JP2001262063A - Inorganic coating material which may form photocatalytically active coating film and coating process using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating material which may form a coating film which exhibits an excellent coating film performance, has a photocatalytic activity and exerts an excellent ability to decompose nitrogen oxides within air, resistances to exposure and stain and antibacterial property. SOLUTION: The inorganic coating material which may form a photocatalytically active coating film contains [I] a dealcoholization condensate of a mixture containing, based on 100 pts.wt. (A) alkylarylalkoxypolysiloxane having a weight average molecular weight of 500 to 4,000 and an alkoxy group content of 10 to 30 wt.% 5 to 1,000 pts.wt. (B) alkyltrialkoxysilane condensate and, based on 100 pts.wt. total of components (A) and (B), 3 to 100 pts.wt. (C) epoxy group-containing alkoxysilane, and [II] a photocatalytically active titanium oxide. In a process for forming the photocatalytically active coating film, the inorganic coating material which may form a photocatalytically active coating film is applied onto the article to be coated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inorganic paint capable of forming a photocatalytically active coating film and a method for forming a photocatalytically active coating film using the inorganic paint.

[0002]

2. Description of the Related Art In recent years,
As part of the purification of living environment, to decompose pollutants such as nitrogen oxides and sulfur oxides in the air due to exhaust gas around the motorway, and to improve the exposure pollution resistance by making the coating film surface hydrophilic. It has also been proposed to apply a photocatalytically active paint for the purpose of imparting antibacterial and antifungal properties to the coating film.

As a coating material having photocatalytic activity, for example, a coating material in which a powder such as titanium dioxide or zinc oxide having photocatalytic activity is blended into a fluororesin-based coating material or an inorganic coating material has been proposed (for example, Japanese Patent Application Laid-Open No. H10-163,878). 10-19533
No. 3, JP-A-10-265713). Titanium dioxide and zinc oxide having photocatalytic activity are optical semiconductors and have a band gap around 3 eV.
It is easily excited by irradiation of sunlight or artificial illumination light, generates holes and OH radicals, exhibits strong oxidizing action, and has an antibacterial property due to the oxidizing action.

[0004] The oxidizing action can decompose pollutants in the air. For example, it has the action of oxidizing nitrogen oxides in the air and eventually converting it into nitric acid, or decomposing it into nitrogen and water. When the surface of the coating film is hydrophilized to improve the resistance to exposure contamination, a powder having photocatalytic activity and, if necessary, an alkyl silicate or a condensate thereof are blended with the resin having an alkoxysilyl group. In addition, the surface of the coating film is made hydrophilic by changing an alkoxysilyl group into a silanol group by an acid generated by the oxidizing action.

[0005] However, the organic resin-based coatings having photocatalytic activity such as the above-mentioned fluororesin-based coatings are liable to be oxidized, and the resulting coating film has poor weather resistance and is easily decomposed and deteriorated. It could not stand and was not practical.

[0006] Further, conventional inorganic coatings having photocatalytic activity have the problems that the coating film properties such as impact resistance and coating film adhesion of the obtained coating film are not sufficient, and the dispersibility of the pigment is not sufficient. there were.

An object of the present invention is to provide a coating film having good oxidation resistance, weather resistance, impact resistance, coating adhesion, etc., without being deteriorated by the oxidizing action of the powder having photocatalytic activity, and being suitable for long-term use. It can withstand, can form a coating film with excellent decomposability of pollutants such as nitrogen oxides in the air, exposure pollution resistance, antibacterial property, and can be dried at room temperature or relatively low temperature, pigment dispersibility It is to provide a good paint.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, as a binder component, an alkylarylalkoxypolysiloxane, an alkyltrialkoxysilane condensate, and an epoxy group-containing alkoxysilane The present inventors have found that the above object can be achieved by an inorganic paint in which a binder component and a photocatalytically active titanium oxide are combined using a dealcoholation condensation reaction product of the present invention and the present invention.

[0009] The present invention, [I] (A) the following rational formula ^{_{R 1 a R 2 b (R}} 3 O) c SiO in _{(4-abc) / 2} Formula, R ¹ and R ³ are the same or different And carbon number 1-8
And R ² represents an aryl group, a is 0.1 ≦ a ≦ 2.0, b is 0.1 ≦ b ≦ 2.0, and b / a is 0.2 ≦ b /A≦2.0, and c is 0.1.
1 ≦ c ≦ 1.0, wherein (a + b + c) is less than 4, wherein the polysiloxane has a weight average molecular weight in the range of 500 to 6,000 and an alkoxyl group content of the polysiloxane. 10-30% by weight based on siloxane
And (B) in the following formula R ⁴ Si (OR ⁵ ) ₃ , wherein R ⁴ and R ⁵ are the same or different and have 1 to 8 carbon atoms.
A condensate of an alkyl trialkoxysilane represented by an alkyl group having a weight average molecular weight in the range of 300 to 3,000, and having an alkoxyl group content of 20 to 55 based on the condensate. 0 to 500 parts by weight of the alkyltrialkoxysilane condensate in the range of weight%, the alkylarylalkoxypolysiloxane (A) and the alkyltrialkoxysilane condensate (B)
Based on the total 100 parts by weight of, (C) the following general formula _{^{R 6 R 7 n Si (OR}} 8) (3-n) wherein the organic group R ⁶ is containing an epoxy radical, n pieces of R ⁷
Are the same or different and each have an alkyl group having 1 to 8 carbon atoms;
R ⁸ is the same or different and is a hydrogen atom or a carbon atom
Wherein n represents an integer of 0 to 2, and comprises a dealcoholation condensation reaction product with 3 to 100 parts by weight of an epoxy group-containing alkoxysilane represented by the formula: and [II] a photocatalytically active titanium oxide. The present invention provides an inorganic paint capable of forming a photocatalytically active coating film.

[0010] The present invention also provides a method for forming a photocatalytically active coating film, which comprises applying an inorganic paint capable of forming the above-mentioned photocatalytically active coating film on an object to be coated.

Further, the present invention provides an inorganic paint capable of forming an inorganic undercoating film containing no photocatalytically active titanium oxide on a substrate to be coated, and forming the photocatalytically active coating film on the inorganic undercoating film. And a method of forming a photocatalytically active coating film, characterized by coating

Further, the present invention provides a method for forming a colored organic coating film on an object to be coated, and forming an inorganic coating film containing no photocatalytically active titanium oxide on the colored organic coating film. A method for forming a photocatalytically active coating film, characterized by applying an inorganic paint capable of forming the above-mentioned photocatalytically active coating film thereon.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. First, the inorganic paint of the present invention will be described in detail.

The inorganic coating composition of the present invention comprises: [I] a dealcoholization condensation product of the following alkylarylalkoxypolysiloxane (A), alkyltrialkoxysilane condensate (B) and epoxy group-containing alkoxysilane (C); [II] A paint capable of forming a photocatalytically active coating film containing photocatalytically active titanium oxide.

Alkylarylalkoxypolysiloxane
(A) An alkylarylalkoxypolysiloxane [hereinafter referred to as “polysiloxane (A)” which is a component (A) for producing a dealcoholization condensation product [I] in the paint of the present invention.
Is a polysiloxane containing an alkyl group, an aryl group, and an alkoxy group, and has the following formula: R ¹ _a R ² _b (R ³ O) _c SiO _{(4-abc) / 2} Wherein R ¹ and R ³ are the same or different and have 1 to 1 carbon atoms.
8, preferably 1 to 4 alkyl groups, R ² represents an aryl group, a is 0.1 ≦ a ≦ 2.0, b is 0.1 ≦ b ≦
2.0 and b / a is 0.2 ≦ b / a ≦ 2.0, c
Is 0.1 ≦ c ≦ 1.0, and (a + b + c) is less than 4.

Since the polysiloxane (A) has an aryl group in the above-mentioned quantitative range, it is excellent in film-forming properties. The polysiloxane (A) has a weight average molecular weight (in terms of polystyrene) of 500 to 6,000, particularly 700 to 6,000.
It is preferred that the content be in the range of 4,000, and the content of the alkoxyl group be in the range of 10 to 30% by weight, particularly in the range of 15 to 25.

Alkyl trialkoxysilane condensate
(B) Alkyl trialkoxysilane condensate (hereinafter sometimes abbreviated as "condensate (B)") as component (B) for producing dealcoholization condensation product [I] in the paint of the present invention is In the formula, R ⁴ Si (OR ⁵ ) ₃ , wherein R ⁴ and R ⁵ are the same or different and have 1 to 1 carbon atoms.
8, preferably a condensate of an alkyl trialkoxysilane represented by 1 to 4 alkyl groups, having a weight average molecular weight of 300 to 3,000, preferably 500 to 2,000. , A condensate having an alkoxyl group content in the range of 20 to 55% by weight, preferably 25 to 50% by weight, based on the condensate.

Specific examples of the alkyltrialkoxysilane used for producing the condensate (B) include, for example, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, hexyltrimethoxysilane And methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltriethoxysilane, methyltripropoxysilane, propyltripropoxysilane, and methyltributoxysilane. When producing the condensate (B), these alkyl trialkoxysilanes can be used alone or in combination of two or more.

Epoxy group-containing alkoxysilane (C) The epoxy group-containing alkoxysilane (hereinafter sometimes abbreviated as “epoxysilane (C)”), which is the component (C), has the following general formula: R ⁶ R ⁷ _n Si (oR ⁸⁾ in _(3-n) formula, R ⁶ is an organic group containing an epoxy radical, n pieces of R ⁷ are the same or different, 1 to 8 carbon atoms, preferably 1 to 4
Wherein R ⁸ is the same or different and represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 4; and n represents an integer of 0 to 2; Compound.

Specific examples of the epoxysilane (C) include, for example, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, γ-
Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyl (methyl) dimethoxysilane, γ-glycidoxypropyl (dimethyl) methoxysilane, γ-glycidoxypropyl (ethyl ) Dimethoxysilane, 3,4-epoxycyclohexylmethyltrimethoxysilane, β-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be mentioned. These epoxy group-containing alkoxysilanes can be used alone or in combination of two or more.

The above polysiloxane (A) and condensate (B)
And an epoxysilane (C), for example, by heating in the presence of a reaction catalyst and water to cause a dealcoholization condensation reaction, thereby producing a dealcoholation condensation product. In producing this dealcoholization condensation reaction product, the polysiloxane (A) is bonded to Si in the polysiloxane (A) by heating the polysiloxane (A) in advance in the presence of a reaction catalyst and water without removing the alcohol from the reaction system. After converting a part of the alkoxy group into a hydroxyl group (silanol group) bonded to Si, a condensate (B) and an epoxysilane (C) are added thereto, and the alcohol is removed from the system by heating. A dealcoholization condensation reaction may be performed. Further, a mixture of the polysiloxane (A) and the condensate (B) is heated in advance in the presence of a reaction catalyst and water without removing the alcohol from the reaction system, so that the polysiloxane (A) and the condensate (B) are heated. After changing a part of the alkoxy group bonded to Si in the above) into a hydroxyl group (silanol group) bonded to Si, epoxysilane (C) is added to this, and the alcohol is removed from the system by heating. The alcohol may be subjected to a dealcoholization condensation reaction. Furthermore, the polysiloxane (A), the condensate (B) and the epoxy silane (C) are simultaneously heated in the presence of a reaction catalyst and water,
The dealcoholization condensation reaction may be advanced while removing the generated alcohol to the outside of the system.

In the above reaction, (A), (B) and / or
Alternatively, the condensation reaction is suppressed by heating the component (C) in the presence of the reaction catalyst and water without removing the alcohol from the reaction system. The part can be changed to a hydroxyl group (silanol group) bonded to Si. Since the generated silanol group is more likely to cause a condensation reaction than the alkoxysilyl group, a part of the alkoxy group bonded to Si, which is a component that is less likely to cause a condensation reaction than other components, is bonded to Si. The condensation reaction can be controlled by changing it to a hydroxyl group (silanol group) in advance.

The mixing ratios of the respective components of the polysiloxane (A), the condensate (B) and the epoxysilane (C) are as follows. The amount of the condensate (B) is from 0 to 500 based on 100 parts by weight of the polysiloxane (A).
It is preferably in the range of 10 parts by weight, particularly 10 to 200 parts by weight, from the viewpoint of room temperature curability, coating film hardness and adhesiveness. The compounding amount of the epoxysilane (C) is in the range of 3 to 100 parts by weight, particularly 5 to 50 parts by weight based on 100 parts by weight of the total of the polysiloxane (A) and the condensate (B). This is preferable from the viewpoints of room temperature curability, pot life and adhesion.

As the reaction catalyst in the dealcoholization condensation reaction, metal alkoxide compounds, metal chelate compounds, metal ester compounds, inorganic acids, organic acids and the like are used. Examples of the metal alkoxide compound include aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum triisobutoxide, aluminum trisec-butoxide, and aluminum. Aluminum alkoxide such as tri-tert-butoxide; Titanium alkoxide such as tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl titanate, tetra n-butyl titanate, tetraisooctyl titanate; tetraethyl zirconate, tetra n-propyl Zirconate, tetraisopropyl zirconate, tetra n-butyl zirconate, tetra n-octyl zirconate And the like. Examples of the metal chelate compound include tris (ethylacetoacetate) aluminum, tris (n-propylacetoacetate) aluminum, tris (isopropylacetoacetate) aluminum, and tris (n). -Butylacetoacetate) aluminum, isopropoxybis (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, tris (proponylacetonato) aluminum, diisopropoxypropionylacetonatoaluminum, acetylacetonatobis (propionylacetone) Nato) aluminum, monoethyl acetoacetate bis (acetylacetonato) aluminum, acetylacetonato aluminum di-sec
Aluminum chelate compounds such as butyrate; diisopropoxy bis (ethylacetoacetate) titanate;
Titanium chelate compounds such as diisopropoxy bis (acetylacetonato) titanate; zirconium chelate compounds such as tetrakis (acetylacetonato) zirconium and tetrakis (n-propylacetoacetate) zirconium; dibutyltin bis (acetylacetonate); Examples of the metal ester compound include tin ester compounds such as dibutyltin diacetate, dibutyltin di (2-ethylhexylate), and dibutyltin dilaurate. Examples of the inorganic acid include nitric acid, hydrochloric acid, and phosphoric acid, and examples of the organic acid include acetic acid, formic acid, and propionic acid. These reaction catalysts can be used alone or in combination of two or more.

The amount of the reaction catalyst used is usually 0.001 parts by weight based on 100 parts by weight of the total of the components (A), (B) and (C).
It is preferred that the amount be in the range of 01 to 1 part by weight. The amount of water is usually 0.02 to 1 equivalent of the alkoxysilyl group in the total of the components (A), (B) and (C).
Preferably it is in the range of 0.4 mol.

In the dealcoholization condensation reaction, the reaction conditions are not particularly limited. However, the reaction is carried out without removing the alcohol from the reaction system in the presence of a reaction catalyst and water without removing (A), (B) ) And / or (C)
When a part of the alkoxy group bonded to Si in the component is changed to a hydroxyl group (silanol group) bonded to Si, it is usually at room temperature to 100 ° C. for 5 minutes to 5 hours, particularly 40 to 100 hours.
Stir without removing alcohol at 80 ° C. for 10 minutes to 3 hours, then stir at 60 to 250 ° C. (preferably 100 ° C.)
(200 ° C. to 200 ° C.), and the reaction is preferably performed for 1 hour to 24 hours while removing the alcohol generated by the reaction. When the step of heating without removing the alcohol from the reaction system in the presence of the reaction catalyst and water is not performed, usually 60 to 250 ° C (preferably 100 ° C to 200 ° C)
The reaction is preferably carried out for 1 hour to 24 hours while removing the alcohol generated by the reaction.

The dealcoholization condensation product has an epoxy equivalent of 300 to 5,000, particularly 500 to 4,000, and a weight average molecular weight (polystyrene conversion) of 1,000.
Absorbance of [absorption based on silanol group (around 3400 cm ⁻¹ ) / absorption based on siloxane (around 1080 cm ⁻¹ )] in the infrared absorption spectrum, which is in the range of 0 to 40,000, especially 2000 to 30,000. The ratio is 0.
It is preferably at most 04, desirably at most 0.03 from the viewpoint of pigment dispersion stability.

Photocatalytically Active Titanium Oxide [II] The photocatalytically active titanium oxide contained in the inorganic paint of the present invention can be used without any particular limitation as long as it has photocatalytic activity. Titanium dioxide can be mentioned. Suitable commercial products of anatase-type titanium dioxide include, for example, ST-01, ST-21, ST-31, manufactured by Ishihara Techno Co., Ltd.
AMT600 and the like can be mentioned.

The photocatalytically active titanium oxide is excited by absorbing ultraviolet light such as sunlight or artificial illumination light, for example, ultraviolet light having a wavelength of 400 nm or less, preferably light having a wavelength of 285 nm to 380 nm. It generates OH radicals, which have a strong oxidizing effect, and also have antibacterial properties due to this oxidizing effect.

By this strong oxidizing action, pollutants in the air can be decomposed. For example, nitrogen oxides in the air can be oxidized to be converted to nitric acid, or chemically converted to nitrogen or water. Also, sulfur oxides in the air can be oxidized and changed to sulfuric acid. Further, the alkoxysilyl group based on the dealcoholization condensation reaction product [I] and the alkyl silicate compounded as necessary and the alkoxysilyl group of the condensation product are changed into silanol groups to hydrophilize the coating film surface to prevent exposure contamination. Performance can be improved.

In the paint of the present invention, the compounding amount of the powder having the photocatalytic activity is 10% of the total solid content of the inorganic paint of the present invention.
The amount is preferably 5 to 90 parts by weight, and more preferably 3 to 90 parts by weight.
More preferably, it is in the range of 0 to 80 parts by weight.

The inorganic paint of the present invention contains the dealcoholization condensation product [I] as a binder component, and usually further contains a curing agent. Examples of the curing agent include amino group-containing alkoxysilanes, and specific examples thereof include N-
(2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and the like. be able to. These compounds can be used alone or in combination of two or more.

In the inorganic coating composition of the present invention, the mixing ratio of the curing agent is not particularly limited. However, when an amino group-containing alkoxysilane is used as the curing agent, the dealcoholization condensation reaction product [I] and the aforementioned The mixing ratio with the amino group-containing alkoxysilane is such that the ratio of the number of equivalents of active hydrogen of the amino group / the number of equivalents of epoxy group in the dealcoholization condensation reaction product [I] is 0.3 to 3.0, particularly 0. 0.5-1.5
It is preferable that the ratio be within the range from the viewpoint of the curability of the obtained paint, the pot life, and the like.

The inorganic coating composition of the present invention may further comprise, if necessary, a curing catalyst other than the above-mentioned dealcoholization-condensation reaction product [I], a photocatalytically active titanium oxide, and a curing agent, if necessary. Color pigments such as titanium oxide, carbon black, cyanine blue, cyanine green and quinacridone red; extenders such as calcium carbonate, talc, clay, silica, barium sulfate and mica; organic solvents; fluidity control used in the paint industry Other additives such as an agent can be contained.

The curing catalyst promotes a curing reaction between the dealcoholization condensation reaction product [I] and a curing agent such as an amino group-containing alkoxysilane, and specific examples of the curing catalyst include sodium hydroxide. Alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as acetic acid and paratoluenesulfonic acid; tetramethylammonium hydroxide, tetraethylammonium hydroxide and tetrabutylammonium hydroxide Ammonium salts such as dibutylamine-2-hexoate, dimethylamine acetate and ethanolamine acetate; quaternary ammonium salts of carboxylic acids such as tetramethylammonium acetate; amines such as tetraethylpentamine And aluminum alkoxides; Rumi bromide chelate; tetraisopropyl titanate, tetrabutyl titanate, organic titanium compounds such as titanium tetra acetyl acetonate; dibutyltin diacetate, organic tin ester compounds such as dibutyltin dilaurate; imidazole, 1-
Imidazole derivatives such as methylimidazole, 2-methylimidazole, and 4-methylimidazole; piperidine, piperazine, and pyrrolidine;
These curing catalysts can be used alone or in combination of two or more.

When the curing catalyst is blended, the amount of the curing catalyst is usually 0.0001 to 1 based on the total of 100 parts by weight of the dealcoholization condensation reaction product [I] and the curing agent.
It is preferably in the range of parts by weight.

Next, a method for forming a photocatalytically active coating film of the present invention will be described.

The method for forming the photocatalytically active coating film of the present invention includes the following three embodiments. (1) As a first embodiment, a photocatalyst for coating an inorganic paint capable of forming the photocatalytically active coating film of the present invention on an object to be coated (hereinafter, may be abbreviated as “photocatalytically active inorganic paint”). A method for forming an active coating. (2) As a second embodiment, an inorganic lower layer coating film containing no photocatalytically active titanium oxide is formed on the object to be coated, and the above-mentioned photocatalytically active inorganic coating material of the present invention is coated on the inorganic lower layer coating film. Of forming a photocatalytically active coating film. (3) As a third embodiment, a colored organic coating film is formed on an object to be coated, and an inorganic coating film containing no photocatalytically active titanium oxide is formed on the colored organic coating film. A method for forming a photocatalytically active coating film on which the above-mentioned photocatalytically active inorganic coating material of the present invention is applied.

In the first, second and third aspects,
Metal substrates such as iron, aluminum, stainless steel, galvanized steel sheet, zinc alloy-plated steel sheet (steel plated with an alloy such as iron-zinc, nickel-zinc, and aluminum-zinc), and tin plate; Plastic substrate;
Inorganic ceramic substrates such as glass, cement, slate, mortar, concrete, and tile; and the like; paper; and coated substrates obtained by coating these substrates with a coating film.

In the first embodiment, the object to be coated is
Since the photocatalytically active inorganic paint of the present invention is applied directly, the object to be coated is hardly deteriorated by the oxidizing action of the photocatalytically active titanium oxide, for example, concrete, an inorganic base material such as mortar, or photocatalytically active. It is preferable that the inorganic paint contains a coloring pigment in an amount sufficient for hiding, so that ultraviolet rays do not reach the vicinity of the object to be coated.

In any of the first, second and third embodiments, the method of applying the photocatalytically active inorganic paint of the present invention is not particularly limited. The coating can be performed using an air spray coating, an airless spray coating, a roll coater, a flow coater, or the like, and the coating film thickness is not particularly limited, but is usually 5 to 60 μm (dry film thickness). Within the range is desirable. The photocatalytically active inorganic paint of the present invention,
Although it can be cured at room temperature, it may be forcibly dried or cured by heating.

In the second embodiment, an inorganic lower coating film containing no photocatalytically active titanium oxide is formed on an object to be coated. By forming the inorganic lower layer coating film, it is possible to suppress or block the adverse effect on the object due to the oxidizing action of the photocatalytically active titanium oxide in the inorganic coating material of the present invention applied on the coating film.

As the coating for forming the inorganic lower layer coating film, known inorganic coatings, such as alkyl silicate condensate and silicone resin coating, can be used. Examples of the inorganic paint include a dealcoholization condensation reaction product in the inorganic paint and, if necessary, a curing agent. These may be colored paints containing a color pigment or clear paints containing no color pigment. Although the thickness of the inorganic lower coating film is not particularly limited, it is usually desirable to be in the range of 3 to 30 μm (dry film thickness). The photocatalytically active inorganic coating material of the present invention is applied on the inorganic lower coating film.

In the third embodiment, the colored organic coating film formed on the object to be coated is for the purpose of sealing the surface of the object to be coated, making the surface uniform, improving the aesthetics by coloring, and the like. As a paint for forming the colored organic coating film (hereinafter, may be abbreviated as “colored organic resin paint”), a paint containing a conventionally known organic resin-based paint resin and a color pigment as essential components is used. be able to. As the above-mentioned colored organic resin paint, an epoxy resin paint and an acrylic silicone paint are particularly preferable.

Examples of the epoxy resin-based paint include epoxy resin-based paints known per se as sealers and undercoats. Representative examples thereof include epoxy-amine resin-based paints and epoxy urethane resin-based paints. And the like.

As the acrylic silicone paint, (1)
Polymer of a monomer mixture comprising an alkoxysilyl group-containing polymerizable unsaturated monomer or polysiloxane macromonomer such as γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, and other polymerizable unsaturated monomers ;
(2) A paint containing, as a resin component, a condensation polymer obtained by subjecting an alkoxysilyl group-containing organopolysiloxane and a hydroxyl group-containing acrylic resin to a dealcoholization reaction. The acrylic silicone-based paint may contain, for example, a curing agent such as a polyisocyanate compound.

The above-mentioned colored organic resin paint contains, in addition to the binder component and the colored pigment, organic solvents, extenders, pigments such as rust-preventive pigments, curing catalysts, paint surface modifiers, paint additives such as anti-sagging agents, and the like. Can be contained.

The organic solvent can be used without any particular limitation as long as it can dissolve or disperse the resin in the colored organic resin coating material. It is necessary that when the colored organic resin paint is applied over the old coating film, lifting of the old coating film does not occur, and therefore, an aliphatic hydrocarbon solvent and a boiling point of 150 ° C. or more are required. It is preferable that the solvent contains at least 95% by weight of a hydrocarbon solvent selected from high-boiling aromatic hydrocarbon solvents, based on the total amount of the organic solvent in the undercoat paint.

Specific examples of the above-mentioned aliphatic hydrocarbon solvents and high-boiling aromatic hydrocarbon solvents include, for example, VM & P
Naphtha, Mineral Spirit, Solvent Kerosene, Aromatic Naphtha, Solvent Naphtha, Solvesso 100, Solvesso 150, Solvesso 200 [“Solvesso” is a registered trademark of Esso Oil Co., Ltd.], Swazol 310, Swazol 1000, Swazol 1500 [“Swazol” is Cosmo Aliphatic or aromatic hydrocarbons having a relatively low dissolving power, such as n-butane, n-hexane, n-heptane, n-octane, isononane, n-decane, n-dodecane And aliphatic hydrocarbons such as cyclopentane, cyclohexane and cyclobutane. In this case, the organic solvent in the colored organic resin paint is most preferably all aliphatic hydrocarbon solvents or high-boiling aromatic hydrocarbon solvents, but among the organic solvents, aliphatic hydrocarbon solvents and It may contain 5% or less, preferably 3% or less of other organic solvents other than the high-boiling aromatic hydrocarbon solvent. When the amount of the other organic solvent increases, lifting of the old coating film easily occurs at the time of recoating.

The above-mentioned colored organic resin paint is dried after application to form a colored organic coating film. The coating film thickness is not particularly limited, but is usually preferably in the range of 20 to 100 μm (dry film thickness), and the drying conditions are appropriately determined according to the type of the paint and the like. It can be set, and can be cured by drying at room temperature, drying by heating, light curing and the like.

In the third embodiment, an inorganic coating film containing no photocatalytically active titanium oxide is formed on the colored organic coating film formed on the substrate. By forming the inorganic coating film, it is possible to suppress or block the adverse effects on the colored organic coating film due to the oxidizing action of the photocatalytically active titanium oxide in the inorganic coating material of the present invention applied on the coating film.

As the inorganic coating material for forming the inorganic coating film, the same coating material as the coating material for forming the inorganic lower coating film used in the second embodiment can be used. The thickness of the inorganic coating film is not particularly limited, but is usually preferably in the range of 3 to 30 μm (dry film thickness). In the third embodiment, the photocatalytically active inorganic paint of the present invention is applied on the inorganic paint film.

According to the method of the present invention, a coating film having excellent photocatalytic activity and excellent in coating film appearance, coating film properties and weather resistance can be formed on an object to be coated.

[0054]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below with reference to embodiments. In the following, “parts” and “%” indicate “parts by weight” and “% by weight”, respectively, unless otherwise specified.

Production Example 1 Production of De-alcohol Condensation Reaction Product Liquid (a) "DC3074" (manufactured by Dow Corning Toray Silicone Co., Ltd., alkylaryl) was placed in a reaction vessel equipped with a thermometer, a thermostat, a stirrer, and a distilling tube. 100 parts of alkoxysilane oligomer, phenyl group content (about 1 equivalent of organic group, the same applies hereinafter), about 50 equivalent%, methoxy group content about 17%, weight average molecular weight about 1600), "XR31B-1
410 "(manufactured by Toshiba Silicone Co., Ltd., partial condensate of alkyl trialkoxysilane, methoxy group content of about 45 to 5).
0% by weight, weight average molecular weight of about 500), 10 parts of γ-glycidoxypropyltrimethoxysilane, 10 parts of methyl alcohol, and 0.2 parts of diisopropoxybisacetylacetonato titanium, and heated to 50 ° C. Thereafter, 5.5 parts of water was added dropwise over 15 minutes. Thereafter, after stirring at 70 ° C. for 1 hour, the mixture was heated to 100 ° C. while blowing in nitrogen gas to remove the distilling solvent, and stirring was continued at the same temperature for 16 hours to produce a dealcoholization condensation reaction liquid (a). . The dealcoholization condensation reaction liquid (a) had a nonvolatile content of 92%, a weight average molecular weight of about 10,300, and an epoxy equivalent of 560. In the infrared absorption spectrum (IR), the ratio of the absorbance of the absorption of silanol (absorption at 3400 cm ^-1 ) / the absorption of siloxane (absorption at 1080 cm ^-1 ) was 0.02.

Production Example 2 Production of Dealcoholization Condensation Reaction Liquid (b) In a reaction vessel equipped with a thermometer, a thermostat, a stirrer, and a distillation pipe, 100 parts of “DC3074” (described above) and “SR2
402 "(manufactured by Dow Corning Toray Silicone Co., Ltd., partial condensate of alkyl trialkoxysilane, methoxy group content: about 34%, weight average molecular weight: about 800), 50 parts, γ
-20 parts of glycidoxypropyltrimethoxysilane, 10 parts of isopropyl alcohol and 0.2 part of diisopropoxybisacetylacetonato titanium were charged, and after raising the temperature to 50 ° C, 4.5 parts of water was added dropwise over 15 minutes. . afterwards,
After stirring at 70 ° C. for 1 hour, the mixture was heated to 120 ° C. while blowing in nitrogen gas to remove the distilling solvent, stirring was continued at the same temperature for 8 hours, 15 parts of xylene was charged, and the dealcoholization condensation reaction liquid (b ) Manufactured. The dealcoholation condensation reaction liquid (b) has a nonvolatile content of 79% and a weight average molecular weight of about 1
8,000 and epoxy equivalent was 2,260. In the infrared absorption spectrum (IR), the ratio of the absorbance of silanol (absorption at 3400 cm ^-1 ) to the absorption of siloxane (absorption at 1080 cm ^-1 ) was 0.01.

Production Example 3 Production of Inorganic White Paint (A) 108.7 parts of a dealcoholization condensation reaction liquid (a) having a non-volatile content of 92% obtained in Production Example 1 was added to "Taipek CR-9".
3 "(manufactured by Ishihara Sangyo Co., Ltd., trade name: titanium white), 100 parts and 20 parts of toluene were added and mixed, and pigment was dispersed using a paint shaker to obtain a paint base (A-1).
Separately, 3.0 parts of γ-aminopropyltriethoxysilane and 0.1 part of dibutyltin diacetate were mixed to obtain a coating curing agent (C). Immediately before coating, 228.7 parts of the base for coating material (A-1) and 3.1 parts of the curing agent for coating material (C) were mixed to prepare an inorganic white paint (A), which was used for coating. The inorganic white paint (A) had good coloring properties.

Production Example 4 Production of Inorganic Clear Paint (B) 208.7 parts of toluene was added to 108.7 parts of the dealcoholization condensation reaction liquid (a) having a nonvolatile content of 92% obtained in the above Production Example 1 and mixed. A paint base (B) was obtained. Immediately before coating, 128.7 parts of the clear paint base (B) and 3.1 parts of the curing agent (C) obtained in Production Example 1 were mixed to obtain an inorganic clear paint (B).

Example 1 Photocatalytically active inorganic paint (D)
Production of "AMT600" (trade name, manufactured by Teica Co., Ltd., anatase-type titanium oxide having photocatalytic activity) in 108.7 parts of a dealcoholation condensation reaction liquid (a) having a nonvolatile content of 92% obtained in Production Example 1 above 500 parts and 5,000 parts of toluene were added and mixed, and pigment was dispersed using a paint shaker to obtain a base (D-1) for a photocatalytically active paint. Immediately before coating, the base for photocatalytically active paint (D-1) 5,60
8.7 parts and 3.1 parts of the curing agent (C) obtained in Production Example 1 were mixed to obtain a photocatalytically active inorganic paint (D).

Example 2 Photocatalytically active inorganic paint (E)
AMT600 500 was added to 105.3 parts of the dealcoholation-condensation reaction liquid (b) having a nonvolatile content of 79% obtained in Preparation Example 2 above.
Parts and 5,000 parts of toluene were added and mixed, and pigment was dispersed using a paint shaker to obtain a base (E-1) for a photocatalytically active paint. Immediately before coating, 5,605.3 parts of the base for photocatalytically active paint (E-1) and 3.1 parts of the curing agent (C) obtained in Production Example 1 were mixed to prepare a photocatalytically active inorganic paint (E). I got

Example 3 Preparation of Photocatalytically Active Inorganic Topcoat (F) 108.7 parts of the alcohol-free condensation reaction liquid (a) having a non-volatile content of 92% obtained in Preparation Example 1 was added to "Taipek CR-9".
3 "100 parts," AMT600 "50 parts and toluene 3
0 parts were added and mixed, and the pigment was dispersed using a paint shaker to obtain a base (F-1) for a photocatalytically active paint.
Immediately before coating, the base (F-
1) 288.7 parts of the curing agent (C) obtained in Production Example 1 3.1
And the resulting mixture were mixed to obtain a photocatalytically active inorganic topcoat paint (F).

Example 4 Production of Photocatalytically Active Inorganic Topcoat (G) [0062] 105.3 parts of a dealcoholization condensation reaction liquid (b) having a nonvolatile content of 79% obtained in Production Example 2 was added to "Taipek CR-9".
3 "100 parts," AMT600 "50 parts and toluene 3
0 parts were added and mixed, and pigment was dispersed using a paint shaker to obtain a base (G-1) for a photocatalytically active paint.
Immediately before coating, the base (F-
1) 285.3 parts of the curing agent (C) obtained in Production Example 1 3.1
And the resulting mixture were mixed to obtain a photocatalytically active inorganic top coat (G).

Comparative Example 1 Production of fluororesin photocatalytically active topcoat (H) (for comparison) "Lumiflon LF-200" (trade name, Asahi Glass Co., Ltd.)
Fluorine resin solution, solid content 60%) 100 parts of "Typek CR-93" and "AMT600" in 166.7 parts
50 parts and 30 parts of toluene were added and mixed, and pigment was dispersed using a paint shaker to obtain a fluororesin-based photocatalytically active topcoat (H). Immediately before coating, 346.7 parts of the fluororesin-based photocatalytically active topcoat paint base (H-1) and "Duranate TPA-100" as a curing agent (trade name, manufactured by Asahi Kasei Corporation, isocyanurate of hexamethylene diisocyanate) 30 parts) to obtain a fluororesin-based photocatalytically active topcoat (H).

Example 5 Newly-installed specification "Multi-tile concrete primer EPO" is applied to a mortar board of 150 x 70 x 20 mm ("Multi-tile concrete primer EPO" is applied to a mortar board of 150 x 70 x 20 mm) (Kansai Paint Co., Ltd., trade name, epoxy-amine resin base coat)
Was brush-coated so as to give a coating amount (paint weight) of 120 g / m ² , dried in a room at a temperature of 20 ° C. and a humidity of 65% RH for 1 day, and then the inorganic white paint (A) obtained in Production Example 3 was obtained. ) To 1
A brush was applied so that the coating amount (coating weight) was 00 g / m ^{2, and} the coating was dried in a room at a temperature of 20 ° C. and a humidity of 65% RH for 1 day, and then the photocatalytically active inorganic coating obtained in Example 1 ( D) was applied with a brush so as to give a coating amount (paint weight) of 10 g / m ² and dried in a room at a temperature of 20 ° C. and a humidity of 65% RH for 10 days to obtain a coated plate.

Example 6 Newly-established specification The procedure of Example 5 was repeated, except that the photocatalytically active inorganic paint (E) obtained in Example 6 was used instead of the photocatalytically active inorganic paint (D). A painted plate was obtained.

Example 7 Newly installed specifications 120 g of “multi-tile concrete primer EPO” was placed on a mortar board having a size of 150 × 70 × 20 mm.
/ M ^{2 with} a coating amount (paint weight),
After drying in a room at a temperature of 20 ° C. and a humidity of 65% RH for 1 day, “Alesletan” (manufactured by Kansai Paint Co., Ltd., trade name, acrylic urethane resin paint, white) was applied, and the temperature was 20 ° C.
It was dried for 1 day in a room having a humidity of 65% RH. Then, on this, 40 g of the inorganic clear paint (B) obtained in Production Example 4 was added.
/ M ^{2 with} a coating amount (paint weight),
After drying in a room at a temperature of 20 ° C. and a humidity of 65% RH for one day, the photocatalytically active inorganic paint (D) obtained in Example 1 was 10 g / m ^2.
Brushing temperature 20 so that the coating amount (paint weight)
The coated plate was dried in a room at a temperature of 65 ° C. and a relative humidity of 65% for 10 days.

Example 8 Newly installed specifications 120 g of “multi-tile concrete primer EPO” was placed on a mortar board having a size of 150 × 70 × 20 mm.
/ M ^{2 with} a coating amount (paint weight),
After drying in a room at a temperature of 20 ° C. and a humidity of 65% RH for one day, 100 g of the photocatalytically active inorganic top coat (F) obtained in Example 3 was obtained.
/ M ^{2 with} a coating amount (paint weight),
The coated plate was dried for 10 days in a room at a temperature of 20 ° C. and a humidity of 65% RH.

Example 9 Newly Specified Example Same as Example 8 except that the photocatalytically active inorganic topcoat (G) obtained in Example 4 was used instead of the photocatalytically active inorganic topcoat (F). And a coated plate was obtained.

Example 10 Coating on Old Coating Film As a top coating, "Alesflon" (manufactured by Kansai Paint Co., Ltd.)
A coated plate having a surface coated with a coating film (trade name, fluororesin-based top coating material) was baked for one year at a bakery field in Okinoerabu, Okinawa Prefecture. The inorganic clear paint (B) was brushed to a coating amount (paint weight) of 40 g / m ² , dried in a room at a temperature of 20 ° C. and a humidity of 65% RH for 1 day, and obtained in Example 1. The photocatalytically active inorganic paint (D) was brushed to a coating amount (paint weight) of 10 g / m ² at a temperature of 20 ° C. and a humidity of 65%.
The coated plate was dried by drying in a room of RH for 10 days.

Example 11 Repainting Specifications As a topcoat, "Alesletan" (manufactured by Kansai Paint Co., Ltd.)
Product name, acrylic urethane resin-based top coating) is coated on the surface of a coated plate that has been baked for three years at a bakery in Okinoerabu, Okinawa Prefecture. Primer EPO 12
After brushing to a coating amount (paint weight) of 0 g / m ² and drying in a room at a temperature of 20 ° C. and a humidity of 65% RH for one day,
100 g of the inorganic white paint (A) obtained in Production Example 3
/ M ^{2 with} a coating amount (paint weight),
After drying in a room at a temperature of 20 ° C. and a humidity of 65% RH for one day, the photocatalytically active inorganic paint (D) obtained in Example 1 was dried for 10 days.
It was brush-coated so as to have a coating amount (paint weight) of g / m ² and dried in a room at a temperature of 20 ° C. and a humidity of 65% RH for 10 days to obtain a coated plate.

Example 12 Recoating Specifications A coating film of "SD Super Marine Topcoat" (manufactured by Kansai Paint Co., Ltd., trade name, long-oil phthalic acid resin-based topcoat, JIS K5516 type 2 compatible product) as a topcoat was applied to the surface. Escomild NB (manufactured by Kansai Paint Co., Ltd., trade name, weak solvent type epoxy resin) Paint) to give a coating amount (paint weight) of 120 g / m ² , and dried in a room at a temperature of 20 ° C. and a humidity of 65% RH for 1 day, and then the inorganic white obtained in Production Example 3 above. The paint (A) was applied with a brush so as to give a coating amount (paint weight) of 100 g / m ² , and the temperature was 20 ° C. and the humidity was 6
After drying in a room at 5% RH for 1 day, the photocatalytically active inorganic paint (D) obtained in Example 1 was brushed to a coating amount (paint weight) of 10 g / m ² at a temperature of 20 ° C. and humidity. 65% R
H was dried in a room for 10 days to obtain a coated plate.

Comparative Example 2 In Example 5, the inorganic white paint (A) obtained in Production Example 3 was applied without applying the photocatalytically active inorganic paint (D) obtained in Example 1, and the temperature was changed to 20 ° C. A coated plate was obtained in the same manner as in Example 5, except that drying was performed in a room at a temperature of 65 ° C and a relative humidity of 65% for 10 days. .

Comparative Example 3 The fluororesin-based photocatalytically active topcoat (H) obtained in Comparative Example 1 was applied instead of the photocatalytically active inorganic topcoat (F) in Example 8, and the temperature was 20 ° C. and the humidity was 65% RH. A coated plate was obtained in the same manner as in Example 8 except that drying was performed in the room for 10 days.

Also, in Examples 5, 6, 8 and 9, and Comparative Examples 2 and 3, except that a 150 × 35 × 0.8 mm aluminum plate was used instead of a 150 × 70 × 20 mm mortar plate. Thus, a test plate for an NOx oxidation test was prepared.

The coated plates obtained in Examples 5 to 12 and Comparative Examples 2 to 3 were tested for the state of coated surface, initial adhesion and weather resistance according to the following test methods. Further, an NOx oxidation test was performed on the test plate for NOx oxidation test. The results of these tests are shown in Table 1 below.

Test Method Painted surface condition: The coated surface of the coated plate was visually observed, and the
Evaluations were made for abnormalities such as cracks, peeling, discoloration, and chalking.

Adhesion: JIS K5400 8.5.
2 (1990), according to the grid-tape method,
Six parallel and vertical knife wounds reaching the substrate were made on the coating surface of the coated plate, and 25 squares of 2 mm x 2 mm were created. A cellophane pressure-sensitive adhesive tape was adhered to the grid, and was instantaneously peeled off, and the ratio of the number of cells remaining without peeling out of the 25 cells was described.

Weather resistance: The coated plate was subjected to an outdoor baking test for 3 months at an outdoor baking place in the Tokyo office of Kansai Paint Co., Ltd. in Ota-ku, Tokyo. With respect to the coating film after the backwash test, the coated surface condition, the adhesion, and the lightness difference ΔL between the coating film before the backwash test and the coating film after the backwash test were determined. Regarding the state of the coated surface and the adhesion, a test was conducted in the same manner as in the case of the initial coating film of the coated plate. Further, regarding the lightness difference ΔL,
3 using "CR-300" (Minolta, colorimeter)
The locations were measured and their average values were taken.

NOx Oxidation Test: Two NOx oxidation test plates (film area 105 cm ² ) were placed in a closed container having a capacity of 6.8 liters, and the NOx concentration (initial concentration) was 3
ppm after filling with NOx-containing air.
The coating surface of the test plate for x oxidation test was irradiated with black light (UV intensity 200 μW) for 60 minutes. The gas in the container was circulated at a rate of 3 liters / minute, and the gas in the container was sampled a total of six times every 10 minutes after the start of black light irradiation to measure the NOx concentration. The measured values were plotted to determine a reaction rate constant k of the following formula. As the test plate for the NOx oxidation test, an initial test plate and a test plate three months after the backlash subjected to the weather resistance test were used.

C = C ₀ exp (−kst) In the above formula, C: NOx concentration (mol / liter) C ₀ : NOx initial concentration (mol / liter) k: reaction rate constant (liter / m ² · min) s : Area of coating part of test plate (m ² ) t: Time (minute)

[0081]

[Table 1]

[0082]

The inorganic paint capable of forming the photocatalytically active coating film of the present invention does not deteriorate due to the oxidizing action of the powder having photocatalytic activity, and has oxidation resistance, weather resistance, impact resistance,
It has good coating performance such as coating adhesion and can withstand long-term use, and can form a coating film with excellent decomposability of contaminants such as nitrogen oxides in the air, exposure contamination resistance, and antibacterial properties. It is a paint that can be dried at room temperature or at a relatively low temperature and has good pigment dispersibility.

Further, the photocatalytically active coating film is formed on the object to be coated by the method for forming a photocatalytically active film (first embodiment) in which the above-mentioned inorganic paint capable of forming the photocatalytically active film is formed on the object to be coated. can do.

Further, a photocatalyst in which an inorganic lower coating film containing no photocatalytically active titanium oxide is formed on an object to be coated, and an inorganic coating material capable of forming the photocatalytically active coating film is coated on the inorganic lower coating film. According to the method for forming the active coating film (second embodiment), even when the object to be coated is easily degraded by the oxidizing action of the photocatalytically active titanium oxide, there is no problem of deterioration by the photocatalytically active titanium oxide, photocatalytic activity, coating film appearance, A coated article having excellent coating film performance can be obtained.

Further, a colored organic coating film is formed on the object to be coated,
A photocatalytically active coating that forms an inorganic coating containing no photocatalytically active titanium oxide on the colored organic coating, and coats the inorganic coating capable of forming the photocatalytically active coating on the inorganic coating. The photocatalytically active, arbitrarily colored coating has no problem of deterioration by the photocatalytically active titanium oxide even when the object to be coated is easily degraded by the oxidizing action of the photocatalytically active titanium oxide by the method of forming (third embodiment). A coated article excellent in appearance and coating film performance can be obtained. In the forming method of the third aspect of the present invention, by using a weak solvent type epoxy resin-based paint or acrylic silicone-based paint as the colored organic film-forming paint, it is applied on the deteriorated old paint film. Also, there is no abnormality such as shrinkage at the time of coating, and an inorganic overcoating film having excellent coating surface appearance and coating film performance can be formed.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] June 1, 2000 (2006.1)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0003

[Correction method] Change

[Correction contents]

As a coating material having photocatalytic activity, for example, a coating material in which a powder such as titanium dioxide or zinc oxide having photocatalytic activity is blended into a fluororesin-based coating material or an inorganic coating material has been proposed (for example, Japanese Patent Application Laid-Open No. H10-163,878). Hei 10-19533
3 JP, see JP flat 10-265713). Titanium dioxide and zinc oxide having photocatalytic activity are optical semiconductors and have a band gap around 3 eV.
It is easily excited by irradiation of sunlight or artificial illumination light, generates holes and OH radicals, exhibits strong oxidizing action, and has an antibacterial property due to the oxidizing action.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0064

[Correction method] Change

[Correction contents]

Example 5 Newly installed specification A multi-tile concrete primer EPO ( manufactured by Kansai Paint Co., trade name, epoxy-amine resin-based primer) was coated on a mortar board having a size of 150 × 70 × 20 mm at a rate of 120 g / m ² , and brushed in a room at a temperature of 20 ° C. and a humidity of 65% RH.
After drying in the sun, the inorganic white paint (A) obtained in Production Example 3 above
Was applied to give a coating amount (paint weight) of 100 g / m ² , dried in a room at a temperature of 20 ° C. and a humidity of 65% RH for 1 day, and then the photocatalytically active inorganic paint obtained in Example 1 was obtained. (D) was applied in a room at a temperature of 20 ° C. and a relative humidity of 65% RH with a brush so as to give a coating amount (paint weight) of 10 g / m ^2.
After drying for days, a coated plate was obtained.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0065

[Correction method] Change

[Correction contents]

Example 6 Newly-established specification The procedure of Example 5 was repeated, except that the photocatalytically active inorganic paint (E) obtained in Example 2 was used instead of the photocatalytically active inorganic paint (D). A painted plate was obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B01J 35/02 B05D 5/00 H 37/02 301 7/24 302Y B05D 5/00 C09D 5/00 Z 7 / 24 302 B01D 53/36 ZABJ C09D 5/00 101B F-term (reference) 4D048 AA02 AA06 AB01 AB03 AB05 BA07X BA41X BB03 BC10 EA01 4D075 AE03 CA45 EA02 EA05 EB42 EC02 4G069 AA03 BA24B ABA BAB ABA BAB BAA BE32B BE34B CA01 CA07 CA10 CA12 CA13 DA06 EA11 EC22Y ED02 ED05 FA02 FB23 FC05 4H011 AA02 AA03 BA01 BB18 BC19 DA23 DH07 4J038 DL031 DL052 GA07 HA216 KA04 KA08 KA12 MA14 NA01 NA03 NA05 NA18 PA14 PB05

Claims (7)

[Claims] During 1. A [I] (A) the following rational formula ^{_{R 1 a R 2 b (R}} 3 O) c SiO (4-abc) / 2 Formula, R ¹ and R ³ are the same or different, carbon Numbers 1-8
And R ² represents an aryl group, a is 0.1 ≦ a ≦ 2.0, b is 0.1 ≦ b ≦ 2.0, and b / a is 0.2 ≦ b /A≦2.0, and c is 0.1.
1 ≦ c ≦ 1.0, wherein (a + b + c) is less than 4, wherein the polysiloxane has a weight average molecular weight in the range of 500 to 6,000 and an alkoxyl group content of the polysiloxane. 10-30% by weight based on siloxane
And (B) in the following general formula R ⁴ Si (OR ⁵ ) ₃ , wherein R ⁴ and R ⁵ are the same or different and have 1 to 8 carbon atoms.
A condensate of an alkyl trialkoxysilane represented by an alkyl group having a weight average molecular weight in the range of 300 to 3,000, and having an alkoxyl group content of 20 to 55 based on the condensate. 0 to 500 parts by weight of the alkyltrialkoxysilane condensate in the range of weight%, the alkylarylalkoxypolysiloxane (A) and the alkyltrialkoxysilane condensate (B)
Based on the total 100 parts by weight of, (C) the following general formula _{^{R 6 R 7 n Si (OR}} 8) (3-n) wherein the organic group R ⁶ is containing an epoxy radical, n pieces of R ⁷
Are the same or different and each have an alkyl group having 1 to 8 carbon atoms;
R ⁸ is the same or different and is a hydrogen atom or a carbon atom
Wherein n represents an integer of 0 to 2, and comprises a dealcoholation condensation reaction product with 3 to 100 parts by weight of an epoxy group-containing alkoxysilane represented by the formula: and [II] a photocatalytically active titanium oxide. An inorganic paint capable of forming a photocatalytically active coating film. 2. The inorganic coating composition according to claim 1, wherein the equivalent of the epoxy group of the dealcoholization condensation reaction product is an amino group-containing alkoxysilane, and the active hydrogen of the amino group is 0.3 to 3.
The inorganic paint according to claim 1, wherein the inorganic paint is contained in an amount equivalent to 0 equivalent. 3. The inorganic paint according to claim 1, further comprising a color pigment. 4. A method for forming a photocatalytically active coating film, comprising applying the inorganic coating material capable of forming the photocatalytically active coating film according to claim 1 on an object to be coated. 5. The photocatalytic activity according to any one of claims 1 to 3, wherein an inorganic lower layer coating containing no photocatalytically active titanium oxide is formed on the substrate, and the inorganic lower layer coating is formed on the inorganic lower layer coating. A method for forming a photocatalytically active coating film, comprising applying an inorganic paint capable of forming a coating film. 6. A colored organic coating film is formed on an object to be coated, an inorganic coating film containing no photocatalytically active titanium oxide is formed on the colored organic coating film, and a colored organic coating film is formed on the inorganic coating film. Item 1
4. A method for forming a photocatalytically active coating film, comprising applying the inorganic paint capable of forming the photocatalytically active coating film according to any one of 3. 7. The method for forming a photocatalytically active coating film according to claim 6, wherein the colored organic coating film is an epoxy resin-based coating film or an acrylic silicone resin-based coating film containing a color pigment.