Aqueous dispersion
Abstract
Problem to be solved.To obtain an aqueous dispersion which has excellent storage stability and can form coating films having excellent adhesion, long-term durability of weatherability, alkali resistance, resistance to organic chemicals, hot-water resistance, staining resistance, etc., and transparency and high hardness by dispersing a polymer containing a polyorganosiloxane component and a vinyl polymer component and a fine particles of a semiconductor having photocatalysis in an aqueous medium.
Solution.The polyorganosiloxane component (A) is represented by the formula: (R<1> )n Si(OR<2> )4-n (R<1> is a 1-8C organic group; R<2> is a 1-5C alkyl or a 1-4C acyl; and n is 0-2) and is exemplified by tetramethoxysilane. The vinyl polymer component has a backbone comprising a vinyl polymer and having 2-20 hydrolyzable silyl groups and hydrosilyl groups as terminals and side chains. The mean particle diameter of polymer A is 0.01-100 μm. The semiconductor (B) having photocatalysis is exemplified by TiO2 or ZnO2 . The amount of component B used is 1-500 pts.wt. per 100 pts.wt. organosilane in polymer A.
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Projected expiry passed 13 June 2017, 9.3 years ago.
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- 1【請求項１】 （Ａ）ポリオルガノシロキサン（ａ）成分とビニル系重合体（ｂ）成分とを含有する重合体、並びに（Ｂ）光触媒能を有する半導体の微粒子および／またはゾルが、水系媒体中に分散してなる水系分散体。
100 paragraphs, as filed
Description: TECHNICAL FIELD [Detailed description of the invention]
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INDUSTRIAL APPLICABILITY The present invention relates to an aqueous dispersion, and more specifically, contains a polymer containing a polyorganosiloxane component and a vinyl-based polymer component, and a semiconductor having photocatalytic activity. In particular, it relates to an aqueous dispersion useful as a coating material.
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[Conventional technology] Traditionally, coating agents have been used in various fields, and their application range has been steadily expanding. However, along with this, the required performance for coating agents has become more sophisticated, and in recent years, adhesion, adhesion, etc. There is a demand for a coating agent that has an excellent balance of performance such as chemical resistance, moisture resistance, weather resistance, (warm) water resistance, and stain recovery, and can form a coating film having high hardness. As a coating agent that satisfies some of these requirements, a composition comprising a partial condensate of organosilane, a dispersion of colloidal silica, and a silicone-modified acrylic resin (Japanese Patent Laid-Open No. 60-135465), or a condensation of organosilane. A composition comprising a product, a chelate compound of zirconium alkoxide, and a hydrolyzable silyl group-containing vinyl resin (Japanese Patent Laid-Open No. 64-1769) has been proposed. However, all of these coating agents are solvent-based, and in recent years, from the viewpoints of low pollution, resource saving, safety and health, etc., there is a strong demand for solvent removal, and there is a shift to water-based coating agents. Under such circumstances, the development of reactive resin emulsions has been enthusiastically studied as those that can be expected to improve performance such as water resistance and chemical resistance, and a resin emulsion having a hydrolyzable silyl group has been proposed as one of them. As an example, JP-A-7-26035 discloses a reactive resin emulsion containing a vinyl polymer having a hydrolyzable silyl group and an amineimide group, and JP-A-7-91510 also discloses. An aqueous coating composition comprising an aqueous dispersion of a vinyl polymer having an alkoxysilyl group and an aqueous dispersion of a tin compound is disclosed. However, these hydrolyzable silyl group-containing resin emulsions are inferior in storage stability, and especially when this emulsion is stored for a long period of time, it gels or the performance of the coating film obtained from the emulsion after long-term storage is improved. Unlike the coating film obtained from the emulsion immediately after production, it has the disadvantage that stable quality cannot be ensured, and even if there is a problem in terms of practicality or the storage stability is relatively good, the adhesion, Chemical resistance, moisture resistance, weather resistance, (temperature resistance) ) It was unsatisfactory in terms of performance balance including water-based and stain resistance. In recent years, many coating compositions containing a photocatalyst component have been proposed, for example, titanium oxide, a hydrolyzate of a hydrolyzable silicon compound (alkylsilicate or silicon halide), and a solvent (water or A composition for forming a titanium oxide coating film for a photocatalyst (Alcohol) (Japanese Patent Laid-Open No. 8-164334), a silicon compound having at least two alkoxy groups, a titanium compound or zirconium compound having at least two alkoxy groups, and guanidyl. A surface treatment composition for imparting antibacterial and antifungal properties, which comprises a hydrophilic inorganic powder such as titanium oxide treated with an alkoxysilane having a group and / or a polysiloxane (Japanese Patent Laid-Open No. 8-176527) has been proposed. ing. However, these compositions are intended to have antibacterial / antifungal properties and decomposition of harmful substances based on an alkoxysilane and / or a polysiloxane component which essentially has a photocatalyst component or a guanidyl group, and are organic such as alcohol. It contains a solvent and low molecular weight components, and is not preferable for the environment. Moreover, even if these compositions are applied to a coating material, the coating film is very brittle and cannot be thickened, and long-term durability, especially crack resistance in the presence of light, water or heat. There is also a problem that it is scarce. A surface treatment composition (Japanese Patent Laid-Open No. 8-176527) for imparting antibacterial and antifungal properties, which is composed of a hydrophilic inorganic powder such as tongue, has been proposed. However, these compositions are intended to have antibacterial / antifungal properties and decomposition of harmful substances based on an alkoxysilane and / or a polysiloxane component which essentially has a photocatalyst component or a guanidyl group, and are organic such as alcohol. It contains a solvent and low molecular weight components, and is not preferable for the environment. Moreover, even if these compositions are applied to a coating material, the coating film is very brittle and cannot be thickened, and long-term durability, especially crack resistance in the presence of light, water or heat. There is also a problem that it is scarce. A surface treatment composition (Japanese Patent Laid-Open No. 8-176527) for imparting antibacterial and antifungal properties, which is composed of a hydrophilic inorganic powder such as tongue, has been proposed. However, these compositions are intended to have antibacterial / antifungal properties and decomposition of harmful substances based on an alkoxysilane and / or a polysiloxane component which essentially has a photocatalyst component or a guanidyl group, and are organic such as alcohol. It contains a solvent and low molecular weight components, and is not preferable for the environment. Moreover, even if these compositions are applied to a coating material, the coating film is very brittle and cannot be thickened, and long-term durability, especially crack resistance in the presence of light, water or heat. There is also a problem that it is scarce.
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PROBLEM TO BE SOLVED: To solve a problem The present invention is based on the above-mentioned problems in the prior art, and the problems are that the storage stability is extremely excellent, and the appearance, adhesion and weather resistance of a coating film are excellent. As an environment-friendly coating material, it has excellent long-term durability such as alkali resistance, organic chemical resistance, (warm) water resistance, and stain resistance, and can form a transparent, hard, and thick film coating film. The purpose is to provide a useful aqueous dispersion.
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A gist of the present invention is to provide a polymer containing (A) a polyorganosiloxane (a) component and a vinyl-based polymer (b) component, and (B) a semiconductor having photocatalytic activity. Consists of an aqueous dispersion, in which the fine particles and / or sol of the above are dispersed in an aqueous medium.
Hereinafter, the present invention will be described in detail. Component (A) The component (A) in the present invention is a polymer containing a polyorganosiloxane (a) component and a vinyl-based polymer (b) component (hereinafter, also referred to as polymer (A)). is there. Here, "containing a polyorganosiloxane (a) component and a vinyl-based polymer (b) component" means that the two components are separated from each other or both components are chemically chemically. Means that it is bound to. Hereinafter, the polyorganosiloxane (a) and the vinyl-based polymer (b) in the polymer (A) will be sequentially described.
<Polyorganosiloxane (a)> The polyorganosiloxane (a), which is one of the constituents of the polymer (A), is an organosilane represented by the following general formula (1) (hereinafter, "organosilane"). A component having a structure in which (a1) is polycondensed is preferable. (R<sup>1</sup>)<sub>n </sub>Si (OR<sup>2</sup>)<sub>4-n </sub> (1) (In the formula, R<sup>1</sup> Is an organic group with 1 to 8 carbon atoms, R<sup>2</sup> Indicates an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms, and n is an integer of 0 to 2. ) In general formula (1), R<sup>1</sup> Examples of the organic group having 1 to 8 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group and a t-butyl group. In addition to alkyl groups such as n-pentyl group, n-hexyl group, n-heptyl group and n-octyl group, γ-chloropropyl group, γ-bromopropyl group, 3,3,3-trifluoropropyl group and γ -Glysidoxypropyl group, γ- (meth) acrylic oxypropyl group, γ-mercaptopropyl group, γ-aminopropyl group, γ-dimethylaminopropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, vinyl Groups, phenyl groups and the like can be mentioned. Also, R<sup>2</sup> Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, and a t-butyl group. Examples thereof include an n-pentyl group and the like, and examples of the acyl group having 1 to 4 carbon atoms include an acetyl group, a propionyl group, a butyl group and the like.
0007 Specific examples of such an organosilane (a1) include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, and n. -Propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3 , 3,3-Trifluoropropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-Mercaptopropyltrimethoxysilane, γ-Mercaptopropyltriethoxysilane, 3,4-epylcyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltri Methoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane , Di-i-propyldiethoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane and other alkoxysilanes; tetraacetoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, dimethyldiacetoxy Examples thereof include acyloxysilanes such as silane and diethyldiacetoxysilane, and preferred are methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane and dimethyldiethoxysilane. These organosilanes (a1) may be used alone or in admixture of two or more.
In the present invention, the organosilane (a1) is used as it is or as a hydrolyzate and / or a partial condensate thereof. In this case, when the polymer (A) is produced, the hydroxysilyl group generated by the hydrolysis of the organosilane (a1) while forming a polyorganosiloxane chain by the polycondensation reaction of the organosilane (a1) will be described later. The hydroxysilyl group in the vinyl polymer (b) can be microscopically dispersed and mixed, or can cause a condensation reaction with each other. The polystyrene-equivalent weight average molecular weight (hereinafter referred to as Mw) of the partial condensate of the organosilane (a1) is preferably 800 to 100,000, more preferably 1,000 to 50,000.
<Vinyl-based polymer (b)> As the vinyl-based polymer (b) which is the other constituent component of the polymer (A), the main chain is composed of a vinyl-based polymer, and the polymer molecular chain thereof. One or more, preferably 2 to 20 hydrolyzable silyl groups and / or hydroxysilyl groups (hereinafter, these groups are collectively referred to as "hydrolyzable silyl group, etc.") at the terminal and / or side chain. A polymer having a polymer (hereinafter, referred to as "vinyl-based polymer (b1)") is preferable. The hydrolyzable silyl group and the like in the vinyl polymer (b1) are generally represented by the following general formula (2).
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[Chemical 1] <img file="000002.tif" id="000002" he="020" wi="041" img-format="tif" img-content="drawing" />
(In the formula, X represents a hydrolyzable group such as a halogen atom, an alkoxy group, an asyloxy group, an aminoxy group, a phenoxy group, a thioalkoxy group, an amino group, or a hydroxyl group, and R<sup>3 </sup>Indicates a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 1 to 10 carbon atoms, and m is an integer of 1 to 3 carbon atoms. ) One or more hydrolyzable silyl groups and the like can be present in the vinyl polymer (b1). The vinyl-based polymer (b1) has, for example, (a) the carbon-carbon double bond of a vinyl-based (co) polymer having a carbon-carbon double bond (hereinafter referred to as unsaturated polymer). , A method of adding a hydrosilane compound having a hydrolyzable silyl group, etc., (b) Polymerization of a vinyl-based monomer having a hydrolyzable silyl group, etc., together with other vinyl-based monomers in some cases (co) It can be manufactured by a method such as The unsaturated polymer used in the method (a) above can be produced, for example, as follows. That is, (a-1) an appropriate functional group (hereinafter referred to as "complementary functional group (α)") in the (co) polymer of the vinyl-based monomer is combined with the complementary functional group (a). By reacting a reactive functional group (hereinafter referred to as "complementary functional group (β)") with an unsaturated compound having a carbon-carbon double bond, carbon-is added to the side chain of the polymer molecular chain. A functional unsaturated polymer having a carbon double bond can be produced. Further, (a-2) a radical polymerization initiator having a complementary functional group (α) (for example, 4,4-azobis-4-cyanovaleric acid, etc.) is used, or both a radical polymerization initiator and a chain transfer agent are used. Using a compound having a functional group (α) complementary to (for example, 4,4-azobis-4-cyanovaleric acid and dithioglycolic acid, etc.), the vinyl-based monomer is (co) polymerized to obtain a polymer. After synthesizing a precursor (co) polymer having a complementary functional group (α) derived from a radical polymerization initiator or a chain transfer agent at one end or both ends of the molecular chain, the complement in the precursor (co) polymer By reacting the functional group (α) with an unsaturated compound having a complementary functional group (β) and a carbon / carbon double bond, a carbon-carbon double is formed at one end or both ends of the polymer molecular chain. A functional unsaturated polymer having a bond can be produced. Further, (a-3) An unsaturated polymer can also be produced by the combination of (a-1) and (a-2). Reaction of complementary functional group (α) with complementary functional group (β) in the methods (a-1) and (a-2) Examples of the above are the esterification reaction of a carboxyl group and a hydroxyl group, the ring-opening esterification reaction of a carboxylic acid anhydride group and a hydroxyl group, the esterification reaction of a carboxyl group and an epoxy group, and the amidation of a carboxyl group and an amino group. Examples thereof include a ring-opening amidation reaction of a carboxylic acid anhydride group and an amino group, a ring-opening addition reaction of an epoxy group and an amino group, and a urethanization reaction of a hydroxyl group and an isocyanate group. Examples of the unsaturated compound having a complementary unsaturated group (β) and a carbon-carbon double bond used in the method (a-1) include unsaturated of the hydrophilic vinyl-based monomers. In addition to carboxylic acids, unsaturated carboxylic acid anhydrides, hydroxyl group-containing vinyl-based monomers or amino group-containing vinyl-based monomers, epoxy groups such as glycidyl (meth) acrylate and (meth) allyl glycidyl ether are not contained. Examples thereof include a saturated compound, an unsaturated compound containing an isocyanate group obtained by reacting the hydroxyl group-containing vinyl monomer with a diisocyanate compound in an equimolar amount.
Examples of the hydrosilane compound having a hydrolyzable group used in the method (a) include halogenated silanes such as methyldichlorosilane, phenyldichlorosilane, and trichlorosilane; methyldimethoxysilane. , Methyldiethoxysilane, phenyldimethoxysilane, trimethoxysilane, triethoxysilane and other alkoxysilanes; methyldiacetoxysilane, phenyldiacetoxysilane, triacetoxysilane and other acyloxysilanes; dimethyl-aminoxisilane, methyl Aminoxysilanes such as diaminoxisilane and triaminoxisilane; phenoxysilanes such as methyldiphenoxysilane and triphenoxysilane; thioalkoxysilanes such as methyldi (thiomethoxy) silane and tri (thiomethoxy) silane; methyl di Examples thereof include aminosilanes such as aminosilane and triaminosilane. These hydrosilane compounds can be used alone or in admixture of two or more.
Next, the vinyl-based monomer having a hydrolyzable silyl group or the like used in the method (b) above is generally represented by the following general formula (3).
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[Chemical 2] <img file="000003.tif" id="000003" he="020" wi="043" img-format="tif" img-content="drawing" />
(In the formula, X, R<sup>3 </sup>And m are synonymous with general formula (2), respectively, and R<sup>4 </sup>Indicates an organic group having a polymerizable carbon / carbon double bond. ) As a specific example of a vinyl-based monomer having such a hydrolyzable silyl group, CH<sub>2 </sub>= CHSi (CH<sub>3</sub>) (OCH<sub>3</sub>)<sub>2 </sub>, CH<sub>2 </sub>= CHSi (OCH<sub>3</sub>)<sub>3 </sub>, CH<sub>2 </sub>= CHSi (CH<sub>3</sub>) Cl<sub>2 </sub>, CH<sub>2 </sub>= CHSiCl<sub>3 </sub>, CH<sub>2 </sub>= CHCOO (CH<sub>2</sub>)<sub>2 </sub>Si (CH<sub>3</sub>) (OCH<sub>3</sub>)<sub>2 </sub>, CH<sub>2 </sub>= CHCOO (CH<sub>2</sub>)<sub>2 </sub>Si (OCH<sub>3</sub>)<sub>3 </sub>, CH<sub>2 </sub>= CHCOO (CH<sub>2</sub>)<sub>3 </sub>Si (CH<sub>3</sub>) (OCH<sub>3</sub>)<sub>2 </sub>, CH<sub>2 </sub>= CHCOO (CH<sub>2</sub>)<sub>3 </sub>Si (OCH<sub>3</sub>)<sub>3 </sub>, CH<sub>2 </sub>= CHCOO (CH<sub>2</sub>)<sub>2 </sub>Si (CH<sub>3</sub>) Cl<sub>2 </sub>, CH<sub>2 </sub>= CHCOO (CH<sub>2</sub>)<sub>2 </sub>SiCl<sub>3 </sub>, CH<sub>2 </sub>= CHCOO (CH<sub>2</sub>)<sub>3 </sub>Si (CH<sub>3</sub>) Cl<sub>2 </sub>, CH<sub>2 </sub>= CHCOO (CH<sub>2</sub>)<sub>3 </sub>SiCl<sub>3 </sub>, CH<sub>2 </sub>= C (CH)<sub>3</sub>) COO (CH<sub>2</sub>)<sub>2 </sub>Si (CH<sub>3</sub>) (OCH<sub>3</sub>)<sub>2 </sub>, CH<sub>2 </sub>= C (CH)<sub>3</sub>) COO (CH<sub>2</sub>)<sub>2 </sub>Si (OCH<sub>3</sub>)<sub>3 </sub>, CH<sub>2 </sub>= C (CH)<sub>3</sub>) COO (CH<sub>2</sub>)<sub>3 </sub>Si (CH<sub>3</sub>) (OCH<sub>3</sub>)<sub>2 </sub>, CH<sub>2 </sub>= C (CH)<sub>3</sub>) COO (CH<sub>2</sub>)<sub>3 </sub>Si (OCH<sub>3</sub>)<sub>3 </sub>, CH<sub>2 </sub>= C (CH)<sub>3</sub>) COO (CH<sub>2</sub>)<sub>2 </sub>Si (CH<sub>3</sub>) Cl<sub>2 </sub>, CH<sub>2 </sub>= C (CH)<sub>3</sub>) COO (CH<sub>2</sub>)<sub>2 </sub>SiCl<sub>3 </sub>, CH<sub>2 </sub>= C (CH)<sub>3</sub>) COO (CH<sub>2</sub>)<sub>3 </sub>Si (CH<sub>3</sub>) Cl<sub>2 </sub>, CH<sub>2 </sub>= C (CH)<sub>3</sub>) COO (CH<sub>2</sub>)<sub>3 </sub>SiCl<sub>3 </sub>、
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[0020] can be mentioned. These vinyl-based monomers having a hydrolyzable silyl group and the like can be used alone or in combination of two or more.
0021. Examples of the vinyl-based monomer constituting the unsaturated polymer used in the method (a) and the other vinyl-based monomer used in the method (b) include methyl (meth) acrylate. , (Meta) ethyl acrylate, (meth) acrylate n-propyl, (meth) acrylate i-propyl, (meth) acrylate n-butyl, (meth) acrylate i-butyl, (meth) acrylate sec -Butyl, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, n-hexyl (meth) acrylate, i-hexyl (meth) acrylate, (meth) acrylic N-Heptyl acid, i-Heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, i-octyl (meth) acrylate, n-nonyl (meth) acrylate, (Meta) i-nonyl acrylate, (meth) n-decyl acrylate, (meth) i-decyl acrylate, (meth) n-undecyl acrylate, (meth) n-dodecyl acrylate, (meth) acrylate (Meta) acrylics such as palmityl, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-methylcyclohexyl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate, benzyl (meth) acrylate Acid esters; 2-methoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 2-methoxybutyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 4 -Acrylic (poly) such as methoxybutyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate (for example, 2 to 20 ethylene glycol units), methoxypolypropylene glycol (meth) acrylate (for example, 2 to 20 propylene glycol units). ) (Meta) acrylic acid esters of alkylene glycol; ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di(Meta) acrylate, glycerin tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate (for example, the number of ethylene glycol units is 2 to 20). , Polyhydric alcohol (meth) acrylic acid esters such as polypropylene glycol di (meth) acrylate (for example, the number of propylene glycol units is 2 to 20);
[2- (Meta) acryloyloxyethyl], di-adipic acid
[2- (Meta) acryloyloxyethyl], di phthalate
[2- (Meta) acryloyloxyethyl] Esters of non-polymerizable polybasic acids such as hydroxyalkyl (meth) acrylate; (meth) acrylonitrile, α-chloroacrylonitrile, α-chloromethylacrylonitrile, α-trifluoromethylacrylonitrile, α-methoxyacrylonitrile, α Cyano group-containing vinyl monomers such as ethoxyacrylonitrile and vinylidene cyanide; (meth) acrylamide, α-ethylacrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl ( Meta) acrylamide, N, N-diethyl (meth) acrylamide, N-methoxy (meth) acrylamide, N, N-dimethoxy (meth) acrylamide, N-ethoxy (meth) acrylamide, N, N-diethoxy (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone (meth) acrylamide, N, N'-methylenebis (meth) acrylamide, N, N'-ethylenebis (meth) acrylamide, crotonamide, maleic acid diamide, fumaric acid diamide, itacon Amid group-containing vinyl-based monomers such as acid diamide; epoxy group-containing vinyl-based monomers such as glycidyl (meth) acrylate and (meth) allylglycidyl ether, styrene, α-methylstyrene, vinyl chloride, vinyl acetate, etc. In addition to vinyl propionate, the following hydrophilic vinyl-based monomers, carbonyl group-containing vinyl-based monomers, and the like can be mentioned.
The hydrophilic vinyl-based monomer is composed of, for example, a vinyl-based monomer having a hydrophilic functional group such as a carboxyl group, a carboxylic acid anhydride group, a hydroxyl group, an amino group, or an amineimide group. One or more such hydrophilic functional groups can be present in the vinyl-based monomer, but for example, it is preferable that any two or more of a carboxyl group, a hydroxyl group or an amineimide group coexist. Examples of the hydrophilic vinyl-based monomer include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, α-chloroacrylic acid, α-chloromethylacrylic acid, and α-trifluoromethylacrylic acid. , Α-methoxyacrylic acid, α-ethoxyacrylic acid, monosuccinate
[2- (Meta) acryloyloxyethyl], monoadipic acid
[2- (Meta) acryloyloxyethyl], monophthalate
[2- (Meta) acryloyloxyethyl] Carboxyl group-containing vinyl monomers such as; maleic anhydride, unsaturated carboxylic acid anhydrides such as itaconic anhydride; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl Hydroxyl-containing vinyl monomers such as (meth) acrylate, N-methylol (meth) acrylamide, N- (2-hydrosiethyl) (meth) acrylamide, 2-hydroxyethyl vinyl ether, and (meth) allyl alcohol; 2-aminoethyl (Meta) acrylate, 2-aminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-dimethylaminopropyl (meth) Amino group-containing vinyl monomers such as acrylate, 3-dimethylaminopropyl (meth) acrylate, 2-aminoethylvinyl ether, N, N-dimethylamino (meth) acrylamide, N, N-diethylamino (meth) acrylamide; 1 , 1,1-trimethylamine (meth) acrylicimide, 1-methyl-1-ethylamine (meth) acrylicimide, 1,1-dimethyl-1- (2-hydroxypropyl) amine (meth) acrylicimide, 1,1- Dimethyl-1- (2'-phenyl-2'-hydroxyethyl) amine (meth) acrylicimide, 1,1-dimethyl-1- (2'-hydroxy-2'-phenoxypropyl) amine (meth) acrylicimide, etc. Examples thereof include vinyl-based monomers containing an amineimide group. Among these hydrophilic vinyl-based monomers, in the group of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, (meth) acrylic acid is particularly preferable, and the hydroxyl group-containing vinyl-based monomer is particularly 2-hydroxy. Ethyl (meth) acrylate is preferable, and in the group of amino group-containing vinyl-based monomers and amineimide group-containing vinyl-based monomers, 1,1-dimethyl-1- (2-hydroxypropyl) amine (meth) acrylicimide is particularly preferable. , 1,1-Dimethyl-1- (2'-phenyl-2'-hydroxye
The carbonyl group-containing vinyl-based monomer is composed of a vinyl-based monomer having at least one carbonyl group composed of a formyl group or a keto group. Among the carbonyl group-containing vinyl-based monomers, examples of the vinyl-based monomer having a formyl group include (meth) acrolein, crotonaldehyde, formylstyrene, formyl-α-methylstyrene, diacetoneacrylamide, and (meth). Examples thereof include acrylamide pivalinaldehyde, 3- (meth) acrylamide methyl-anisaldehyde, β- (meth) acryloxy-α and α-dialkylpropanals represented by the following general formula (4).
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[Chemical 7] <img file="000008.tif" id="000008" he="020" wi="063" img-format="tif" img-content="drawing" />
(In the formula, R<sup>5 </sup>Indicates a hydrogen atom or a methyl group, R<sup>6 </sup>Indicates a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R<sup>7 </sup>Indicates an alkyl group having 1 to 3 carbon atoms, and R<sup>8 </sup>Indicates an alkyl group having 1 to 4 carbon atoms. ] Specific examples of β- (meth) acryloxy-α and α-dialkylpropanals represented by the general formula (4) include β- (meth) acryloxy-α and α-dimethylpropanal (that is, β-(that is, β-(. Meta) acryloxy pivalinaldehyde), β- (meth) acryloxy-α, α-diethylpropanal, β- (meth) acryloxy-α, α-dipropylpropanal, β- (meth) acryloxy-α-methyl- Examples thereof include α-butylpropanal, β- (meth) acryloxy-α, α, β-trimethylpropanal and the like. Examples of the vinyl-based monomer having a keto group include diacetone (meth) acrylamide and vinyl alkyl ketones having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl-n-). Propyl ketone, vinyl-i-propyl ketone, vinyl-n-butyl ketone, vinyl-i-butyl ketone, vinyl-t-butyl ketone, etc.), vinyl phenyl ketone, vinyl benzyl ketone, divinyl ketone, diacetone (meth) acrylate, acetonitrile (meth) ) Acrylic, 2-Hydroxypropyl (meth) acrylate-acetylacetate, 3-Hydroxypropyl (meth) acrylate-acetylacetate, 2-Hydroxybutyl (meth) acrylate-acetylacetate, 3-Hydroxybutyl (meth) acrylate-acetylacetate , 4-Hydroxybutyl (meth) acrylate-acetylacetate, butanediol-1,4- (meth) acrylate-acetylacetate and the like. Among these carbonyl group-containing vinyl-based monomers, acrolein, diacetone acrylamide, vinyl methyl ketone and the like are particularly preferable. In the present invention, the vinyl-based monomer can be used alone or in combination of two or more.
When the vinyl-based polymer (b1) is a (co) polymer of a hydrophilic vinyl-based monomer, the content of the vinyl-based monomer in the vinyl-based polymer (b1) is preferably. It is 0.05 to 50% by weight, more preferably 0.05 to 40% by weight. Further, in the present invention, the vinyl polymer (b1) The particularly preferable content of the hydrophilic vinyl-based monomer in the medium varies depending on the type of the vinyl-based monomer. That is, the total content of (i) unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride is particularly preferably 0.5 to 10% by weight, and (ii) the content of the hydroxyl group-containing vinyl-based monomer is In particular, 5 to 30% by weight is preferable, and (iii) the total content of the amino group-containing vinyl-based monomer and / or the amineimide group-containing vinyl-based monomer is particularly preferably 0.05 to 3% by weight. By setting the content of the hydrophilic vinyl-based monomer within the above range, the aqueous dispersion obtained by using the vinyl-based polymer (b1) composed of the (co) polymer of the hydrophilic vinyl-based monomer The storage stability is particularly excellent. Further, in the vinyl-based polymer (b1) composed of the (co) polymer of the hydrophilic vinyl-based monomer, any one of the vinyl-based monomers shown in (i), (ii) and (iii) above. It is preferable to use two or more kinds in combination, and it is particularly preferable to use one or more kinds of vinyl-based monomers shown in (i), (ii) and (iii) in combination.
When the vinyl-based polymer (b1) is a (co) polymer of a carbonyl group-containing vinyl-based monomer, the content in the vinyl-based polymer (b1) is preferably 0.5 to. It is 30% by weight, more preferably 2 to 20% by weight, and particularly preferably 5 to 15% by weight. In this case, if the content of the carbonyl group-containing vinyl monomer is less than 0.5% by weight, the solvent resistance and damage resistance of the coating film tend to decrease, while if it exceeds 30% by weight, the coating film tends to be coated. The water resistance of the film tends to decrease.
The polystyrene-equivalent number average molecular weight (hereinafter referred to as Mn) of the vinyl polymer (b) in the present invention is preferably 2,000 to 100,000, more preferably 4,000 to 50,000. Is. In the present invention, the vinyl-based polymer (b) can be used alone or in combination of two or more. The amount of the vinyl polymer (b) used in the present invention is usually 2 to 900 parts by weight, preferably 10 to 400 parts by weight, more preferably 20 to 200 parts by weight, based on 100 parts by weight of the organosilane (a1). It is a department. In this case, if the amount of the vinyl polymer (b) used is less than 2 parts by weight, the alkali resistance of the coating film formed from the aqueous dispersion tends to decrease, while if it exceeds 900 parts by weight, the coating film of the coating film tends to have low alkali resistance. Weather resistance tends to decrease.
The polymer (A) can be produced by any method as long as the polyorganosiloxane (a) and the vinyl-based polymer (b) can be dispersed in the aqueous medium, but (c) is preferable. Organosilane (a1) and vinyl polymer (b1) By a method of hydrolyzing and / or partially condensing in an organic solvent in the presence of an organometallic compound and a catalytic amount of water, which will be described later, and then dispersing the reaction solution in an aqueous medium and then removing the organic solvent. Can be manufactured. In the method (c) above, the amount of water present during hydrolysis and / or partial condensation is usually 0.5 to 3.0 mol, preferably 0.7 mol, relative to 1 mol of organosilane (a1). It is about 2.0 mol. Further, in the method (c) above, the aqueous medium is essentially composed of water, but in some cases, an organic solvent such as alcohol may be contained up to about several weight%, and the reaction product is contained in the aqueous medium. An emulsifier, a pH adjuster, or the like can be used to disperse the solvent. Examples of the emulsifier include anionic surfactants such as alkyl sulfate ester salts, alkylaryl sulfate ester salts, alkyl phosphate ester salts and fatty acid salts; and cationic surfactants such as alkyl amine salts and alkyl quaternary amine salts. Nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, block-type polyethers; and amphoteric surfactants such as carboxylic acid type (for example, amino acid type, betaine type, etc.), sulfonic acid type, etc. Any can be used. These emulsifiers can be used alone or in admixture of two or more. As the organic solvent used in the method (c), for example, alcohols, aromatic hydrocarbons, ethers, ketones, esters and the like are suitable. Some of these organic solvents can also be removed before the reaction solution is dispersed in the aqueous medium. The reaction conditions at the time of hydrolysis and / or partial condensation in the method (c) above are that the temperature is usually 40 to 70 ° C. and the reaction time is usually 1 to 8 hours.
In the method (c) above, when the vinyl-based polymer (b1) has an acidic group such as a carboxyl group or a carboxylic acid anhydride group, at least one basic type after hydrolysis and / or partial condensation. It is preferable to add a compound to adjust the pH, and if the vinyl polymer (b1) has a basic group such as an amino group or an amineimide group, at least one acidic type after hydrolysis and / or partial condensation. It is preferable to add a compound to adjust the pH, and further, a vinyl-based polymer (b1). If has the acidic group and the basic group, after hydrolysis and / or partial condensation, at least one basic compound or acidic compound is added depending on the proportion of these groups to adjust the pH. By doing so, the hydrophilicity of the obtained specific polymer can be increased, and the emulsion dispersibility of the specific polymer can be improved. Examples of the basic compound include amines such as ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethanolamine, diethanolamine and dimethylaminoethanol: alkali metal hydroxides such as Kaseikari and Kaseisoda. Examples of the acidic compound include inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, and nitrate; formic acid, acetic acid, propionic acid, lactic acid, oxalic acid, oxalic acid, adipic acid, (meth) acrylic acid, and the like. Examples thereof include organic acids such as maleic acid, fumaric acid and itaconic acid. The pH value at the time of pH adjustment is usually 6 to 10, preferably 7 to 8.
In the aqueous dispersion of the present invention, the polymer (A) is dispersed in the aqueous medium, for example, in the form of particles or an aqueous sol. In this case, the average particle size of the particulate polymer (A) is usually 0.01 to 100 μm.
Component (B) The component (B) in the present invention comprises semiconductor particles and / or a sol having photocatalytic activity. Examples of semiconductors having photocatalytic activity include TiO.<sub>2</sub> , TIO<sub>3</sub> , SrTIO<sub>3</sub> , FeTIO<sub>3</sub> , WO<sub>3</sub> , SnO<sub>2</sub> , Bi<sub>2</sub> O<sub>3</sub> , In<sub>2</sub> O<sub>3</sub> , ZnO, Fe<sub>2</sub> O<sub>3</sub> , RuO<sub>2</sub> , CdO, CdS, CdSe, GaP, GaAs, CdFeO<sub>3</sub> , MoS<sub>2</sub> , LaRhO<sub>3</sub> Etc., preferably TIO<sub>2</sub> , ZnO. These semiconductors can be used alone or in admixture of two or more. In the present invention, the photocatalytic activity of the semiconductor makes the coating film surface hydrophilic in a short time even with weak light, and as a result, the stain resistance of the coating film is not substantially impaired. It became clear that this can be significantly improved. Moreover, in the coating film obtained from the aqueous dispersion of the present invention, the semiconductor is co-condensed with the component (A) and the like, and the hydrophilicity and stain resistance of the coating film are maintained for a long period of time. The existing forms before the component (B) is dispersed in the aqueous medium include particulate powder, aqueous sol in which fine particles are dispersed in water, and non-polar solvents such as methanol and isopropyl alcohol and non-toluene and the like. There are three types of solvent-based sol dispersed in a polar solvent. In the case of a solvent-based sol, it may be further diluted with water or a solvent depending on the dispersibility of the semiconductor fine particles. The average particle size of the semiconductor fine particles in these existing forms is preferably as small as possible from the viewpoint of photocatalytic ability, and is usually 1 μm or less, preferably 0.5 μm or less. Further, in the case of an aqueous sol and a solvent-based sol, the surface treatment may be performed in advance with a surfactant, a dispersant, or an organometallic compound in order to improve the stability and dispersibility of the fine particles. When the component (B) is an aqueous sol or a solvent-based sol, the solid content concentration is preferably 50% by weight or less, more preferably 40% by weight or less. As a method of dispersing the component (B) in the aqueous dispersion, it may be added after the preparation of the aqueous dispersion containing the component (A) and the components (C) to (K) described later, or the above. It can also be added at the time of preparation of the aqueous dispersion to hydrolyze or partially condense the organosilane (aI), the vinyl polymer (b1) or the like in the presence of the component (B). When the component (B) is added at the time of preparation of the aqueous dispersion, the semiconductor compound in the component (B) can be co-condensed with the organosilane (aI), the vinyl polymer (b1), etc., and the obtained aqueous dispersion can be obtained. The storage stability of the coating material can be improved, and the long-term durability of the stain-proofing property of the coating film can be further improved. In addition, the component (B) is an aqueous sol. In the case of, it is preferable to add the component (B) at the time of preparation of the aqueous dispersion, and also when the viscosity in the system is increased by the combination of the component (E) and / or the component (F) described later, the component (B) is added. It is preferable to add it at the time of preparing the aqueous dispersion. The amount of the component (B) used in the present invention is, in terms of solid content, usually 1 to 500 parts by weight, preferably 5 to 400 parts by weight, based on 100 parts by weight of the organosilane (a1).
Further, the following components (C) to (J) can be blended in the aqueous dispersion of the present invention. Component (C) Component (C) consists of an organometallic compound selected from the group zirconium, titanium and aluminum. The organometallic compound is considered to have an action of promoting the hydrolysis and / or partial condensation reaction of the organosilane (a1) and the vinyl-based polymer (b1). An example of such an organometallic compound is the general formula Zr (OR).<sup>9</sup>)<sub>p </sub>(R<sup>10</sup>COCHCOR<sup>11</sup>)<sub>4-p</sub>(However, p = 0-4), Ti (OR<sup>9</sup>)<sub>q </sub>(R<sup>10</sup>COCHCOR<sup>11</sup>)<sub>4-q</sub>(However, q = 0-4) or Al (OR)<sup>9</sup>)<sub>r </sub>(R<sup>10</sup>COCHCOR<sup>11</sup>)<sub>3-r</sub>(However, compounds represented by r = 0 to 3) or partial hydrolysates of these compounds can be mentioned. In the above general formula, R<sup>9 </sup>And R<sup>10</sup>Are independently monovalent hydrocarbon groups having 1 to 6 carbon atoms, specifically, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, and a t-butyl group. , N-pentyl group, n-hexyl group, cyclohexyl group, phenyl group, etc.<sup>11</sup>Is R<sup>9 </sup>And R<sup>10</sup>In addition to the same monovalent hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, specifically, a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, n- It shows a butoxy group, a sec-butoxy group, a t-butoxy group, a lauryloxy group, a stearyloxy group and the like.
0034 Specific examples of the organic metal compound include tetra-n-butoxyzirconium, tri-n-butoxyethylacetoneacetone zirconium, di-n-butoxybis (ethylacetoneacetate) zirconium, and n-butoxytris (ethylacetate). Zyrosine compounds such as (acetate) zirconium, tetrakis (n-propylacetone) zirconium, tetrakis (acetylacetoneacetone) zirconium, tetrakis (ethylacetoneacetate) zirconium; tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (tetrakis) 2-Ethylhexyloxy) titanium, tetrastearyloxytitanium, di-i-propoxybis (ethylacetate acetate) titanium, di-i-propoxybis (acetylacetone) titanium, di-i-propoxybis (acetylacetone) titanium , Titanium compounds such as di-n-butoxybis (triethanolaminoto) titanium; triethoxyaluminum, tri-i-propoxyaluminum, mono-2-butoxydi-i-propoxyaluminum, tri-n-butoxyaluminum , Di-i-propoxyethylacetoneacetate aluminum, di-i-propoxyacetylacetonate aluminum, i-propoxybis (ethylacetoneacetate) aluminum, i-propoxybis (acetylacetonate) aluminum, tris (ethyl) Examples thereof include aluminum compounds such as acetoacetate) aluminum, tris (acetylacetonate) aluminum, and monoacetylacetonate-bis (ethylacetoneacetate) aluminum. Among these compounds, tri-n-butoxy ethylacetoacetate zirconium, di-i-propoxybis (acetylacetonate) titanium, di-i-propoxyethylacetacetate aluminum, and tris (ethylacetacetate) aluminum preferable. These organometallic compounds can be used alone or in admixture of two or more. The organometallic compound is favorable Furthermore, it is used by dissolving it in an organic solvent. As the organic solvent in this case, for example, alcohols, aromatic hydrocarbons, ethers, ketones, esters and the like are suitable.
The amount of the component (C) used in the present invention is preferably 0.01 to 50 parts by weight, more preferably 0.1 to 50 parts by weight, particularly preferably 0.1 part by weight, based on 100 parts by weight of the organosilane (a1). Is 0.5 to 10 parts by weight. In this case, if the amount of the component (C) used is less than 0.01 parts by weight, the formation of a cocondensate of the organosilane (a1) and the vinyl polymer (b1) becomes insufficient, and the mixture can be obtained from the aqueous dispersion. The weather resistance of the coating film tends to decrease, while when it exceeds 50 parts by weight, the storage stability of the aqueous dispersion tends to decrease and the coating film tends to easily crack.
(D) component (D) component is the following general formula R<sup>10</sup>COCH<sub>2 </sub>COR<sup>11</sup> (In the formula, R<sup>10</sup>And R<sup>11</sup>Each represents R in the above general formula representing the organometallic compound of the component (C).<sup>10</sup>And R<sup>11</sup>Is synonymous with. ) Consists of at least one selected from the group of β-diketones and / or β-ketoesters, carboxylic acid compounds, dihydroxy compounds, amine compounds and oxyaldehyde compounds. When the aqueous dispersion of the present invention contains the component (C), it is preferable to further add the component (D). Specific examples of the component (D) include acetylacetone, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, i-propyl acetoacetic acid, n-butyl acetoacetic acid, sec-butyl acetoacetic acid, and t-butyl acetoacetic acid. 2,4-hexanedione, 2,4-heptandione, 3,5-heptandione, 2,4-octanedione, 2,4-nonandione, 5-methyl-2,4-hexanedione, malonic acid, oxalic acid , Phthalic acid, glycolic acid, salicylic acid, aminoacetic acid, iminoacetic acid, ethylenediamine tetraacetic acid, glycol, catechol, ethylenediamine, 2,2-bipyridine, 1,10-phenanthroline, diethylenetriamine, 2-ethanolamine, dimethylglycime, dithizone, Examples thereof include methionine and salicylaldehyde. Of these, acetylacetone and ethyl acetoacetate are preferable, and acetylacetone is particularly preferable. The amount of the component (D) used in the present invention is usually 2 mol or more, preferably 3 to 20 mol, with respect to 1 mol of the component (C). In this case, if the amount of the component (D) used is less than 2 mol, the effect of improving the storage stability of the obtained aqueous dispersion tends to decrease.
Component (E) Component (E) is composed of particles and / or sol or colloid of an inorganic compound other than the component (B), depending on desired properties of the coating film such as increasing the hardness of the coating film. Is compounded. As a specific example of the inorganic compound forming the component (E), SiO<sub>2</sub> , Al<sub>2</sub> O<sub>3</sub> , Al (OH)<sub>3</sub> , Sb<sub>2</sub> O<sub>5</sub> , Si<sub>3</sub> N<sub>4</sub> , Sn-In<sub>2</sub> O<sub>3</sub> , Sb-In<sub>2</sub> O<sub>3</sub> , MgF, CeF<sub>3</sub> , CeO<sub>2</sub> , Al<sub>2</sub> O<sub>3</sub> 3, 3Al<sub>2</sub> O<sub>3</sub> 2SiO<sub>2</sub> , BeO, SiC, AlN, Al<sub>2</sub> O<sub>3</sub> , Fe, Fe<sub>2</sub> O<sub>3</sub> , Co, Co-FeO<sub>X </sub>, CrO<sub>2</sub> , Fe<sub>4</sub> N, Ba ferrite, SmCO<sub>5</sub> , YCO<sub>5</sub> , CeCO<sub>5</sub> , PrCO<sub>5</sub> , Sm<sub>2</sub> CO<sub>17</sub>, Nd<sub>2</sub> Fe<sub>14</sub>B, ZrO<sub>2</sub> , Al<sub>4</sub> O<sub>3</sub> , AlN, SiC, BeO and the like. These inorganic compounds can be used alone or in admixture of two or more. The existing forms before the component (E) is blended into the aqueous dispersion include particulate powder, aqueous sol or colloid in which fine particles are dispersed in water, and polar solvents such as isopropyl alcohol and toluene and the like. There are solvent-based sol or colloids dispersed in non-polar solvents. In the case of a solvent-based sol or colloid, it may be further diluted with water or a solvent depending on the dispersibility of the semiconductor fine particles. When the component (E) is an aqueous sol or colloid and a solvent-based sol or colloid, the solid content concentration is preferably 40% by weight or less. Among the components (E), the colloidal silica is, for example, Snowtex, methanol silica sol, isopropanol silica sol (above, manufactured by Nissan Chemical Industry Co., Ltd.); Cataloid SN, Oscar (above, manufactured by Catalysis Chemical Industry Co., Ltd.); Under trade names such as Ludex (manufactured by DuPont in the United States); Syton (manufactured by Monsanto in the United States); Nalcoag (manufactured by Narco Chemical in the United States), the colloidal alumina is, for example, alumina sol-100, alumina sol-200, alumina sol-520. It is commercially available under trade names such as (above, manufactured by Nissan Chemical Industry Co., Ltd.), alumina clear sol, alumina sol 10, and alumina sol 132 (above, manufactured by Kawaken Fine Chemical Co., Ltd.). As a method of blending the component (E) into the aqueous dispersion of the present invention, the component (E) is added after preparation of the aqueous dispersion containing the components (A) to (D) and the components (F) to (J) described later. Alternatively, it may be added at the time of preparation of the aqueous dispersion to hydrolyze or partially condense the organosilane (a1), the vinyl polymer (b1) or the like in the presence of the component (E). The amount of the component (E) used in the present invention is, in terms of solid content, usually 0 to 500 parts by weight, preferably 0.1 to 400 parts by weight, based on 100 parts by weight of the organosilane (a1).
(F) component The component (F) is composed of another filler for exhibiting coloring, designability or thickening of the coating film, and further enhancing corrosion resistance, weather resistance and the like. Examples of such other fillers include metals and alloys; compounds such as metal oxides, hydroxides, carbides, nitrides and sulfides; and water-insoluble pigments such as organic pigments and inorganic pigments. be able to. These components are used in particulate, fibrous, whisker-like or scaly form. Specific examples of other fillers include iron, nickel, aluminum, zinc, copper, silver, carbon black, graphite, stainless steel, ferric oxide, ferrite, cobalt oxide, manganese oxide, chromium oxide, and zirconium oxide for pigments. , Titanium oxide for pigments, zirconium oxide, silicon dioxide, lead phosphite, aluminum oxide, zinc oxide, copper borooxide, ferric hydroxide, aluminum hydroxide, limestone, barium carbonate, calcium carbonate, magnesium carbonate, lead sulfate, Basic lead sulfate, barium sulfate, gypsum, molybdenum disulfide, lead sulfide, copper sulfide, lead silicate, calcium leadate, copper borate, potassium titanate, silicon carbide, silicon nitride, boron nitride, lead phthalate, synthetic murite, Clay, diatomaceous soil, talc, bentonite, mica, green soil, cobalt green, manganese green, billijan, guinea green, cobalt chrome green, schule green, green soil, chrome green, zinc green, pigment green, ultramarine, rock ultramarine, dark blue, Cobalt blue, cerulean blue, molybdenum blue, cobalt purple, mars purple, manganese purple, pigment violet, zinc oxide, chrome yellow, cadmium yellow, strontium yellow, titanium yellow, litharge, pigment yellow, ocher, cadmium red, selenium red, chrome bar Million, red iron oxide, zinc oxide, bunchison white, manganese white, bone black, diamond black, thermatomic black, vegetable black and the like can be mentioned. These other fillers can be used alone or in admixture of two or more. The amount of the component (F) used in the present invention is usually 300 parts by weight or less with respect to 100 parts by weight of the total solid content of the components (A) to (E). In this case, the amount of component (F) used is 30. If it exceeds 0 parts by weight, the adhesion of the coating film tends to decrease. Further, if necessary, a dehydrating agent such as methyl orthoformate, methyl orthoacetate, tetraethoxysilane, a silane coupling agent, a titanium coupling agent, a dye, a pigment, a dispersant, a thickener, a pressure-sensitive agent, and a leveling agent. , Antifungal agents, preservatives, antiaging agents, antioxidants, antifogging agents, flame retardants and the like can also be blended.
Component (G) Component (G) is composed of a curing accelerator other than the component (C). By using such a component (G), the curing rate of the coating film formed from the aqueous dispersion of the present invention can be increased, and in order to cure at a relatively low temperature, (G) is further added. It is more effective to add it. Examples of the component (G) include alkali metal salts such as naphthenic acid, octyl acid, nitrite, sulfite, aluminic acid, and carbonic acid; ethylenediamine, hexanediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperidine, piperazine, and the like. Metaphenylenediamine, Ethanolamine, Triethylamine, 3-Aminopropyltriethoxysilane, 3- (2-aminoethyl) -aminopropyltrimethoxysilane, 3- (2-aminoethyl) -aminopropylmethyldimethoxysilane, 3-ani Amine compounds such as linopropyltrimethoxysilane and various modified amines used as curing agents for epoxy resins; (C<sub>4</sub> H<sub>9</sub>)<sub>2</sub> Sn (OCOC<sub>11</sub>H<sub>23</sub>)<sub>2</sub>, (C<sub>4</sub> H<sub>9</sub>)<sub>2</sub> Sn (OCOCH = CHCOOCH<sub>3</sub>)<sub>2</sub> , (C<sub>4</sub> H<sub>9</sub>)<sub>2</sub> Sn (OCOCH = CHCOO (C)<sub>4</sub> H<sub>9</sub>)<sub>2</sub> , (C<sub>8</sub> H<sub>17</sub>)<sub>2</sub>Sn (OCOC<sub>11</sub>H<sub>23</sub>)<sub>2</sub>, (C<sub>8</sub> H<sub>17</sub>)<sub>2</sub>Sn (OCOCH = CHCOOCH<sub>3</sub>)<sub>2</sub> , (C<sub>8</sub> H<sub>17</sub>)<sub>2</sub>Sn (OCOCH = CHCOO (C)<sub>4</sub> H<sub>9</sub>)<sub>2</sub> , (C<sub>8</sub> H<sub>17</sub>)<sub>2</sub>Sn (OCOCH = CHCOOC<sub>8</sub> H<sub>17</sub>)<sub>2</sub>, Sn (OCOCC<sub>8</sub> H<sub>17</sub>)<sub>2</sub>Carboxylic acid type organotin compounds such as (C)<sub>4</sub> H<sub>9</sub>)<sub>2</sub> Sn (SCH<sub>2</sub> COOC<sub>8</sub>H<sub>17</sub>)<sub>2</sub>, (C<sub>4</sub> H<sub>9</sub>)<sub>2</sub> Sn (SCH<sub>2</sub> CH<sub>2</sub> COOC<sub>8</sub>H<sub>17</sub>)<sub>2</sub>, (C<sub>8</sub> H<sub>17</sub>)<sub>2</sub>Sn (SCH<sub>2</sub> COOC<sub>8</sub>H<sub>17</sub>)<sub>2</sub>, (C<sub>8</sub> H<sub>17</sub>)<sub>2</sub>Sn (SCH<sub>2</sub> CH<sub>2</sub> COOC<sub>8</sub>H<sub>17</sub>)<sub>2</sub>, (C<sub>8</sub> H<sub>17</sub>)<sub>2</sub>Sn (SCH<sub>2</sub> COOC<sub>12</sub>H<sub>25</sub>)<sub>2</sub>, (C<sub>8</sub> H<sub>17</sub>)<sub>2</sub>Sn (SCH<sub>2</sub> CH<sub>2</sub> COOC<sub>12</sub>H<sub>25</sub>)<sub>2</sub>、
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[Chemical 8] <img file="000009.tif" id="000009" he="020" wi="051" img-format="tif" img-content="drawing" />Such as mercaptide type organic tin compounds;
(C)<sub>4</sub> H<sub>9</sub>)<sub>2</sub> Sn = S, (C<sub>8</sub> H<sub>17</sub>)<sub>2</sub>Sn = S,
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[Chemical 9] <img file="000010.tif" id="000010" he="020" wi="025" img-format="tif" img-content="drawing" />
Sulfide-type organic tin compounds such as (C)<sub>4</sub> H<sub>9</sub>)<sub>2</sub> SnO, (C<sub>8</sub> H<sub>17</sub>)<sub>2</sub>Examples thereof include organic tin oxides such as SnO, and reaction products of these organic tin oxides with ester compounds such as ethyl silicate, dimethyl maleate, diethyl maleate, and dioctyl phthalate. These curing accelerators can be used alone or in combination of two or more. The amount of the component (G) used in the present invention is usually 0 to 100 parts by weight, preferably 0.1 to 80 parts by weight, more preferably 0.5 to 50 parts by weight, based on 100 parts by weight of the organosilane (a1). It is a part by weight.
Component (H) The component (H) is composed of a polyfunctional hydrazine derivative having two or more hydrazino groups in the molecule, and the vinyl-based polymer (b) constituting the polymer (A) is a carbonyl group. Is preferably blended when it contains. In the drying process after the construction of the aqueous dispersion of the present invention, the polyfunctional hydrazine derivative reacts with the hydrazine group in the carbonyl group contained in the polymer (A) to form a network structure, thereby forming a coating film. Has the effect of cross-linking. Examples of the polyfunctional hydrazine derivative include dihydrazide oxalate. Dihydrazide malonate, dihydrazide adihydric acid, dihydrazide glutalide, dihydrazide adipic acid, dihydrazide sebacic acid, dihydrazide phthalic acid, dihydrazide isophthalic acid, dihydrazide terephthalate, dihydrazide maleate, dihydrazide fumarate, dihydrazide adipic acid dihydric acid 10, especially dicarboxylic acid dihydrazides having a total carbon number of 4 to 6; trifunctional or higher hydrazides such as citrate trihydrazide, nitriloacetate trihydrazide, cyclohexanetricarboxylic acid trihydrazide, ethylenediamine tetraacetate tetrahydrazide; ethylene-1,2 -Dihydrazine, propylene-1,2-dihydrazine, propylene-1,3-dihydrazine, butylene-1,2-dihydrazine, butylene-1,3-dihydrazine, butylene-1,4-dihydrazine, butylene Water-soluble dihydrazines such as aliphatic dihydrazines having a total carbon number of 2 to 4 such as 2,3-dihydrazine are preferable. Furthermore, at least a part of the hydradino groups of these water-soluble dihydrazines are reacted with carbonyl compounds such as acetaldehyde, propionaldehyde, butylaldehyde, acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl butyl ketone and diacetone alcohol. Thereby, blocked compounds (hereinafter referred to as "blocked polyfunctional hydrazine derivatives"), for example, dihydrazide monoacetone hydrazone adipate, dihydrazidodiacetone hydrazone adipate, and the like can also be used. By using such a blocked polyfunctional hydrazine derivative, the progress of the cross-linking reaction of the aqueous dispersion can be appropriately suppressed, so that the redispersibility, which is particularly important as a printing ink, can be further improved. Among these polyfunctional hydrazine derivatives, adipic acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide diacetone hydrazone and the like are preferable. The polyfunctional hydrazine derivative can be used alone or in combination of two or more.
As for the amount of the component (H) used in the present invention, the equivalent ratio of the carbonyl group in the polymer (A) to the hydrazino group in the component (H) is usually 1: 0.1 to 5, preferably 1: 0.1 to 5. Is an amount in the range of 1: 0.5 to 1.5, more preferably 1: 0.7 to 1.2. In this case, if the hydrazino group is less than 0.1 equivalent with respect to 1 equivalent of the carbonyl group, the solvent resistance and damage resistance of the coating film tend to decrease, while if it exceeds 5 equivalent, the coating film tends to be deteriorated. Water resistance, transparency, etc. tend to decrease. However, when a blocked polyfunctional hydrazine derivative is used as the polyfunctional hydrazine derivative, the equivalent ratio is based on the equivalent ratio of the carbonyl group to the hydrazino group in the polyfunctional hydrazine derivative before blocking. .. The component (H) can be blended in an appropriate step for preparing the aqueous dispersion of the present invention, but in order to suppress the generation of coagulated matter during the production of the polymer (A) and maintain the polymerization stability. Is desirable to add the entire amount of the component (H) after the production of the polymer (A).
Component (I) Component (I) comprises a resinous additive. Examples of the resinous additive include a water-soluble polyester resin usually used for water-based paints, a water-soluble or water-dispersible epoxy resin, a water-soluble or water-dispersible acrylic resin, a styrene-maleic acid copolymer, and the like. Examples thereof include carboxyl group-containing aromatic vinyl resins and urethane resins. These resinous additives can be used alone or in admixture of two or more. The amount of the component (I) used in the present invention is usually 50 parts by weight or less, preferably 30 parts by weight or less, based on 100 parts by weight of the total solid content of the aqueous dispersion.
(J) component The component (K) is composed of an organic solvent that improves film forming property and wettability. Examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, n-amyl alcohol, and n-hexyl alcohol, and ethylene. Glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-i-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol Examples thereof include monoethyl ether, diethylene glycol mono-i-propyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, tributoxymethyl phosphate and the like. These organic solvents can be used alone or in admixture of two or more. The amount of the component (K) used in the present invention is usually 50% by weight or less, preferably 20% by weight or less of the total aqueous dispersion. Further, the aqueous dispersion of the present invention contains, if desired, a thickener, a dispersant, a silane coupling agent, a titanium coupling agent, a leveling agent, a dye, a fungicide, a preservative, an antioxidant, an antioxidant. , Adhesives, antifogging agents, flame retardants and other additives can also be added.
When the aqueous dispersion of the present invention is not used, the mixing method of each component is not particularly limited, but the component (C) and the component (D) are not particularly limited. In the case of using, a method of obtaining a mixture of the components (A) to (D) excluding the component (D) and then adding the component (D) to the mixture, specifically, the following methods are preferable. .. The method of mixing the remaining components and other additives in the present invention is not particularly limited. A predetermined amount of water is added to a mixture of the organosilanes (a1), (B) and (C) constituting the component (A) to carry out a hydrolysis / partial condensation reaction, and then the component (D) is added. How to add. A predetermined amount of water is added to a mixture composed of the organosilanes (a1) and (B) constituting the component (A) to carry out a hydrolysis / partial condensation reaction, and then the component (C) is added and mixed. (D) Method of adding a component. Further, in the aqueous dispersion of the present invention, in some cases, the above-mentioned or method is carried out using each of the components (A) to (D) excluding the component (B), and then the component (B) is added. It can also be prepared by the method of
The total solid content concentration of the aqueous dispersion of the present invention is usually 5 to 80% by weight, preferably 5 to 50% by weight, and is appropriately adjusted according to the intended use. For example, when the main purpose of the coating material is to form a thin film and / or impregnate the substrate, the total solid content concentration is usually 5 to 20% by weight, and when a thick film is formed or a filler is blended. The total solid content concentration is usually 20 to 45% by weight, preferably 25 to 40% by weight.
0050 The aqueous dispersion of the present invention is particularly useful as a coating material, and can be used for both clears containing no coloring component and enamel containing coloring components. When the coating material made of the aqueous dispersion of the present invention is applied to a base material, a brush, a roll coater, a flow coater, a centrifugal coater, an ultrasonic coater, etc. are used. Depending on the application method such as dip coating, sink coating, spray, screen process, electrodeposition, vapor deposition, etc., the thickness is about 0.5 to 40 μm for one coating, and the thickness is 1 to 3 for 2-3 coatings. A coating film of about 80 μm can be formed. After that, a coating film can be formed on various substrates by drying at room temperature or heating at a temperature of about 30 to 200 ° C. and drying. Examples of the base material to which the coating material made of the aqueous dispersion of the present invention can be applied include metals such as iron, aluminum and stainless steel; cement, concrete, ALC, flexible board, mortar, slate and gypsum. , Ceramics, inorganic ceramic materials such as bricks; plastic molded products such as phenol resin, epoxy resin, polyester, polycarbonate, polyethylene, polypropylene, ABS resin (acrylonitrile-butadiene-styrene resin); polyethylene, polypropylene , Polyvinyl alcohol, polycarbonate, polyethylene terephthalate, polyurethane, plastic films such as polyimide, wood, paper, glass and the like. Further, the coating material made of the aqueous dispersion of the present invention is also useful for recoating a deteriorated coating film. These base materials can be surface-treated in advance for the purpose of adjusting the base, improving the adhesion, sealing the porous base material, smoothing, patterning, and the like. For example, examples of the surface treatment for the metal-based base material include polishing, degreasing, plating treatment, chromate treatment, flame treatment, and coupling treatment, and examples of the surface treatment for the plastic-based base material include, for example. , Blast treatment, chemical treatment, degreasing, flame treatment, oxidation treatment, steam treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, ion treatment, etc.
0051 The coating operation using the coating material composed of the aqueous dispersion of the present invention differs depending on the type and state of the base material and the coating method. For example, in the case of a metal-based base material, a primer is used if rust prevention is required, and in the case of an inorganic ceramic-based base material, the hiding property of the coating film depends on the characteristics of the base material (surface roughness, impregnation, alkalinity, etc.). Since they are different, a primer is usually used, and even in the case of an organic resin-based base material, a primer is usually used. In the case of repainting the deteriorated coating film, a primer is used when the deterioration of the old coating film is remarkable. In the case of other base materials, for example, metals, tiles, glass, etc. that do not require rust prevention, a primer may or may not be used depending on the application. The type of primer is not particularly limited, and any primer may be used as long as it has an effect of improving the adhesion between the base material and the coating material, and is selected according to the type of base material and the purpose of use. The primer can be used alone or in combination of two or more, and may be an enamel containing a coloring component such as a pigment, a clear containing the coloring component, or a special curing accelerator added. You may. As for the type of primer, when the coating material is enamel, organic matter decomposition at the interface between the primer and the coating film containing the photocatalyst component ((B) component) is unlikely to occur, so the adhesion that is usually used as a primer is used. An organic resin having good properties may be used, for example, alkyd resin, aminoalkyd resin, epoxy resin, polyester, acrylic resin, urethane resin, fluororesin, acrylic silicon resin, acrylic emulsion, epoxy emulsion, polyurethane emulsion, polyester emulsion. , Silicon acrylic emulsion, polysiloxane and the like. Further, when the coating material is clear, organic substances are likely to be decomposed at the interface between the primer and the coating film containing the photocatalyst component ((B) component). Therefore, as the primer, an organic resin having high oxidation resistance, for example, , Silicon acrylic emulsion, acrylic silicone resin, polysiloxane, fluorine resin, alkoxysilyl-modified polyester, acrylic urethane resin, (A) A composition composed of the component and the component (B) is preferable. Further, various functional groups can be added to these primers when adhesion between the base material and the coating film is required under severe conditions. Examples of such a functional group include a hydroxyl group, a carboxyl group, a carbonyl group, an amide group, an amine group, a glycidyl group, an alkoxysilyl group, an alkylsilyl group, an ether bond, an ester bond and the like.
The form in which the coating material made of the aqueous dispersion of the present invention is applied to the base material is as follows. Base material / coating material (clear-, enamel) Base material / coating material (enamel) / coating material (clear-) Base material / coating material containing no photocatalytic component (clear-, enamel) / coating material (clear-) In the above cases, the base material can be pretreated and / or primed as necessary, as described above. For the purpose of further enhancing the wear resistance and gloss of the coating film on the surface of the coating film formed from the coating material composed of the aqueous dispersion of the present invention, for example, US Pat. No. 3,986,997, It is also possible to form a clear layer made of a siloxane resin-based paint such as a stable dispersion of colloidal silica and a siloxane resin described in US Pat. No. 4,027,073. The coating material made of the aqueous dispersion of the present invention is useful for a wide range of applications, and in particular, the surface of a packaging material, a magnetic tape, a photographic film, a film for an overhead projector, an information recording card, a material to be printed, or a concrete structure. It can be extremely suitably used for painting objects, wood building materials, synthetic building materials, precast materials, interior and exterior of buildings, interior and exterior of automobiles, cans and the like. Further, the coating material made of the aqueous dispersion of the present invention can also be used as a functional coating material having antibacterial property, antifungal property, anti-algae property, deodorant property, antistatic property and the like.
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BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. The parts and% in the examples are based on weight unless otherwise specified. The measurements and evaluations in the examples and comparative examples were carried out as follows. Mw and Mn Measured by gel permeation chromatography (GPC) method under the following conditions. Sample solution: 1 g of component (I) or 0.1 g of component (II) dissolved in 100 cc of tetrahydrofuran, standard polystyrene: manufactured by US Pressure Chemical Co., Ltd., equipment: high-temperature high-speed gel permeation chromatogram manufactured by US Waters, Inc. Model 150-C ALC / GPC), Column: SHOWEX A-8M (length 50 cm) manufactured by Showa Denko KK, Measurement temperature: 40 ° C., Flow velocity: 1 cc / min. Storage stability The composition to which no curing accelerator was added was stored in a glass bottle in a tightly closed container at room temperature for 3 months, and the dispersed state and transparency were visually judged. Appearance of coating film The appearance of the coating film was observed visually and by a stereomicroscope (magnification: 100 times). Hardness JIS It was based on the pencil hardness of K5400. Adhesion The tape peeling test was carried out three times by the grid test (100 grids) by JIS K5400, and the average was used. Weather resistance JIS K5400 was used to carry out an irradiation test for 3,000 hours with a sunshine weather meter, and the appearance (cracking, peeling, etc.) of the coating film was visually observed. In addition, the gloss of the coating film before and after the test was measured and evaluated according to the following criteria. Gloss retention rate is 90% or more: Gloss retention rate is 50% to less than 90%: Gloss retention rate is less than 50%: × Alkali resistance 1 cc of sodium hydroxide aqueous solution with a concentration of 1 to 40% is dropped on the coating film. Then, after allowing to stand in a chalet with a lid for 6 hours and washing with water, the state of the coating film was visually observed to determine the maximum concentration of the aqueous sodium hydroxide solution having no abnormality in the coating film. Organic chemical resistance 2 cc of isopropyl alcohol was dropped onto the coating film, and after 5 minutes, it was wiped off with a cloth, and then the state of the coating film was visually observed. A test piece using a heat-resistant water-resistant inorganic base material was immersed in warm water at 60 ° C. for 14 days, and then the state of the coating film was visually observed. 0.05mW / cm for hydrophilic coating film<sup>2 </sup>After irradiating with a black light fluorescent lamp for 5 hours, the contact angle of water was measured. The lower the contact angle of water, the better the stain resistance. Transparency Each composition was applied onto quartz glass so as to have a dry film thickness of 10 μm, and then the transmittance of visible light was measured and evaluated according to the following criteria. Transmittance exceeds 80%: Transparent Transmittance 60-80%: Translucent Transmittance less than 60%: Opacity
Reference Example 1 <Preparation of partial condensate of organosilane (a1)> In a reactor equipped with a reflux condenser and a stirrer, 100 parts of methyltrimethoxysilane, 30 parts of dimethyldimethoxysilane, and 12 parts of ion-exchanged water. , 0.1 part of 0.1N hydrochloric acid and 10 parts of i-propyl alcohol were added and mixed, then heated to 60 ° C. with stirring and reacted at the same temperature for 3 hours to obtain an organogen having a solid content concentration of 44%. A solution of a partial condensate of silane (aI) was obtained. The Mw of this partial condensate was 12,000.
Reference Example 2 <Production of Vinyl Polymer (b1)> 70 parts of methyl methacrylate, 40 parts of n-butyl acrylate, and γ-methacryloxypropyltrimethoxysilane in a reactor equipped with a reflux cooler and a stirrer. 20 parts, 5 parts of acrylic acid, 13 parts of 2-hydroxyethyl methacrylate, 2 parts of 1,1,1-trimethylamine methacrylate and 130 parts of i-propyl alcohol are added and mixed, and then heated to 80 ° C. with stirring. A solution prepared by dissolving 4 parts of azobisisovaleronitrile in 10 parts of xylene was added dropwise to this mixture over 30 minutes, and then reacted at 80 ° C. for 5 hours to obtain a vinyl polymer (b1) having a solid content concentration of 50%. Solution was obtained. This vinyl-based polymer (b1) had an Mn of 12,000 and had an average of 6 silyl groups per molecule of the polymer. This vinyl-based polymer (b1) is referred to as a vinyl-based polymer (b1-1).
Reference Examples 3 to 5 <Production of Vinyl Polymer> The reaction formulation is the same as that of Reference Example 2 except that the reaction formulation is as shown in Table 1, and the vinyl polymer (b1-2) and the vinyl polymer for comparison are used. The vinyl-based polymers (c-1) to (c-2) of the above were obtained.
Reference Example 6 <Preparation of Primer> In a reactor equipped with a reflux condenser and a stirrer, 100 parts of methyltrimethoxysilane, 50 parts of dimethyldimethoxysilane, and the vinyl polymer obtained in Reference Example 2 (b1- 1) After mixing 50 parts with a solution of 25 parts of di-i-propoxyethylacetacetate aluminum dissolved in 50 parts of i-propyl alcohol, 40 parts of ion-exchanged water is added, and the mixture is reacted at 60 ° C. for 4 hours. It was. Then, after cooling the reaction solution to room temperature, 15 parts of acetylacetone and 15 parts of ethyl acetoacetate were added to obtain a primer.
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[Example]
Example 1 <Preparation of polymer (A) solution> In a reactor equipped with a stirrer and a reflux cooler, 100 parts of methyltrimethoxysilane, 50 parts of the vinyl-based polymer (b1-1) obtained in Reference Example 2, And 120 parts of an aqueous sol of titanium oxide (titanium oxide content 40%, water 40%, alcohol 20%) and 20 parts of di-i-propoxy ethylacetate acetate aluminum (0.07 mol equivalent) are added to i-propyl alcohol 40. After mixing with the solution dissolved in the parts, 30 parts of ion-exchanged water was added, and the mixture was reacted at 60 ° C. for 4 hours. Then, after cooling the reaction solution to room temperature, 20 parts (0.2 molar equivalent) of acetylacetone was added to obtain a polymer (A) solution in which titanium oxide was dispersed. <Emulsification dispersion> To the polymer (A) solution, 2 parts of an alkyl sulfate ester salt as an emulsifier and 5 parts of 10% aqueous ammonia were added and mixed well at a temperature of 30 ° C. or lower to adjust the pH to 7.5. .. Then, it was diluted with 200 parts of i-propyl alcohol, and the obtained solution was gradually added to 500 parts of ion-exchanged water over 2 hours to form an emulsion. Next, i-propyl alcohol and water were removed from this emulsion at a temperature of 50 ° C. or lower under reduced pressure, and then the total solid content concentration was adjusted to 35% to prepare the aqueous dispersion A of the present invention. The evaluation results of the storage stability of the aqueous dispersion A are shown in Table 2.
Examples 2 to 5 The aqueous dispersions B to E of the present invention were prepared in the same manner as in Example 1 except that the amount or type of titanium oxide was changed as shown in Table 2. Table 2 shows the evaluation results of the storage stability of each aqueous dispersion.
Example 6 <Preparation of Polymer (A) Solution> 130 parts (solid content) of the partial condensate of organosilane (aI) obtained in Reference Example 1, the vinyl-based polymer obtained in Reference Example 2. (B1-1) 50 parts and 300 parts of an aqueous sol of titanium oxide (titanium oxide content 40%, water 40%, alcohol 20%) were reacted at 60 ° C. for 4 hours to disperse a polymer (titanium oxide). A) A solution was obtained. <Emulsification dispersion> The aqueous dispersion F of the present invention was prepared by emulsification and dispersion in the same manner as in Example 1 except that the polymer (A) solution was used. The evaluation results of the storage stability of the aqueous dispersion F are shown in Table 2.
Examples 7 to 9 and Comparative Example 1 The aqueous dispersions GI of the present invention and comparative formulations were used in the same manner as in Example 1 except that the formulation was changed as shown in Table 2 or Table 3. An aqueous dispersion J was prepared. The evaluation results of the storage stability of the aqueous dispersions G to J are shown in Tables 2 and 3.
2% (solid content) of aqueous dibutyltin dilaurate was added as a curing accelerator to the aqueous dispersions A to I of Examples 1 to 10 and the aqueous dispersion J of Comparative Example 1 and mixed. Then, a coating material (clear) was prepared. Mighty Epo Sealer
[Epoxy resin sealer manufactured by Dai Nippon Toryo Co., Ltd.] with a dry weight of 50 g / m<sup>2</sup> The primer obtained in Reference Example 6 was added to a slate plate (JIS A5043F) coated and dried by a dry weight of 30 g / m.<sup>2</sup> After coating, each of the above coating materials is further subjected to a dry weight of 50 g / m.<sup>2</sup> It was applied and heated at 120 ° C. for 10 minutes to prepare a test piece. Various evaluations were performed on each of the obtained test pieces. The evaluation results are shown in Table 4.
Test Examples 11 to 13 Using the aqueous dispersions A to C of Examples 1 to 3, the mixture of the compounding formulations shown in Table 5 was kneaded with a sand mill to obtain a composition, and then these compositions were obtained. 2% (solid content) of water-based dibutyltin dilaurate was added to the product as a curing accelerator and mixed to prepare a coating material (enamel). Mighty Epo Sealer
[Epoxy resin sealer manufactured by Dai Nippon Toryo Co., Ltd.] with a dry weight of 50 g / m<sup>2</sup> On a slate plate (JIS A5043F) that has been applied and dried, each of the above coating materials is subjected to a dry weight of 50 g / m.<sup>2</sup> It was applied and heated at 120 ° C. for 10 minutes to prepare a test piece. Various evaluations were performed on each of the obtained test pieces. The evaluation results are shown in Table 5.
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[Table 1] <img file="000011.tif" id="000011" he="085" wi="080" img-format="tif" img-content="drawing" />
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[Table 2] <img file="000012.tif" id="000012" he="160" wi="108" img-format="tif" img-content="drawing" />
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[Table 3] <img file="000013.tif" id="000013" he="155" wi="049" img-format="tif" img-content="drawing" />
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[Table 4] <img file="000014.tif" id="000014" he="065" wi="110" img-format="tif" img-content="drawing" />
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[Table 5] <img file="000015.tif" id="000015" he="090" wi="055" img-format="tif" img-content="drawing" />
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[Effects of the Invention] Although the aqueous dispersion of the present invention has photocatalytic activity, it has extremely excellent storage stability, and also has adhesiveness, weather resistance, alkali resistance, organic chemical resistance, and thermal water resistance. It has excellent long-term durability such as stain resistance, and can form a coating film that is transparent, has high hardness, and can be thickened, and can be extremely suitably used as an environment-friendly coating material.
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Numbers
- Application
- 17128897
Titles
- English
- AQUEOUS DISPERSION
Classification
- IPC, 4
- C08K3 00
- C08K3 22
- C08L83 07
- C08L101 10