JP5362416B2 - Organic / inorganic composite composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To easily form an organic-inorganic composite composition in a simple manner and with low environmental load without using a special apparatus, the organic-inorganic composite composition having excellent weatherability, chemical resistance, optical characteristics, anti-fouling properties, anti-fogging properties, antistatic properties, transparency, glossiness holding properties and the like. <P>SOLUTION: The organic-inorganic composite composition includes a metal oxide (A) having &le;100 nm particle diameter and polymer emulsion particles (B), which are dispersed in water, wherein the metal oxide (A) includes at least one of metal oxide having a refractive index of 1.8 to 2.8. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to an organic / inorganic composite composition 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 for architectural exteriors, automobiles, displays, and lenses.

  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 made. 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.

  In JP-A-6-322136 and JP-A-2003-41198, an inorganic substance and an organic polymer, or an inorganic polymer-organic polymer copolymer is dissolved or dispersed in an organic solvent, whereby film forming property or It is disclosed to improve moldability.

  However, in order to obtain an organic / inorganic composite material from these materials, there has been a problem in that an organic solvent having a problem of toxicity or environmental pollution and a risk of fire is released into the atmosphere at the time of use.

  WO 2007/069596 discloses an organic / inorganic composite that is improved in this point and is excellent in stain resistance and weather resistance.

JP-A-6-322136 JP 2003-41198 A JP2007 / 079596

  An object of the present invention is to provide an organic / inorganic composite excellent in weather resistance, chemical resistance, optical characteristics, antifouling property, antifogging property, antistatic property, transparency, gloss retention, etc. It is easy to form easily and with little environmental load without using.

  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. An organic-inorganic composite composition comprising a metal oxide (A) having a particle size of 100 nm or less and polymer emulsion particles (B) dispersed in water, wherein the metal oxide (A) has a refractive index of 1. An organic / inorganic composite composition comprising at least one metal oxide of 8 to 2.8.

  2. The metal oxide (A) contains at least zirconium oxide (a1) and silicon oxide (a2), and has a mass ratio of (A) / (B) = 10/90 to 90/10, (a1) /{(A)+(B)}=0.01 to 0.5 and (a2) / {(A) + (B)} = 0.1 to 0.8 Composition.

  3. The polymer emulsion particles (B) are obtained by polymerizing a hydrolyzable silicon compound (b1) and a vinyl monomer (b2) in the presence of water and an emulsifier, and have a particle size of 10 to 10. The composition according to invention 1 or 2, which is 800 nm.

  4). The composition according to the invention 2 or 3, wherein the zirconium oxide (a1) is an aqueous dispersion and has a pH of 8 to 11.

  5. The composition according to any one of Inventions 2 to 4, wherein the zirconium oxide (a1) is a zirconium oxide-yttrium oxide mixture colloid (a3).

  6). The composition according to any one of Inventions 1 to 5, wherein the metal oxide (A) contains at least one metal oxide (a4) having photocatalytic activity.

  7). The composition according to Invention 6, wherein the metal oxide (a4) is titanium oxide (a5).

  8). A functional inorganic composite comprising the composition according to any one of inventions 1 to 7 formed on a substrate.

  9. A building characterized in that the functional composite according to the invention 8 is used for an exterior.

  The aqueous organic / inorganic composite of the present invention is excellent in weather resistance, chemical resistance, optical properties, antifouling properties, antifogging properties, antistatic properties, transparency, gloss retention, etc., and an organic solvent. And can be formed easily without using a special apparatus.

  Hereinafter, the present invention will be described in detail.

  The organic / inorganic composite composition of the present invention comprises a metal oxide (A) having a particle size of 100 nm or less and polymer emulsion particles (B) dispersed in water, the metal oxide (A). Contains at least one metal oxide having a refractive index of 1.8 to 2.8.

  By blending a metal oxide having a refractive index of 1.8 to 2.8, the refractive index of the coating film can be controlled. Examples of such metal oxides include titanium oxide, zirconium oxide, zinc oxide, chromium oxide, cadmium oxide, iron oxide, copper oxide, and the like.

  Of these, zirconium oxide (a1) is preferable. The state of zirconium oxide (a1) is not particularly limited, but an aqueous dispersion is preferable for handling. Among these, an aqueous dispersion having a pH of 8 to 11 is preferable from the viewpoint of blending stability. The particle size is required to be 100 nm or less from the viewpoint of transparency, preferably 50 nm or less, more preferably 30 nm or less.

  In particular, the organic / inorganic composite obtained from a composition using zirconium oxide-yttrium oxide mixture colloid (a3), which is stabilized with yttrium oxide, has particularly high transparency and inhibits the design of the base. This is preferable.

  Zirconium oxide includes nano-use ZR-30BS (trade name), ZR-30BH (trade name), ZR-30AH (trade name), ZR-30AL (trade name), first rare earth, manufactured by Nissan Chemical Industries, Ltd. Examples include ZSL-10A (trade name), ZSL-10T (trade name), and ZSL-20N (trade name) manufactured by Chemical Corporation. Among these, ZR-30BS (trade name) is particularly preferable in terms of transparency and blending stability.

  In the aqueous organic / inorganic composite composition of the present invention, when silicon oxide (a2) is blended, an organic / inorganic composite having excellent weather resistance and hydrophilicity can be obtained. In particular, when interacting with the polymer emulsion particles (B), an organic / inorganic composite having further excellent weather resistance, chemical resistance, optical properties, antifouling properties, antifogging properties, antistatic properties and the like is formed. It becomes possible.

  Here, as an example of the interaction between the silicon oxide (a2) and the polymer emulsion particles (B), for example, the hydroxyl group of the silicon oxide (a2) and the hydrolyzable metal constituting the polymer emulsion particles (B) Examples include condensation (chemical bonding) of the compound (b1) with the polymerization product and bonding (hydrogen bonding) with secondary and / or tertiary amide groups constituting part of the polymer emulsion particles (B). can do.

  Although there is no restriction | limiting in particular as a state of silicon oxide (a2), if it is disperse | distributing in water and / or a hydrophilic organic solvent, it is easy to handle and preferable. Here, silicon oxide (a2) is a hydrophilic organic solvent, for example, alcohols such as ethylene glycol, butyl cellosolve, n-propanol, isopropanol, n-butanol, ethanol and methanol, and 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 a mixture of two or more of these.

  The particle diameter of silicon oxide (a2) is required to be 100 nm or less, and preferably 50 nm or less, from the viewpoint of transparency.

  The mass ratio (A) / (B) between the metal oxide (A) and the polymer emulsion particles (B) is preferably 10/90 to 90/10. Further, the mass blending ratio of zirconium oxide (a1) is (a1) / {(A) + (B)} = 0.01 to 0.5, and the mass blending ratio of silicon oxide (a2) is (a2) / {(A) + (B)} = A range of 0.1 to 0.8 is preferable. An organic / inorganic composite composition blended in these ranges is preferable because an organic / inorganic composite having excellent transparency and stain resistance can be obtained.

  Further, it is possible to further add a photocatalyst to the organic / inorganic composite of the present invention. In this case, the organic / inorganic composite of the present invention is very preferable because it exhibits photocatalytic activity and / or hydrophilicity by light irradiation.

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, and V Layered oxides having various 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-10-244. Mention may be made of reference 65 discloses etc.).

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. Among them, an organic / inorganic composite composition using rutile type titanium oxide is preferable because the photocatalytic activity can be controlled.

  As the polymer emulsion particles (B) used in the aqueous organic / inorganic composite composition of the present invention, various known ones can be used.

  For example, acrylic emulsion, styrene-butadiene emulsion, PTFE emulsion, etc. can be exemplified.

  In this embodiment, polymer particles obtained by a method such as emulsion polymerization can be used as the polymer emulsion particles (B). Examples of the polymer constituting the polymer emulsion particles include conventionally known poly (meth) acrylate-based, polyvinyl acetate-based, vinyl acetate-acrylic-based, ethylene acetic acid obtained by radical polymerization, anionic polymerization, cationic polymerization, etc. in an aqueous medium. Vinyl, silicone, polybutadiene, styrene butadiene, NBR, polyvinyl chloride, chlorinated polypropylene, polyethylene, polystyrene, vinylidene chloride, polystyrene- (meth) acrylate, styrene-maleic anhydride And a modified copolymer represented by a silicone-modified acrylic, a fluorine-acrylic, an acrylic-silicone, and an epoxy-acrylic. These are in the state of an aqueous dispersion, and are used alone or in combination of two or more. Preferred examples thereof include an acrylic resin emulsion and an acrylic-silicon resin emulsion. The polymer emulsion particles can be obtained by emulsion polymerization of monomers such as acrylic acid ester and methacrylic acid ester.

  Among them, polymer emulsion particles (B) having a particle diameter of 10 to 800 nm obtained by polymerizing hydrolyzable silicon compound (b1) and vinyl monomer (b2) in the presence of water and an emulsifier are used. From the organic / inorganic composite composition obtained in this way, an organic / inorganic composite having particularly high weather resistance, transparency and flexibility can be obtained, which is particularly preferable.

  Examples of the hydrolyzable silicon compound (b1) used to produce the polymer emulsion particles (B) of the present invention include compounds represented by the following formula (1), condensation products thereof, and silane coupling agents. can do.

SiWxRy (1)
Wherein W is 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. R represents at least one group selected from: 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 substituted group; 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. (It is an integer of 4 or less, and y is an integer of 0 to 3. Further, 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, silicon alkoxides having a phenyl group, for example, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, and the like 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 are vinyl. By copolymerization or chain transfer reaction with dimer (b2) it is possible to produce 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) and the polymer product of the vinyl monomer (b2) constituting the polymer emulsion particles (B) can be combined by chemical bonding. The aqueous organic / inorganic composite composition containing such polymer emulsion particles (B) can form an organic / inorganic composite having excellent weather resistance, chemical resistance, optical properties, strength, etc. Highly preferred.

  Examples of the vinyl monomer (b2) include acrylic acid ester, methacrylic acid ester, aromatic vinyl compound, vinyl cyanide, carboxyl group-containing vinyl monomer, hydroxyl group-containing vinyl monomer, and epoxy group-containing vinyl. And monomers containing functional groups such as monomers, carbonyl group-containing vinyl monomers, and anionic vinyl monomers.

  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.

  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 the vinyl monomers as 1 type, or 2 or more types of mixtures.

  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.

  The amount of the hydroxyl group-containing vinyl monomer mentioned above is preferably 0 to 80% by mass, more preferably 0.1 to 50% by mass in the total vinyl monomer as one or a mixture of two or more. is there.

  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.

  It is preferable to use at least one vinyl monomer (b3) having a secondary and / or tertiary amide group as the vinyl monomer (b2).

  As an example of the vinyl monomer (b3) having a secondary and / or tertiary amide group, N-alkyl or N-alkylene-substituted (meth) acrylamide can be exemplified. 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-propylacrylamide, N- Methyl-N-isopropyla Rilamide, 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 methacrylamide and the like.

  Among the vinyl monomers (b3) having a secondary and / or tertiary amide group, it is preferable to use a vinyl monomer having a tertiary amide group. In particular, N, N-diethylacrylamide is very excellent in polymerization stability in the presence of water and an emulsifier, and also the hydroxyl group of the polymerization product of the hydrolyzable silicon compound (b1) and the hydroxyl group of the metal oxide (A). It is very preferable because a strong hydrogen bond can be formed.

  The amount of the vinyl monomer (b3) having the secondary and / or tertiary amide group is 0.1 or more in terms of mass ratio [(b3) / (B)] to the resulting polymer emulsion particles (B). The mass ratio (b3) / (A) to the metal oxide (A) is preferably 0.1 or more and 1.0 or less.

  Specific examples of the vinyl monomer (b2) other than the above include, for example, (meth) acrylamide, olefins such as ethylene, propylene, and isobutylene, dienes such as butadiene, vinyl chloride, vinylidene chloride, tetrafluoroethylene, and the like. , Haloolefins such as chlorotrifluoroethylene, vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl benzoate, vinyl pt-butylbenzoate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl versatic acid Carboxylic acid vinyl esters such as vinyl laurate, isopropenyl acetate, isopropenyl carboxylic acid such as isopropenyl propionate, vinyl ethers such as ethyl vinyl ether, isobutyl vinyl ether and cyclohexyl vinyl ether, styrene , Aromatic vinyl compounds such as vinyl toluene, 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, perfluoropropylo Examples thereof include methyl (meth) acrylate, vinyl pyrrolidone, trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate and the like and combinations thereof.

  In the present invention, a chain transfer agent may be used for the purpose of controlling the molecular weight of the polymerization product of the vinyl monomer (b2).

  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 dimer 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.

  The mass ratio (b2) / (b1) of the vinyl monomer (b2) to the hydrolyzable silicon compound (b1) is 5/95 to 95/5, preferably 10/90 to 90/10.

  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, it is preferable from the surface of superposition | polymerization stability that 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).

  In the present invention, it is possible to use a cyclic siloxane oligomer 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 aqueous organic / inorganic composite composition of the present invention.

  As said cyclic siloxane oligomer, the compound represented by following formula (2) can be illustrated.

(R ′ ₂ SiO) m (2)
(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, and m is an integer of 2 ≦ m ≦ 20. )
Among the cyclic siloxane oligomers, cyclic dimethylsiloxane oligomers such as octamethylcyclotetrasiloxane are preferable from the viewpoint of reactivity.

  In the present invention, the hydrolyzable silicon compound (b1) described above can be used in combination with a titanium alkoxide, a zirconium alkoxide, a condensation product thereof, or a chelated product thereof. By using these compounds in combination, an organic / inorganic composite excellent in water resistance, hardness and the like can be formed from the aqueous organic / inorganic composite composition of the present invention.

  Specific examples of the titanium alkoxide include, for example, tetramethoxy titanium, tetraethoxy titanium, tetraisopropoxy titanium, tetra-n-propoxy titanium, tetra-n-butoxy titanium, tetra-sec-butoxy titanium, tetra-tert-butoxy. Examples include titanium.

  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, tetraisopropoxy zirconium, tetra-n-propoxy zirconium, tetra-n-butoxy zirconium, tetra-sec-butoxy zirconium, tetra-tert-butoxy. Zirconium 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.

  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, for example , 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 aqueous 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. preferable.

  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 of these include, for example, Eleminol JS-2 (trade name) (manufactured by Sanyo Kasei Co., Ltd.), Latemul S-120 (trade name), S-180A (trade name) or S-180 (trade name) ( And Kao Corporation).

  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 (trade name) or SR-1025 (trade name) (Asahi Denka Kogyo) For example).

  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) 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, and p-toluenesulfonic acid Sulfonic acids 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, etc., acidic or weakly acidic emulsifier Acidic compounds such as inorganic salts, phthalic acid, phosphoric acid, nitric acid; sodium hydroxide, potassium hydroxide, sodium methylate, sodium acetate, tetramethylammonium chloride, tetramethylammonium hydroxide, tributylamine, diazabicyclounde SE , Basic compounds such as ethylenediamine, diethylenetriamine, ethanolamine, γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane; tin such as dibutyltin octylate, dibutyltin dilaurate A compound etc. can be mentioned.

  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, the polymerization catalyst for the vinyl monomer (b2) is preferably a radical polymerization catalyst that undergoes radical decomposition by heat or a reducing substance to cause addition polymerization of the vinyl monomer, and is 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 aqueous organic / inorganic composite composition of the present invention contain a hydrolyzable silicon compound (b1) and a vinyl monomer (b2) in the presence of water and an emulsifier. It can be preferably obtained by polymerization in the presence of a polymerization catalyst.

  Here, the polymerization of the hydrolyzable silicon compound (b1) and the vinyl monomer (b2) can be carried out separately. 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 the particle diameter to such a range and combining it with a metal oxide (A) having a particle diameter of 100 nm or less to form an aqueous organic / inorganic composite composition, weather resistance, chemical resistance, optical characteristics, Can 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 polymer emulsion particles (B) having such a particle size, the hydrolyzable metal compound (b1) and the vinyl monomer (b2) in the presence of a sufficient amount of water for the emulsifier to form micelles. So-called emulsion polymerization is the most suitable method.

  As a method of emulsion polymerization, for example, the hydrolyzable silicon compound (b1) and the vinyl monomer (b2) are dropped into the reaction vessel as they are or in an emulsified state, in a lump, in a divided manner, or continuously. In the presence of the polymerization catalyst, polymerization is preferably performed at a reaction temperature of about 30 to 150 ° C., preferably from atmospheric pressure to a pressure of 10 MPa if necessary. 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 compound (b1) and vinyl in the presence of water and an emulsifier necessary for polymerizing the hydrolyzable silicon compound (b1). Although the monomer (b2) is polymerized in the presence of a solvent, if necessary, a method of adding water until the polymerization product becomes an emulsion can also be applied, but the resulting polymer emulsion particles are compared with the emulsion polymerization method described above. It is difficult to control the particle size of (B).

  In the present invention, when the polymer emulsion particles (B) have a core / shell structure formed of two or more layers, the aqueous organic / inorganic composite composition containing the polymer emulsion particles (B) is mechanically 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) to the hydrolyzable silicon compound (b1) in the innermost layer is 1.0 or less, and the mass ratio (b2) of the outermost layer. When / (b1) is 0.1 or more and 5.0 or less, the obtained composite is preferable because both weather resistance and mechanical properties are particularly good.

  Multi-stage emulsion polymerization is very useful as a method for producing the core / shell structured polymer emulsion particles (B).

  Here, multistage emulsion polymerization means that two or more different hydrolyzable silicon compounds (b1) and vinyl monomers (b2) having different compositions are prepared and polymerized in separate stages. To do.

  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 (b2) and / or the hydrolyzable silicon compound (b1) is polymerized in the presence of water and an emulsifier. A method of polymerizing the hydrolyzable silicon compound (b1) vinyl monomer (b2) in the presence of the obtained seed particles can be exemplified.

  The synthesis of the polymer emulsion particles (B) by the two-stage emulsion polymerization is a first stage in which emulsion polymerization is performed by supplying a first series (vinyl monomer (b2) and / or hydrolyzable metal compound (b1)). And the second stage (the hydrolyzable metal compound (b1) and the vinyl monomer (b2)) are supplied to the second stage, followed by emulsion polymerization in an aqueous medium. It is carried out by a staged polymerization process. At this time, the mass ratio of the solid content mass (M1) in the first series to the solid content mass (M2) in the second series is preferably (M1) / (M2) = 9/1 to 1/9. 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) in the presence of water and an emulsifier, the hydrolyzable silicon compound (b1) and the vinyl monomer ( When b2) is polymerized, the polymerization stability is excellent, which is preferable.

  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. The aqueous organic / inorganic composite composition to be contained is preferable because it can form an organic / inorganic composite that is excellent in flexibility at room temperature and hardly causes cracking.

  In the present invention, when multi-stage emulsion polymerization of three or more stages is performed, 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.

  In addition, alcohols can be added to the aqueous organic / inorganic composite composition of the present invention for the purpose of controlling the interaction between the metal oxide (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.

  The organic / inorganic composite of the present invention includes at least one selected from the group consisting of a benzophenone-based UV absorber, a benzotriazole-based UV absorber, and a triazine-based UV absorber as a UV absorber, and a hindered amine as a light stabilizer. At least one selected from the group consisting of system 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. Moreover, since it is excellent in a weather resistance, it is preferable to use an ultraviolet absorber and a light stabilizer in combination.

  These ultraviolet absorbers and light stabilizers can be simply blended with the metal oxide (A) and the polymer emulsion particles (B), and are allowed to coexist when the polymer emulsion particles (B) are synthesized. It is also possible.

  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′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy- - 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] pro Condensation product of pionate and polyethylene glycol (molecular weight 300) (product name: TINUVIN 1130, manufactured by Ciba Geigy Japan), 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) ) Benzotriazole, 2- (2′-hydroxy-4′-octoxy) Phenyl) benzotriazole, 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 (manufactured by 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] phenylpropio Nate (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 Geigy 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.

  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.
The functional composite of the present invention is preferably heat-treated at 20 ° C. to 500 ° C., more preferably 40 ° C. to 250 ° C., if desired, after applying the aqueous organic / inorganic composite composition to a substrate and drying, for example. Or an ultraviolet ray 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.
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.

  Examples of the application of the organic / inorganic composite composition of the present invention to the antifouling technology field include, for example, building materials, building exteriors, building interiors, window frames, window glass, structural members, housing and other building equipment, particularly toilets, bathtubs, and washbasins Tables, lighting fixtures, lighting covers, kitchen utensils, tableware, dishwashers, tableware dryers, sinks, cooking ranges, kitchen hoods, ventilation fans, etc. Therefore, the present invention also relates to a building using the functional composite as an exterior. The organic / inorganic composite composition or functional composite of the present invention can also be used for the exterior and coating of vehicles, and the interior thereof depending on the application, such as covers for vehicle lighting, window glass, instruments, display panels, etc. It is effective for use in parts that require high performance, and is used for exteriors of mechanical devices and articles, dust-proof covers and coatings, display devices, covers, traffic signs, various display devices, advertising towers and other display objects, and 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. It can also be used for exteriors such as greenhouses 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.

  The following examples, reference examples and comparative examples will specifically explain the present invention, but these do not limit the scope of the present invention.

In Examples, Reference Examples and Comparative Examples, various physical properties were measured by the following methods.
1. 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. Color Difference Color difference ΔE was measured using a color guide manufactured by BYK Gardler.
[Reference example]
Synthesis of polymer emulsion particles (B) aqueous dispersion [Reference Example 1]
Synthesis of Aqueous Dispersion of Polymer Emulsion Particles (B-1) 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 liquid of 50 g of dimethyldimethoxysilane and 50 g of phenyltrimethoxysilane was dropped over about 2 hours while keeping the temperature in the reaction vessel at 80 ° C., and then the temperature in the reaction vessel was 80 ° C. 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, and 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% solid content aqueous solution), a mixed solution of ammonium persulfate 2% by mass aqueous solution 40 g, and ion-exchanged water 1000 g, the temperature in the reaction vessel was kept at 80 ° C. In the state, 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. An aqueous dispersion of polymer emulsion particles (B-1) having a number average particle diameter of 130 nm was obtained.
[Reference Example 2]
Synthesis of aqueous dispersion of polymer emulsion particles (B-2) Copolymerized with 609 parts by mass of ion-exchanged water and ethylenically unsaturated monomer in a reactor equipped with a stirrer, reflux condenser, dropping tank and thermometer. Sulfosuccinic acid diester ammonium salt having a possible double bond in the molecule (trade name “Latemul S-180A”, manufactured by Kao Corporation) 10 parts by mass of 25% aqueous solution, 26 parts by mass of cyclohexyl methacrylate, n-methacrylic acid n- 8 parts by weight of butyl, 14 parts by weight of methyl methacrylate, 2.5 parts by weight of butyl acrylate, 0.8 parts by weight of methacrylic acid, 0.8 parts by weight of acrylic acid, and 0.4 parts by weight of acrylamide were added to the reaction vessel. After raising the temperature to 80 ° C., 5 parts by mass of a 2% aqueous solution of ammonium persulfate, 1 part by mass of γ-methacryloxypropyltrimethoxysilane, Tokishishiran 68 parts by mass, and was charged with dimethyl dimethoxy silane 27 parts by weight into the reaction vessel. After the generation of heat due to the initiation of polymerization was confirmed, the temperature in the reaction vessel was raised to 85 ° C. and maintained for 30 minutes. Next, in a state where the temperature in the reaction vessel is maintained at 80 ° C., 45 parts by mass of ion exchanged water, sulfosuccinic acid diester ammonium salt having a double bond copolymerizable with an ethylenically unsaturated monomer in the molecule ( Trade name "Latemul S-180A", manufactured by Kao Corporation) 10 parts by weight of 25% aqueous solution, 26 parts by weight of cyclohexyl methacrylate, 8 parts by weight of n-butyl methacrylate, 14 parts by weight of methyl methacrylate, butyl acrylate 2 0.5 parts by weight, 0.8 parts by weight of methacrylic acid, 0.8 parts by weight of acrylic acid, 0.4 parts by weight of acrylamide, and 5 parts by weight of 2% aqueous solution of ammonium persulfate, and 46 parts by weight of methyltrimethoxysilane And a mixed solution consisting of 18 parts by mass of dimethyldimethoxysilane are poured into a reaction vessel from a separate dropping tank over 30 minutes, and further at 80 ° C. Was time held. Next, in a state where the temperature in the reaction vessel is maintained at 80 ° C., 130 parts by mass of ion-exchanged water, a sulfosuccinic acid diester ammonium salt having a double bond copolymerizable with an ethylenically unsaturated monomer in the molecule ( 50 parts by mass of 25% aqueous solution of trade name “Latemul S-180A” manufactured by Kao Corporation, 7 parts by mass of 20% aqueous solution of polyoxyethylene lauryl ether (trade name “Emulgen 130K” manufactured by Kao Corporation), Mixed liquid consisting of 123 parts by weight of cyclohexyl methacrylate, 37 parts by weight of n-butyl methacrylate, 4 parts by weight of methyl methacrylate, 79 parts by weight of butyl acrylate, 4 parts by weight of methacrylic acid, and 12 parts by weight of 2% aqueous solution of ammonium persulfate. Γ-methacryloxypropyltrimethoxysilane 2 parts by mass, methyltrimethoxysilane 170 parts by mass, and dimethyl And a mixture consisting dimethoxysilane 68 parts by weight was injected over a period of 2 hours from separate dropping funnel into the reaction vessel and held for 1.5 hours at 80 ° C.. After cooling to room temperature, the hydrogen ion concentration of the liquid in the reaction vessel was measured and found to be pH 2.8. A 25% aqueous ammonia solution was added to the reaction vessel to adjust the pH of the solution to 8, and then filtered through a 100 mesh wire net. The solid content was adjusted to 10.0% by mass with ion-exchanged water to obtain an aqueous dispersion of polymer emulsion particles (B-2) having a number average particle size of 127 nm.
[Example 1]
To 100 g of the polymer emulsion particles (B-1) aqueous dispersion synthesized in Reference Example 1, an aqueous dispersion 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 and an aqueous dispersion colloidal zirconia having a number average particle size of 4 nm (trade name “Nanouse ZR-30BS”, manufactured by Nissan Chemical Industries, Ltd., solid content 30%) and 30 g of water-based organic / inorganic composite A composition was obtained.

This water-based organic / inorganic composite composition was spray-coated on a black glass plate so as to have a film thickness of 1 μm and baked at 70 ° C. for 10 minutes to obtain a sample. The color difference ΔE before and after coating was 1.0.
[Example 2]
To 100 g of the polymer emulsion particles (B-2) aqueous dispersion synthesized in Reference Example 2, an aqueous dispersion colloidal silica having a number average particle size of 12 nm (trade name “Snowtex O”, manufactured by Nissan Chemical Industries, Ltd., solid content) 20%) 50 g and an aqueous dispersion colloidal zirconia having a number average particle size of 4 nm (trade name “Nanouse ZR-30BS”, manufactured by Nissan Chemical Industries, Ltd., solid content 30%) and 30 g of water-based organic / inorganic composite A composition was obtained.

This aqueous organic / inorganic composite composition was spray-coated on a black slate plate to a thickness of 1 μm and baked at 70 ° C. for 10 minutes to obtain a sample. The color difference ΔE before and after coating was 1.1.
[Comparative Example 1]
To 100 g of the polymer emulsion particles (B-1) aqueous dispersion synthesized in Reference Example 1, an aqueous dispersion 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 was mixed to obtain a water-based organic / inorganic composite composition.

  This water-based organic / inorganic composite composition was spray-coated on a black glass plate so as to have a film thickness of 1 μm and baked at 70 ° C. for 10 minutes to obtain a sample. The color difference ΔE before and after coating was 3.0.

  The organic / inorganic composite that provides a high level of weather resistance, stain resistance, and transparency provided by the present invention is useful as a coating agent for architectural exteriors, exterior display applications, automobiles, displays, lenses, and the like. .

Claims (7)

An organic-inorganic composite composition comprising a metal oxide (A) having a particle size of 100 nm or less and polymer emulsion particles (B) dispersed in water, wherein the metal oxide (A) has a refractive index of 1 And zirconium oxide (a1) that is not less than 2.8 and not more than 2.8, and silicon oxide (a2), the zirconium oxide (a1) is a zirconium oxide-yttrium oxide mixture colloid, and the polymer emulsion particles (B) hydrolyzable silicon compound in the presence of water and an emulsifier (b1) and has been obtained by polymerizing a vinyl monomer (b2), organic and characterized in that the particle size is 10-300nm Inorganic composite composition.   The metal oxide (A) and the polymer emulsion particles (B) are in a mass ratio of (A) / (B) = 10/90 to 90/10, (a1) / {(A) + (B)} = The composition of Claim 1 which is 0.01-0.5 and the range of (a2) / {(A) + (B)} = 0.1-0.8. The composition according to claim 1 or 2, wherein the zirconium oxide (a1) is an aqueous dispersion and has a pH of 8 to 11. The composition according to any one of claims 1 to 3, wherein the metal oxide (A) contains at least one metal oxide (a4) having photocatalytic activity.   The composition according to claim 4, wherein the metal oxide (a4) is titanium oxide (a5).   A functional composite comprising the composition according to any one of claims 1 to 5 formed on a substrate.   A building comprising the functional composite according to claim 6 as an exterior.