good, the crack resistance was poor.

[Comparative Example 3]
Reference Example 1 was prepared by mixing 121 g of distilled water and 49 g of ethanol with 25 g of water-dispersed colloidal silica (trade name “Snowtex O”, manufactured by Nissan Chemical Industries, Ltd., solid content 20%) having a number average particle size of 12 nm. Polymer emulsion particles (B-1) 50 g of an aqueous dispersion synthesized in the above, silica-coated titanium oxide hydrosol (trade name “TSK-5”, manufactured by Ishihara Sangyo Co., Ltd., solid content 30%) 1.7 g, tetraethoxy Silane (trade name “KBE-04”, manufactured by Shin-Etsu Chemical Co., Ltd.) 7.1 g (total hydrolysis-condensation weight is 2.0 g) is mixed and stirred at 23 ° C. for 1 hour to obtain an organic / inorganic composite composition. A product (E-11) was obtained.
The organic / inorganic composite composition (E-11) is bar-coated on a 6 cm × 6 cm acrylic plate so that the film thickness becomes 0.5 μm, dried at 70 ° C. for 10 minutes, and then cured at 23 ° C. for 1 week. As a result, a test plate (F-11) was obtained.
The organic / inorganic composite composition (E-11) is bar-coated on a 20 cm × 20 cm PVC film so that the film thickness is 0.5 μm, dried at 70 ° C. for 10 minutes, and then cured at 23 ° C. for 1 week. As a result, a test plate (G-11) was obtained.
The evaluation results of the test plates (F-11) and (G-11) are shown in Table 1. Although the alcohol resistance and stain resistance were good, the crack resistance was poor.

[Comparative Example 4]
Reference Example 1 was prepared by mixing 121 g of distilled water and 49 g of ethanol with 25 g of water-dispersed colloidal silica (trade name “Snowtex O”, manufactured by Nissan Chemical Industries, Ltd., solid content 20%) having a number average particle size of 12 nm. Polymer emulsion particles (B-1) synthesized in the above (B-1) 50 g of water dispersion, silica-coated titanium oxide hydrosol (trade name “TSK-5”, manufactured by Ishihara Sangyo Co., Ltd., solid content 30%) 1.7 g, methyltri Methoxysilane (trade name “KBM-13”, manufactured by Shin-Etsu Chemical Co., Ltd.) (4.1 g) (complete hydrolysis-condensation conversion weight is 2.0 g) is mixed, and stirred at 23 ° C. for 1 hour. A composition (E-12) was obtained.
The organic / inorganic composite composition (E-12) is bar-coated on a 6 cm × 6 cm acrylic plate so that the film thickness is 0.5 μm, dried at 70 ° C. for 10 minutes, and then cured at 23 ° C. for 1 week. As a result, a test plate (F-12) was obtained.
The organic / inorganic composite composition (E-12) is bar-coated on a 20 cm × 20 cm PVC film so that the film thickness becomes 0.5 μm, dried at 70 ° C. for 10 minutes, and then cured at 23 ° C. for 1 week. As a result, a test plate (G-12) was obtained.
The evaluation results of the test plates (F-12) and (G-12) are shown in Table 1. Alcohol resistance and crack resistance were good, but the contamination resistance was poor.

  Provided by the present invention, an organic / inorganic composite composition capable of forming an organic / inorganic composite exhibiting high levels of weather resistance, stain resistance, and transparency is used for building exteriors, exterior display applications, It is useful as a coating agent for automobiles, displays, lenses and the like.

Claims (15)

Inorganic oxide particles (A) composed of one selected from silicon oxide, aluminum oxide, antimony oxide, and composite oxides thereof, polymer emulsion particles (B), and the following formula (1) An organic / inorganic composite composition comprising a polyfunctional silane (C) having 3 to 20 atomic groups (c1) in one molecule,
R ¹ _n SiX _3-n A- (1)
{Wherein R ¹ represents hydrogen or an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, or an aryl group. Moreover, you may have a halogen group, a hydroxy group, a mercapto group, an amino group, a (meth) acryloyl group, and an epoxy group on these substituents. X represents a hydrolyzable group, and n is an integer of 0-2. A is a site containing 2 to 20 methylene groups. } The polymer emulsion particles (B) polymerize a hydrolyzable silicon compound (b1) and a vinyl monomer (b2) having a secondary amide group and / or a tertiary amide group in the presence of water and an emulsifier. An organic / inorganic composite composition obtained by   The organic / inorganic composite composition according to claim 1, wherein the polyfunctional silane (C) is a reaction product of aminosilane and isocyanate silane.   The organic / inorganic composite composition according to claim 1, wherein the polyfunctional silane (C) is a reaction product of a polyamine and an isocyanate silane.   The organic / inorganic composite composition according to claim 1, wherein the polyfunctional silane (C) is a reaction product of a polyol and an isocyanate silane.   The organic / inorganic composite composition according to claim 1, wherein the polyfunctional silane (C) is tris- (3-trialkoxysilylpropyl) isocyanurate.   The organic-inorganic composite composition according to any one of claims 1 to 5, wherein the polymer emulsion particles (B) have a core / shell structure formed of two or more layers. _{TiO 2, ZnO, SrTiO 3,} BaTiO 3, BaTiO 4, BaTi 4 O 9, K 2 NbO 3, Nb 2 O 5, Fe 2 O 3, Ta 2 O 5, K 3 Ta 3 Si 2 O 3, WO 3 , SnO ₂ , Bi ₂ O ₃ , BiVO ₄ , NiO, Cu ₂ O, RuO ₂ , CeO ₂ , a metal oxide (D) having photocatalytic activity, and inorganic oxide particles (A) The organic-inorganic composite composition according to any one of claims 1 to 6, characterized by comprising:   An aqueous composition comprising the organic-inorganic composite composition according to any one of claims 1 to 7.   The organic-inorganic composite which consists of solid content of the composition as described in any one of Claims 1-8.   The organic-inorganic composite which comprises solid content of the composition as described in any one of Claims 1-8.   The continuous layer is formed in a state where the inorganic oxide particles (A) and the shell phase of the polymer emulsion particles (B) having a core / shell structure interact with each other, and the particulate core phase is present in the continuous layer. The organic-inorganic composite according to 9 or 10.   The functional composite which has the organic-inorganic composite as described in any one of Claims 9-11 on a base material.   The functional composite according to claim 12, wherein the substrate is an organic substrate.   The functional composite according to claim 12, wherein the substrate is a resin substrate.   The functional composite according to any one of claims 12 to 14, wherein the functional composite is a functional composite for building exterior.