JP2001048608A - Road pavement material and road pavement construction method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a road pavement material (aggregate) which has a photocatalytic function and can be applied to various kinds of pavement construction of a road whether the road is to be newly paved or already paved, is easy in pavement construction and has high capability with respect to exhaust gas purification treatment by subjecting a soil material containing silty and/or clayey soil and a photocatalyst in a specified ratio or higher of the total of the silty and/or clayey soil and photocatalyst to the weight of the soil material, to granulation processing and firing the granulated soil material. SOLUTION: This road pavement material is aggregate having a photocatalyst and is obtained by subjecting a soil material to granulation processing and firing the granulated soil material, wherein the soil material contains silty and/or clayey soil and a photocatalyst in a >=50 wt.% ratio of the total of the silty and/or clayey soil and photocatalyst to the weight of the soil material; the road pavement material (i.e., aggregate) has 0. 075-19. 000 mm particle size and contains 1-80 pts.wt. of the photocatalyst to 100 pts. wt. of the total of the slity and/or clayey soil and photocatalyst; as the photocatalyst, any photocatalyst can be used without special limitation, however, for example, a single compound selected from titanium oxide, zinc oxide, tin oxide, or a mixture of plural compounds selected from them is used; and as the aggregate having such a photocatalyst, two kinds of such aggregate having different forms, i.e., photocatalyst-containing aggregate having the photocatalyst inside the aggregate, and photocatalyst-coated aggregate having the photocatalyst as a coating formed on the surface of a base material of the aggregate, can be used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pavement method for providing a road having an ability to purify harmful gases such as NOx contained in exhaust gas of automobiles, and a pavement material used therefor.

[0002]

2. Description of the Related Art The technology for purifying harmful gases such as NOx contained in exhaust gas from automobiles has become very important from the viewpoint of global environmental problems, and various purification technologies have been studied and developed. Have been. In particular, recently, it has been noted that a photocatalyst is useful for the purification treatment. For example, a photocatalyst incorporating a photocatalyst into a guardrail, a protective wall, or the like has been developed and partially put into practical use.

Further, a technique of imparting a purification function to a road surface itself has been studied very recently.
No. 2,256,919 and Japanese Patent Application Laid-Open No. 10-272356 disclose aggregates, cement,
And a member (block) made of a photocatalyst. Further, a method of spraying and applying a coating agent containing a photocatalyst to a road surface has been disclosed (Chemical Industry Daily, March 26, 1999).

[0004]

However, Japanese Patent Application Laid-Open Nos. 10-225719 and 10-27 mentioned above disclose the above problems.
The harmful substance removing member disclosed in Japanese Patent No. 2356,
Since it is a processed product as a member, it is expensive, and since the member is laid on a road and used, it is difficult to apply it to a road that is too wide. In addition, March 2, 1999
In the method disclosed in the Chemical Daily on 6th, since the coating is directly applied to the road surface, the effective layer for the purification treatment is only a shallow portion on the road surface,
Scattering of the coating agent during construction is also a problem.

Therefore, an object of the present invention is to apply to various types of road pavement, regardless of whether it is new or existing, to be easy to construct, and to provide a road pavement having a high exhaust gas purification processing ability and a photocatalytic function. An object of the present invention is to provide a material and a road pavement method using the same.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems. As a result, they have found that all of the above problems can be solved by introducing a photocatalytic function into the aggregate itself used for conventional road pavement. That is, the photocatalyst-containing aggregate as a road pavement material according to the present invention is a photocatalyst-containing aggregate obtained by subjecting a soil material to granulation and firing, wherein 50% by weight or more of the soil material is silty soil. And / or a clayey soil and a photocatalyst.

A photocatalyst-coated aggregate as another road pavement material according to the present invention is a photocatalyst-coated aggregate in which a photocatalyst is coated on the surface of a granular aggregate, and the coating is performed by the following method (i). To (v). (I) a first coating layer composed of a cured coating of an acrylic-modified silicone resin coating material containing the following components (A), (B), (C) and (D); and a first coating layer formed on the surface of the first coating layer. A coating method for forming a coating layer comprising a second coating layer comprising a cured coating of a functional coating material containing the following components (E) and (F). Component (A): represented by the general formula R ¹ _m SiX _4-m (1) (where R ¹ represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms) , M is an integer of 0 to 3, and X represents a hydrolyzable group.) In a colloidal silica dispersed in an organic solvent, water or a mixed solvent thereof, the hydrolyzable group ( X) A silica-dispersed oligomer solution of an organosilane, which is partially hydrolyzed under the condition of using 0.001 to 0.5 mol of water per 1 mol equivalent. Component (B): represented by the average composition formula R ² _a Si (OH) _b O _{(4-ab) / 2} (2) (where R ² is the same or different, substituted or unsubstituted C 1 -C 1) 8 represents a monovalent hydrocarbon group, wherein a and b are respectively 0.2 ≦ a ≦ 2, 0.0001 ≦ b ≦
3, a number that satisfies the relationship of a + b <4. ), Polyorganosiloxanes containing silanol groups in the molecule. Component (C): curing catalyst. Component (D): a monomer represented by the general formula CH ₂ ＣＲCR ³ (COOR ⁴ ) (where R ³ represents a hydrogen atom and / or a methyl group), wherein R ⁴ is substituted or A group consisting of an unsubstituted first (meth) acrylic acid ester which is a monovalent hydrocarbon group having 1 to 9 carbon atoms, wherein R ⁴ is an epoxy group, a glycidyl group or a hydrocarbon group containing at least one of these groups; A second (meth) acrylate which is at least one group selected from the group consisting of: and a third (meth) acryl wherein R ⁴ is a hydrocarbon group containing an alkoxysilyl group and / or a halogenated silyl group. Acrylic resin which is a copolymer of acid ester and Component (E): 20 to 200 parts by weight of a silicon compound and / or colloidal silica represented by the general formula Si (OR ⁵ ) ₄ and 100 parts by weight of a silicon compound represented by the general formula R ⁶ Si (OR ⁵ ) ₃ When the general formula _{^{R 6 2 Si (OR 5)}} 2
(Wherein R ⁵ and R ^{6 each} represent a monovalent hydrocarbon group) having a weight average molecular weight of 800 or more in terms of polystyrene. An organosiloxane that has been adjusted to be Component (F): photocatalyst.

(Ii) a first coating layer comprising a cured coating of an acrylic-modified silicone resin coating material containing the following components (A), (B), (C) and (D);
The following (A), (B), and (C) formed on the surface of the coating layer
And a second coating layer comprising a cured coating film of a functional coating material containing the component (F). Component (A): represented by the general formula R ¹ _m SiX _4-m (1) (where R ¹ represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms) , M is an integer of 0 to 3, and X represents a hydrolyzable group.) In a colloidal silica dispersed in an organic solvent, water or a mixed solvent thereof, the hydrolyzable group ( X) A silica-dispersed oligomer solution of an organosilane, which is partially hydrolyzed under the condition of using 0.001 to 0.5 mol of water per 1 mol equivalent. Component (B): represented by the average composition formula R ² _a Si (OH) _b O _{(4-ab) / 2} (2) (where R ² is the same or different, substituted or unsubstituted C 1 -C 1) 8 represents a monovalent hydrocarbon group, wherein a and b are respectively 0.2 ≦ a ≦ 2, 0.0001 ≦ b ≦
3, a number that satisfies the relationship of a + b <4. ), Polyorganosiloxanes containing silanol groups in the molecule. Component (C): curing catalyst. Component (D): a monomer represented by the general formula CH ₂ ＣＲCR ³ (COOR ⁴ ) (where R ³ represents a hydrogen atom and / or a methyl group), wherein R ⁴ is substituted or A group consisting of an unsubstituted first (meth) acrylic acid ester which is a monovalent hydrocarbon group having 1 to 9 carbon atoms, wherein R ⁴ is an epoxy group, a glycidyl group or a hydrocarbon group containing at least one of these groups; A second (meth) acrylate which is at least one group selected from the group consisting of: and a third (meth) acryl wherein R ⁴ is a hydrocarbon group containing an alkoxysilyl group and / or a halogenated silyl group. Acrylic resin which is a copolymer of acid ester and Component (F): photocatalyst.

(Iii) A coating method using a coating material consisting of a cured coating of a functional coating material containing the following components (E) and (F): Component (E): 20 to 200 parts by weight of a silicon compound and / or colloidal silica represented by the general formula Si (OR ⁵ ) ₄ and 100 parts by weight of a silicon compound represented by the general formula R ⁶ Si (OR ⁵ ) ₃ When the general formula _{^{R 6 2 Si (OR 5)}} 2
(Wherein R ⁵ and R ^{6 each} represent a monovalent hydrocarbon group) having a weight average molecular weight of 800 or more in terms of polystyrene. An organosiloxane that has been adjusted to be Component (F): photocatalyst.

(Iv) An antistatic inorganic material containing a photocatalyst in an inorganic coating containing silicone resin as a main component in an amount of 2 to 80 parts by weight based on 100 parts by weight of the total of the solid content in terms of the total condensed compound and the total photocatalytic component. A coating method using paint as a coating material. (V) A solution containing an additive, ammonium titanium fluoride, and water, which promotes equilibrium of the following reaction formula (4) in an aqueous solution containing ammonium titanium fluoride, is brought into contact with the aggregate, and a photocatalyst is applied to the surface of the aggregate. A photocatalytically active titanium oxide film coating method for forming an active titanium oxide film, wherein the concentration of the additive is 0.05 to the total amount of the solution.
And 0.5 mol / l, and the concentration of titanium ammonium fluoride is 0.01 to 0.
2 mol / l, and a film thickness of 10 on the surface of the aggregate.
After forming a titanium oxide film of 0 nm to 2 μm,
A coating method characterized by firing at 0 to 700 ° C.

(NH ₄ ) ₂ TiF ₆ + 2H ₂ O = TiO ₂ + 4HF + 2NH ₄ F (4) Further, the road paving method according to the present invention provides a photocatalyst-containing aggregate or a road paving material according to the present invention. The present invention is characterized in that a road surface is paved using a photocatalyst-coated aggregate.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION [Road Pavement Material] The road pavement material according to the present invention is obtained by introducing a photocatalytic function into the aggregate itself used for conventional road pavement. By providing the aggregate itself with a photocatalytic function, it is possible to have a purification treatment function over the entire road and from the surface to a relatively deep layer, and the pavement process using this is also very easy. .

Here, the term "aggregate" as used in the present invention refers to a granular material used for pavement of a road, which is a relatively large granular material such as gravel, crushed stone or sand, or a granular material obtained by granulating a soil material. This is a concept that includes relatively small particles. The road pavement material according to the present invention takes two forms, a photocatalyst-containing aggregate in which the photocatalyst is contained in the aggregate, and a photocatalyst-coated aggregate in which the photocatalyst is coated on the surface of the aggregate.
Hereinafter, these will be described in detail. (Photocatalyst-containing aggregate) The photocatalyst-containing aggregate of the present invention is a photocatalyst-containing aggregate obtained by subjecting a soil material to granular processing and firing.

The above-mentioned soil material includes silty soil and clayey soil such as sandy silt, clayey silt, and silty clay. In the present invention, in particular, in the present invention, 50% by weight or more of the soil material is included. , Silty soil and / or clay soil and a photocatalyst. The total amount of silty soil and / or clay soil and photocatalyst is 50% of the total soil material.
If the amount is less than% by weight, the effects of the present invention cannot be sufficiently exerted, which is not preferable.

Although silt soil and clay soil can be obtained by excavation from the ground, etc., in recent years, from the viewpoint of resource recycling and the like, sludge and the like discharged from construction residual soil, water purification plant facilities, sewage facilities, etc. Industrial waste is also available. Since these soil materials including silty soil and clay soil have a strong ability to retain moisture, when they are granulated and fired under predetermined conditions, porous unfired granules can be obtained. Therefore, if the photocatalytic fine particles are kneaded in advance with the above-mentioned soil material, and then subjected to granulation processing and firing processing, a granular material having high exhaust gas adsorption and decomposability can be easily obtained.

The photocatalyst which can be used in the present invention is not particularly limited as long as it has a usual photocatalytic function. For example, titanium oxide, zinc oxide, tin oxide, iron oxide, zirconium oxide, tungsten oxide Chromium oxide, molybdenum oxide, ruthenium oxide, germanium oxide, lead oxide, cadmium oxide, copper oxide, vanadium oxide, niobium oxide, tantalum oxide, manganese oxide, cobalt oxide, rhodium oxide, rhenium oxide, and these alone or 2 Mixtures of more than one kind are mentioned, and among them, titanium oxide and zinc oxide are particularly preferable in that the effect of the present invention is more exhibited.

The content of the photocatalyst may be from 1 to 80 parts by weight, based on 100 parts by weight of the total of the silty soil and / or clay soil and the photocatalyst. The amount is preferably 20 to 70 parts by weight, more preferably 30 to 60 parts by weight. When the content of the photocatalyst is lower than 1 part by weight, the exhaust gas purification treatment ability does not sufficiently appear. Is not sufficient, which is not preferable.

The photocatalyst-containing aggregate has a particle size of 0.07.
It is preferably from 5 to 26.5 mm. 26.5mm
Exceeding is not preferable because it is too large for surface pavement. On the other hand, if it is smaller than 0.075 mm, it is not preferable because when used in the "sand filling method", the open particle size asphalt is clogged and the water permeability and drainage property are extremely reduced.

It is preferable to use a spray dryer or pulverization after calcination as the means for the granular processing, and the former is particularly preferable for processing having a relatively small particle size (for example, 0.075 to 0.075).
(About 2.5 mm).
m). The baking treatment conditions are not particularly limited as long as a porous unbaked granular material can be obtained. In particular, the baking treatment is preferably performed in a temperature range of 800 to 1200 ° C., and the baking time is several minutes to several hours. It is preferred to do so. Particularly preferably, 30 minutes or more
It takes about 2 hours. If the firing conditions are too strict,
If the sintering proceeds too much to lose the porosity and the sintering conditions are too weak, the sintering will be weak and the strength as a granular material will be poor. (Photocatalyst-coated aggregate) The photocatalyst-coated aggregate of the present invention is an aggregate in which the photocatalyst is coated on the surface of the granular aggregate by at least one selected from specific coating methods (i) to (v).

First, the specific coating method (i)
(V) will be described below in order. The coating method (i) (ii) the first coating method (i) and the second coating method (ii) are an acrylic modified silicone resin containing the following components (A), (B), (C) and (D) A first coating layer formed of a cured coating of a coating material, and a functional coating material (1) or (A) formed on the surface of the first coating layer and containing the following components (E) and (F):
This is a coating method using a coating material composed of a cured coating of a functional coating material (2) containing components (B), (C) and (F).

The functional coating material (1) of (E) a silicon compound used as a raw material for the component in which the organosiloxane (E) (E ₁₎ ~ (E ₃₎ of the general formula R ⁶ _n Si (OR ⁵⁾ _4-n (5) (where R ⁵ and R ^{6 each} represent a monovalent hydrocarbon group, and n is an integer of 0 to 2).

R ⁶ is not particularly limited, and includes, for example, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. Specifically, methyl, ethyl, propyl, butyl, pentyl, hexyl,
Alkyl groups such as heptyl group and octyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aralkyl groups such as 2-phenylethyl group, 2-phenylpropyl group and 3-phenylpropyl group; phenyl group and tolyl group Aryl group; alkenyl group such as vinyl group and allyl group; chloromethyl group, γ-chloropropyl group, 3,3,
Halogen-substituted hydrocarbon groups such as 3-trifluoropropyl group; substituted hydrocarbon groups such as γ-methacryloxypropyl group, γ-glycidoxypropyl group, 3,4-epoxycyclohexylethyl group, γ-mercaptopropyl group, etc. Can be exemplified. Among these, an alkyl group having 1 to 4 carbon atoms and a phenyl group are preferable from the viewpoint of ease of synthesis or availability.

[0023] As the R ^5, it is not particularly limited, for example, is used which the alkyl group of 1 to 4 carbon atoms as a main raw material. Particularly, tetramethoxysilane, tetraethoxysilane and the like can be exemplified as n = 0 tetraalkoxysilane, and methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane can be exemplified as n = 1 organotrialkoxysilane. Phenyltrimethoxysilane, phenyltriethoxysilane, and 3,3,3-trifluoropropyltrimethoxysilane. Examples of the diorganodialkoxysilane having n = 2 include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane.

R ⁵ and R ⁶ may be the same or different among the silicon compounds (E ₁ ) to (E ₃ ). The organosiloxane (E) is prepared by, for example, diluting the raw materials (E ₁ ) to (E ₃ ) with an appropriate solvent, adding water and a catalyst as necessary in a required amount to the hydrolysis and polycondensation reaction. To obtain a prepolymer, in which case the weight average molecular weight (Mw) of the obtained prepolymer becomes 800 or more, preferably 850 or more, more preferably 900 or more in terms of polystyrene. Adjust as follows. When the molecular weight distribution (weight-average molecular weight (Mw)) of the prepolymer is smaller than 800, the shrinkage upon curing of the functional coating material during the polycondensation is large and cracks are likely to occur in the coating film after curing.

The amount of the raw materials (E ₁ ) to (E ₃ ) used in preparing the organosiloxane (E) is _{20 to} 200 parts by weight of (E ₁ ) per 100 parts by weight of (E ₂ ) (preferably). 40-160 parts by weight, more preferably 60 to 120 parts by weight), (E ₃₎ 0 to 60 parts by weight (preferably 0 to 40
Parts by weight, more preferably 0 to 30 parts by weight). If the amount of (E ₁ ) is less than the above range, there is a problem that a desired hardness of the cured film cannot be obtained (the hardness is lowered). There is a problem that the hardness is too high and cracks are easily generated. If the amount of (E ₃ ) is more than the above range, there is a problem that a desired hardness of the cured film cannot be obtained (the hardness is lowered).

The colloidal silica that can be used as the raw material (E ₁ ) is not particularly limited, and for example, water-dispersible or non-aqueous organic solvent-dispersible colloidal silica such as alcohol can be used. Generally, such colloidal silica has a solid content of 20 to 5 silica.
0% by weight, and the silica content can be determined from this value. When water-dispersible colloidal silica is used, water present as a component other than the solid content can be used as a curing agent as described later. Water-dispersible colloidal silica is usually made from water glass,
It can be easily obtained as a commercial product. The organic solvent-dispersible colloidal silica can be easily prepared by replacing water of the water-dispersible colloidal silica with an organic solvent. Such an organic solvent-dispersible colloidal silica can be easily obtained as a commercial product similarly to the water-dispersible colloidal silica. In the organic solvent dispersible colloidal silica, the type of the organic solvent in which the colloidal silica is dispersed is not particularly limited, for example,
Lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol and isobutanol;
Ethylene glycol derivatives such as ethylene glycol, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether acetate; diethylene glycol;
Examples thereof include diethylene glycol derivatives such as diethylene glycol monobutyl ether; diacetone alcohol; and one or more selected from the group consisting of these. In combination with these hydrophilic organic solvents, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime and the like can also be used.

When colloidal silica is used as the raw material (E ₁ ), the proportion of (E ₁ ) is part by weight including the dispersion medium. Further, the raw material as the (E ₁₎ ~ curing agent used in the hydrolysis polycondensation reaction of (E _3), although the water is used, as this amount is a silicon compound (E ₁₎
(E ₃ ) OR ⁵ groups per mole equivalent of OR ⁵ , water 0.01 to
3.0 mol is preferable, and 0.3 to 1.5 mol is more preferable.

The diluting solvent used in the hydrolysis and polycondensation reaction of the raw materials (E ₁ ) to (E ₃ ) is not particularly limited, and for example, the above-mentioned colloidal silica dispersion solvents can be used. The pH of the organosiloxane (E) is not particularly limited, but is preferably adjusted to 3.8 to 6. When the pH is within this range, the organosiloxane (E) can be used stably within the above-mentioned range of molecular weight. pH
Is out of the above range, the stability of the organosiloxane (E) deteriorates, so that the usable period from the time of preparing the paint is limited. Here, the pH adjustment method is not particularly limited. For example, when mixing the raw materials of the organosiloxane (E) and the pH becomes less than 3.8, for example, a basic reagent such as ammonia is added. The pH may be adjusted to a value within the above range, and when the pH exceeds 6, it may be adjusted using, for example, an acidic reagent such as hydrochloric acid. Depending on the pH, when the reaction does not proceed while the molecular weight is small and it takes time to reach the molecular weight range, the organosiloxane (E) may be heated to accelerate the reaction, After the reaction is advanced by lowering the pH with a reagent, the pH may be returned to a predetermined pH with a basic reagent.

The functional coating material (1) does not need to contain a curing catalyst when cured by heating, but promotes the condensation reaction of the organosiloxane (E) to form a coating film of the functional coating material (1). A curing catalyst may be included, if necessary, for the purpose of promoting heat curing and curing the coating film at room temperature. The curing catalyst is not particularly limited, for example, alkyl titanates; tin octylate, dibutyltin dilaurate,
Carboxylic acid metal salts such as dioctyltin dimaleate; amine 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;
Amine silane coupling agents such as N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane; p-toluenesulfonic acid, phthalic acid, hydrochloric acid, etc. Acids; aluminum compounds such as aluminum alkoxides and aluminum chelates; lithium acetate, potassium acetate, lithium formate, sodium formate, potassium phosphate;
Alkali metal salts such as potassium hydroxide; titanium compounds such as tetraisopropyl titanate, tetrabutyl titanate, and titanium tetraacetylacetonate; and halogenated silanes such as methyltrichlorosilane, dimethyldichlorosilane, and trimethylmonochlorosilane. However, other than these, there is no particular limitation as long as it is effective for accelerating the condensation reaction of the organosiloxane (E).

When the functional coating material (1) also contains a curing catalyst (C), its amount is preferably at most 45% by weight, more preferably at most 25%, based on the organosiloxane (E). If it exceeds 45% by weight, the storage stability of the coating solution may be impaired. The photocatalyst (photocatalyst (F)) used as the component (F) of the functional coating materials (1) and (2) is not particularly limited, but, for example, titanium oxide, zinc oxide, tin oxide, zirconium oxide, oxide Tungsten, chromium oxide, molybdenum oxide, iron oxide, nickel oxide, ruthenium oxide, cobalt oxide, copper oxide, manganese oxide, germanium oxide, lead oxide, cadmium oxide, vanadium oxide, niobium oxide, tantalum oxide, rhodium oxide, rhenium oxide, etc. And the like. Among these, titanium oxide,
Zinc oxide, tin oxide, zirconium oxide, tungsten oxide, iron oxide, and niobium oxide are preferred because they exhibit activity even when baked and cured at a low temperature of 100 ° C. or lower. If transparency of the coating is required, use photocatalyst (F)
Is preferably 50 μm or less, more preferably 5 μm or less, and 0.5 μm or less.
It is more preferred that: The photocatalyst (F) is 1
Only one kind may be used, or two or more kinds may be used in combination.

It is known that the photocatalyst (F) generates active oxygen (photocatalytic property) when irradiated with ultraviolet rays in the atmosphere. Since active oxygen can oxidize and decompose organic substances, its characteristics are used to make use of the properties of carbon-based dirt components adhering to painted products (for example, carbon fraction contained in exhaust gas of automobiles, dust of tobacco, etc.). Etc.); deodorizing effect of decomposing malodorous components represented by amine compounds and aldehyde compounds; and antibacterial effect of preventing the generation of bacterial components represented by Escherichia coli and Staphylococcus aureus. . In addition, there is also an effect that the wettability of the coating film with respect to water is improved by decomposing and removing dirt such as organic substances repelling water adhered to the coating film surface by the photocatalyst (F). This effect is exhibited irrespective of the film thickness and the photocatalyst content.

The photocatalyst (F) may support a metal. The metal that may be supported is not particularly limited, and includes, for example, gold, silver, copper, iron, zinc, nickel, cobalt, platinum, ruthenium, palladium, rhodium, cadmium, and the like. Alternatively, two or more types can be appropriately selected and used. By carrying the metal, the charge separation of the photocatalyst (F) is promoted, and the photocatalysis is more effectively exhibited. Photocatalyst supporting metal (F)
Has an oxidizing performance in the presence of light, and exerts effects such as deodorization and antibacterial by the oxidizing performance. Furthermore, you may use the clay crosslinked body which carried the photocatalyst (F) between the layers. By introducing the photocatalyst (F) between the layers, the photocatalyst (F) is supported on the fine particles and the photocatalytic performance is improved.

Functional coating material (1) or (2)
The method of dispersing the photocatalyst (F) therein is not particularly limited. The silica-dispersed oligomer solution (A) used as the component (A) of the acrylic-modified silicone resin coating material and the functional coating material (2) has a hydrolyzable group (A) as a functional group that is subjected to a curing reaction when forming a cured film. X) is the main component of the base polymer having This is because, for example, the colloidal silica dispersed in an organic solvent or water (including a mixed solvent of an organic solvent and water) is mixed with one of the hydrolyzable organosilanes represented by the general formula (1).
Water (water previously contained in colloidal silica and / or water added separately) by adding one or more species
Of water per 1 molar equivalent of the hydrolyzable group (X)
It is obtained by partially hydrolyzing the hydrolyzable organosilane under conditions using 1 to 0.5 mol.

The group R ¹ in the hydrolyzable organosilane represented by the general formula (1) is particularly the same or different and is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. Although not limited, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; Group, 2-phenylpropyl group,
Aralkyl groups such as 3-phenylpropyl group; aryl groups such as phenyl group and tolyl group; alkenyl groups such as vinyl group and allyl group; chloromethyl group, γ-chloropropyl group and 3,3,3-trifluoropropyl group Halogen-substituted hydrocarbon groups such as; γ-methacryloxypropyl group,
Examples thereof include a substituted hydrocarbon group such as a γ-glycidoxypropyl group, a 3,4-epoxycyclohexylethyl group, and a γ-mercaptopropyl group. Among them, an alkyl group having 1 to 4 carbon atoms and a phenyl group are preferable from the viewpoint of ease of synthesis or availability.

In the general formula (1), the hydrolyzable group X is not particularly restricted but includes, for example, alkoxy, acetoxy, oxime, enoxy, amino, aminoxy, amide and the like. Can be Among these, an alkoxy group is preferable because it is easily available and the silica dispersed oligomer solution of organosilane (A) is easily prepared.

Specific examples of the hydrolyzable organosilane include mono-, di-, tri- and tetra-functional alkoxysilanes wherein m in the general formula (1) is an integer of 0 to 3. , Acetoxysilanes, oxime silanes,
Examples include enoxysilanes, aminosilanes, aminoxysilanes, amidosilanes and the like. Among these, alkoxysilanes are preferable because they are easily available and the silica-dispersed oligomer solution of organosilane (A) is easily prepared.

Among the alkoxysilanes, m = 0
Examples of the tetraalkoxysilane include tetramethoxysilane and tetraethoxysilane. Examples of the organotrialkoxysilane having m = 1 include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, and phenyltrimethoxysilane. ,
Examples thereof include phenyltriethoxysilane and 3,3,3-trifluoropropyltrimethoxysilane. Further, as the diorganodialkoxysilane of m = 2,
Examples thereof include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane. Examples of the triorganoalkoxysilane having m = 3 include trimethylmethoxysilane, trimethylethoxysilane, and trimethylisopropoxysilane. And dimethylisobutylmethoxysilane. Further, an organosilane compound generally called a silane coupling agent is also included in the alkoxysilanes.

Of these hydrolyzable organosilanes represented by the general formula (1), at least 50 mol%, preferably at least 60 mol%, more preferably at least 70 mol%,
It is a trifunctional compound represented by m = 1. This is 50
If it is less than mol%, sufficient coating film hardness cannot be obtained,
Dry curing properties are likely to be poor. The colloidal silica in the component (A) has the effect of increasing the hardness of the cured film of the coating material and improving smoothness and crack resistance. The colloidal silica is not particularly limited, but for example, those described above as the raw material (E ₁ ) of the organosiloxane (E) can be used. When water-dispersible colloidal silica is used, water present as a component other than the solid content can be used for the hydrolysis of the hydrolyzable organosilane and also as a curing agent for the coating material.

In the component (A), the colloidal silica preferably has a silica content of 5 to 95% by weight, more preferably 10 to 90% by weight, and still more preferably 20 to 90% by weight.
It is contained within the range of 85% by weight. When the content is less than 5% by weight, a desired coating hardness tends to be not obtained. On the other hand, if it exceeds 95% by weight, it becomes difficult to uniformly disperse the silica, and the component (A) becomes gelled, and the cured film becomes too hard, which tends to cause cracks in the film. Sometimes.

In the present specification, the compounding ratio of the component (A) in the coating material is a value including the dispersion medium of colloidal silica. As described above, the amount of water used in preparing the silica-dispersed oligomer solution of organosilane (A) is 0.001 water per 1 mol equivalent of the hydrolyzable group (X) of the hydrolyzable organosilane. The range is from 0.5 to 0.5 mol, preferably from 0.01 to 0.4 mol. If the amount of water used is less than 0.001 mol, a sufficient partial hydrolyzate cannot be obtained, and if it exceeds 0.5 mol, the stability of the partial hydrolyzate deteriorates. Here, the amount of water used in the partial hydrolysis reaction of the hydrolyzable organosilane is separately determined when colloidal silica containing no water (for example, colloidal silica using only an organic solvent as a dispersion medium) is used. It is the amount of water added. When colloidal silica containing water (for example, colloidal silica using only water or a mixed solvent of an organic solvent and water as a dispersion medium of colloidal silica) is used, It is the amount of water previously contained in at least the colloidal silica of the water previously contained and the water separately added. If the amount of water was previously contained in the colloidal silica alone and the amount used was sufficient, it was not necessary to separately add water, but the amount of water was previously contained in the colloidal silica. If water alone is not sufficient for the above usage, it is necessary to separately add water until the usage reaches the above usage. In that case, the amount of water used is
It is the total amount of water previously contained in the colloidal silica and water added separately. In addition, even when only the water previously contained in the colloidal silica is sufficient for the above usage amount,
Water may be separately added, and in that case, the amount of the water used is the total amount of water previously contained in the colloidal silica and the separately added water. However, water is separately added so that the total amount does not exceed the upper limit (0.5 mol per 1 mol equivalent of the hydrolyzable group (X)).

The method of partially hydrolyzing the hydrolyzable organosilane is not particularly limited. For example, the hydrolyzable organosilane may be mixed with colloidal silica (whether the colloidal silica contains no water or If the required amount is not contained, add water here. At that time, the partial hydrolysis reaction proceeds at room temperature,
In order to accelerate the partial hydrolysis reaction, if necessary, heating (for example, 60 to 100 ° C.) or a catalyst may be used. Examples of the catalyst include, but are not limited to, hydrochloric acid, acetic acid, halogenated silane, chloroacetic acid, citric acid, benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, maleic acid, and malonic acid. , And one or more of organic acids and inorganic acids such as toluenesulfonic acid and oxalic acid.

The component (A) preferably has a pH of 2.0 to 2.0 in order to stably obtain its performance over a long period of time.
It is good to set it to 7.0, More preferably, it is 2.5-6.5, More preferably, it is 3.0-6.0. When the pH is out of this range, the performance continuity of the component (A) is remarkably reduced particularly under the condition that the amount of water used is 0.3 mol or more per 1 mol equivalent of the hydrolyzable group (X). When the pH of the component (A) is out of the above range, the pH may be adjusted by adding a basic reagent such as ammonia or ethylenediamine if the pH is more acidic than the above range. The pH may be adjusted using an acidic reagent such as hydrochloric acid, nitric acid, and acetic acid. But,
The adjustment method is not particularly limited.

The silanol group-containing polyorganosiloxane (B) used as the component (B) of the acrylic-modified silicone resin coating material and the functional coating material (2) has a hydrolyzable group as a functional group to be subjected to a curing reaction. A cross-linking agent for forming a three-dimensional cross-link in the cured film by a condensation reaction with the component (A) which is a base polymer having the effect of preventing crack generation by absorbing distortion due to curing shrinkage of the component (A). It is a component with.

R in the above average composition formula (2) representing (B)
² is not particularly limited, and R ¹ in the above formula (1)
The same is exemplified, but preferably, it has 1 to 4 carbon atoms.
Alkyl group, phenyl group, vinyl group, γ-glycidoxypropyl group, γ-methacryloxypropyl group, γ-aminopropyl group, substituted hydrocarbon group such as 3,3,3-trifluoropropyl group, more preferably Is a methyl group and a phenyl group. In the above formula (2), a and b
Is a number satisfying the above relationship, and if a is less than 0.2 or b exceeds 3, there is an inconvenience that cracks occur in the cured film. When a is more than 2 and 4 or less, or when b is less than 0.0001, curing does not proceed well.

The silanol group-containing polyorganosiloxane (B) is not particularly limited.
Methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane,
Alternatively, it can be obtained by hydrolyzing one or a mixture of two or more of the corresponding alkoxysilanes with a large amount of water by a known method. When a silanol group-containing polyorganosiloxane (B) is hydrolyzed by a known method using alkoxysilane, a small amount of an unhydrolyzed alkoxy group may remain. That is, a polyorganosiloxane in which a silanol group and a trace amount of an alkoxy group coexist may be obtained, but in the present invention, such a polyorganosiloxane may be used.

The curing catalyst (C) used as the component (C) of the acrylic-modified silicone resin coating material and the functional coating material (2) promotes a condensation reaction between the components (A) and (B) to form a film. Is a component that cures.
Examples of the curing catalyst (C) include all those exemplified above as the curing catalyst that the functional coating material (1) may optionally contain. However, the curing catalyst (C) is not particularly limited as long as it is effective in promoting the condensation reaction between the component (A) and the component (B) other than those exemplified above.

The acrylic resin (D) used as the component (D) contained in the acrylic-modified silicone resin coating material has the effect of improving the toughness of the cured film of the acrylic-modified silicone resin coating material, thereby reducing the occurrence of cracks. Prevention to allow for a thicker film. Further, the acrylic resin (D) is taken into a condensation cross-linked product of the component (A) and the component (B), which becomes a three-dimensional skeleton of a cured film of the acrylic-modified silicone resin coating material, and converts the condensation cross-linked product to an acrylic modification. I do. When the condensation crosslinked product is acrylic-modified, the adhesion between the cured film of the acrylic-modified silicone resin coating material and the substrate is improved. Since the cured film of the acrylic-modified silicone resin coating material and the cured film of the functional coating material (1) or (2) are both silicone resin cured materials having a polysiloxane structure, the adhesion between the two films is low. high. Therefore, between the cured film of the functional coating material (1) or (2) and the base material, the cured film of the acryl-modified silicone resin coating material having high adhesion to them is interposed.
As a result, the adhesion between the cured film of the functional coating material (1) or (2) and the substrate is improved.

The first (meth) acrylate ester, which is one of the constituent monomers of the acrylic resin (D), is represented by the above formula (3) wherein R ⁴ has 1 to 9 carbon atoms, substituted or unsubstituted. A monovalent hydrocarbon group such as methyl, ethyl, n-propyl, i-propyl, n-butyl,
alkyl groups such as i-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group and octyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; 2-phenylethyl group; Aralkyl groups such as phenylpropyl group and 3-phenylpropyl group; aryl groups such as phenyl group and tolyl group; halogenated hydrocarbons such as chloromethyl group, γ-chloropropyl group and 3,3,3-trifluoropropyl group A hydroxy hydrocarbon group such as a 2-hydroxyethyl group; and the like.

The second (meth) acrylate ester, which is another constituent monomer of the acrylic resin (D), is represented by the formula (3) in which R ⁴ is an epoxy group, a glycidyl group or at least one of these. It is at least one selected from the group consisting of at least one group selected from the group consisting of hydrocarbon groups containing one of them (for example, γ-glycidoxypropyl group).

The third (meth) acrylate ester, which is another constituent monomer of the acrylic resin (D), is represented by the formula (3) wherein R ⁴ is an alkoxysilyl group and / or a halogenated silyl group. Hydrocarbon groups including, for example, trimethoxysilylpropyl group, dimethoxymethylsilylpropyl group, monomethoxydimethylsilylpropyl group, triethoxysilylpropyl group, diethoxymethylsilylpropyl group, ethoxydimethylsilylpropyl group, trichlorosilylpropyl group , A dichloromethylsilylpropyl group, a chlorodimethylsilylpropyl group, a chlorodimethoxysilylpropyl group, a dichloromethoxysilylpropyl group, or the like.

The acrylic resin (D) comprises the first, second,
The third (meth) acrylic acid ester is a (meth) acrylic acid ester copolymer containing at least one kind and a total of at least three kinds in the first, second, and third (meth) acrylic acids. Another one selected from esters
Or one or more selected from (meth) acrylic esters other than the above, or two or more.
Copolymers containing more than one species may be used.

The first (meth) acrylic ester is an essential component for improving the toughness of the cured film of the acrylic-modified silicone resin coating material.
There is also an effect of improving the compatibility between the component (A) and the component (B). In order to further enhance these effects, the substituted or unsubstituted hydrocarbon group of R ⁴ preferably has a certain volume or more, and preferably has 2 or more carbon atoms.

The second (meth) acrylic acid ester is an essential component for improving the adhesion between the cured film of the acrylic-modified silicone resin coating material and the substrate. The third (meth) acrylic acid ester forms a chemical bond between the acrylic resin (D) and the components (A) and (B) when the acrylic-modified silicone resin coating material is cured. The acrylic resin (D) is fixed in the cured film. Further, the third (meth) acrylic acid ester is composed of the acrylic resin (D), the component (A) and the component (B).
It also has the effect of improving compatibility with the components.

The molecular weight of the acrylic resin (D) greatly affects the compatibility of the acrylic resin (D) with the components (A) and (B). When the weight average molecular weight in terms of polystyrene of the acrylic resin (D) exceeds 50,000, phase separation occurs,
The coating may whiten. Therefore, the weight average molecular weight in terms of polystyrene of the acrylic resin (D) is 50,000
It is desirable to set it to 0 or less. The lower limit of the weight average molecular weight in terms of polystyrene of the acrylic resin (D) is 1,
000 is desirable. If the molecular weight is less than 1,000, the toughness of the coating film tends to decrease and cracks tend to occur, which is not preferable.

The second (meth) acrylate is desirably 2% or more in terms of a monomer molar ratio in the copolymer as the acrylic resin (D). If it is less than 2%, the adhesion of the coating film tends to be insufficient. The third (meth) acrylic acid ester has a monomer molar ratio of 2 to 2 in the copolymer.
It is desirable to be in the range of 50%. If it is less than 2%, the compatibility between the acrylic resin (D) and the components (A) and (B) is poor, and the coating film may be whitened. Also,
If it exceeds 50%, the bond density between the acrylic resin (D) and the components (A) and (B) becomes too high, and the improvement in toughness, which is the original purpose of the acrylic resin, tends to be lost.

As a method for synthesizing the acrylic resin (D), for example, a known radical polymerization method by solution polymerization, emulsion polymerization or suspension polymerization in an organic solvent, or an anionic polymerization method or a cationic polymerization method can be used. However, it is not specific to this. In the radical polymerization method by solution polymerization, for example, the first, second and third (meth) acrylate monomers are dissolved in an organic solvent in a reaction vessel by a known method, and the radical polymerization is started. The agent is added, and the mixture is reacted by heating under a nitrogen stream. The organic solvent used at this time is not particularly limited. For example, toluene, xylene, ethyl acetate, butyl acetate,
Methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate and the like are used. Further, the radical polymerization initiator is not particularly limited, and examples thereof include cumene hydroperoxide, tertiary butyl hydroperoxide, dicumyl peroxide, ditertiary butyl peroxide, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, and azo peroxide. Bisisobutyronitrile, hydrogen peroxide-Fe ²⁺ salt, persulfate-NaHSO ₃ , cumene hydroperoxide-F
e2 ⁺ salts, benzoyl peroxide-dimethylaniline, peroxide-triethylaluminum and the like are used. In order to control the molecular weight, a chain transfer agent can be added. The chain transfer agent is not particularly limited, for example, monoethyl hydroquinone,
quinones such as p-benzoquinone; thiols such as mercaptoacetic acid-ethyl ester, mercaptoacetic acid-n-butyl ester, mercaptoacetic acid-2-ethylhexyl ester, mercaptocyclohexane, mercaptocyclopentane and 2-mercaptoethanol Thiophenols such as di-3-chlorobenzenethiol, p-toluenethiol and benzenethiol; thiol derivatives such as γ-mercaptopropyltrimethoxysilane; phenylpicrylhydrazine; diphenylamine; tert-butylcatechol and the like.

The proportion of the photocatalyst (F) in the functional coating material (1) is not particularly limited, since the photocatalytic performance is exhibited regardless of the size of the photocatalyst (F). 90 to 10 parts by weight, preferably 90 to 10 parts by weight, more preferably 50 to 10 parts by weight (however, the resin solid content of (E) and (F)
Is 100 parts by weight). When the amount of the photocatalyst (F) is less than 10 parts by weight, sufficient photocatalytic performance tends not to be obtained, and when the amount exceeds 90 parts by weight, a brittle and non-smooth coating film tends to be obtained.

In the functional coating material (2), the mixing ratio of the photocatalyst (F) is not particularly limited, since the photocatalytic performance is exhibited regardless of the size thereof.
The total resin solid content of the component (A) and the component (B) is 10 to 90.
The amount is preferably 90 to 10 parts by weight, more preferably 50 to 10 parts by weight, with respect to parts by weight (however, the total of the resin solids of the components (A) and (B) and the component (F) is 100 parts by weight). . When the amount of the photocatalyst (F) is less than 10 parts by weight, sufficient photocatalytic performance tends not to be obtained, and when the amount exceeds 90 parts by weight, a brittle and non-smooth coating film tends to be obtained.

In the functional coating material (2), the mixing ratio of the component (A) and the component (B) is not particularly limited.
For example, it is preferably 99 to 1 part by weight of the component (B) to 1 to 99 parts by weight of the component (A), and more preferably 95 to 5 parts by weight of the component (B) to 5 to 95 parts by weight of the component (A).
Parts by weight, and more preferably 10 to 90 parts of component (A).
Component (B) is 90 to 10 parts by weight relative to parts by weight (provided that the total of components (A) and (B) is 100 parts by weight). If the amount of the component (A) is less than 1 part by weight, the curability at room temperature tends to be inferior or sufficient film hardness cannot be obtained. On the other hand, when the amount of the component (A) exceeds 99 parts by weight, the curability tends to be unstable or the coating film tends to crack.

The mixing ratio of the component (C) in the functional coating material (2) is not particularly limited.
For the total of 100 parts by weight of the component (A) and the component (B),
Preferably 0.0001 to 10 parts by weight, more preferably 0.005 to 8 parts by weight, even more preferably 0.007 to 10 parts by weight.
5 parts by weight. If the amount of the component (C) is less than 0.0001 parts by weight, curing tends to be difficult at normal temperature. On the other hand, if the amount exceeds 10 parts by weight, the heat resistance and weather resistance of the cured film tend to deteriorate.

The proportion of the component (C) in the acrylic-modified silicone resin coating material is not particularly limited,
For example, based on a total of 100 parts by weight of the components (A), (B) and (D), preferably 0.001 to 10 parts by weight, more preferably 0.005 to 8 parts by weight, and still more preferably 0.007 parts by weight. -5 parts by weight. 0.001 component (C)
If the amount is less than part by weight, curing tends to be difficult at normal temperature. on the other hand,
If the amount exceeds 10 parts by weight, the heat resistance and weather resistance of the cured film tend to deteriorate.

The mixing ratio of the component (A), the component (B) and the component (D) in the acrylic-modified silicone resin coating material is not particularly limited.
It is preferable that the amount of the component (B) is 94 to 1 part by weight and the component (D) is 5 to 35 parts by weight, based on the total weight of the composition,
Component (B) 95 to 5 with respect to component (A) 5 to 95 parts by weight.
The amount is more preferably from 5 to 35 parts by weight and from 10 to 94 parts by weight of the component (A), from 94 to 10 parts by weight of the component (B) and from 5 to 35 parts by weight of the component (D).
More preferably, it is by weight (provided that (A),
(The total of the components (B) and (D) is 100 parts by weight.)
If the amount of the component (A) is less than 1 part by weight, the curability at room temperature tends to be inferior or sufficient film hardness cannot be obtained.
On the other hand, when the amount of the component (A) exceeds 94 parts by weight, the curability tends to be unstable or the coating film tends to crack. When the amount of the component (D) is less than 5 parts by weight, sufficient toughness and adhesion tend to be not obtained. (D) component is 3
If the amount exceeds 5 parts by weight, the possibility that the deterioration of the coating film is accelerated by the photocatalyst in the upper layer increases.

The functional coating material (1) is heated at a low temperature or left at room temperature after adding a curing catalyst, whereby the hydrolyzable groups of the component (E) undergo a condensation reaction to form a cured film. I do. Therefore, the functional coating material (1) is hardly affected by humidity even when it is cured at room temperature. Further, by performing the heat treatment, the condensation reaction can be promoted without using a curing catalyst to form a cured film.

In the functional coating material (2), the hydrolyzable group of the organosilane oligomer contained in the component (A) and the silanol group of the component (B) are formed in the presence of the curing catalyst (C). Then, when left at room temperature or heated at a low temperature, a condensation reaction occurs to form a cured film. Therefore, the functional coating material (2) is hardly affected by humidity even when it is cured at room temperature. In addition, a heat treatment can promote a condensation reaction to form a cured film.

The acrylic-modified silicone resin coating material comprises a hydrolyzable group of the organosilane oligomer contained in the component (A) and a hydrolyzable group of the acrylic resin (D) and a silanol group of the component (B). In the presence of the curing catalyst (C), the group undergoes a condensation reaction when left at room temperature or heated at a low temperature to form a cured film. Therefore, the acrylic-modified silicone resin coating material is hardly affected by humidity even when cured at room temperature. In addition, a heat treatment can promote a condensation reaction to form a cured film.

The acrylic-modified silicone resin coating material may contain a pigment, if necessary. Examples of pigments that can be used include, but are not particularly limited to, organic pigments such as carbon black, quinacridone, naphthol red, cyanine blue, cyanine green, and Hansa Yellow; Inorganic pigments are preferred, and one or more selected from these groups may be used in combination. The dispersion of the pigment is not particularly limited, and may be a usual method, for example, a method of directly dispersing the pigment powder using a dyno meal, a paint shaker, or the like. At that time, a dispersant, a dispersing aid, a thickener, a coupling agent, and the like can be used. The amount of the pigment to be added is not particularly limited because the concealing property varies depending on the type of the pigment.
The amount is preferably 5 to 80 parts by weight, more preferably 10 to 60 parts by weight, based on 100 parts by weight of the total of the components (B) and (D). When the amount of the pigment is less than 5 parts by weight, the concealing property tends to deteriorate, and when the amount exceeds 80 parts by weight, the smoothness of the coating film may deteriorate.

It should be noted that a leveling agent, a dye, a metal powder, a glass powder, an antibacterial agent, an antioxidant, an antistatic agent, an ultraviolet absorber, and the like may also be used as long as the effects of the present invention are not adversely affected. May be included. The functional coating materials (1) and (2) and the acryl-modified silicone resin coating material can be used by diluting them with various organic solvents as necessary, because of the ease of handling. May be done.
The type of the organic solvent is the type of the monovalent hydrocarbon group contained in the component (A), (B), (D) or (E), or
It can be appropriately selected according to the molecular weight of the component (A), (B), (D) or (E). Such an organic solvent is not particularly limited. For example, methanol, ethanol, isopropanol, n-
Lower aliphatic alcohols such as butanol and isobutanol; ethylene glycol derivatives such as ethylene glycol, ethylene glycol monobutyl ether and ethylene glycol monoethyl ether; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; and toluene, xylene, hexane, Heptane, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime, diacetone alcohol and the like can be mentioned, and one or more selected from the group consisting of these can be used. The dilution ratio in the organic solvent is not particularly limited, and the dilution ratio may be appropriately determined as needed.

The method of applying each coating material to the substrate is not particularly limited, and for example, various common coating methods such as brush coating, spraying, dipping, flow, roll, curtain, knife coating, spin coating and the like. Can be selected. A method for curing each coating material applied to the base material may be a known method, and is not particularly limited. In addition, the temperature at the time of curing is not particularly limited, and can be in a wide range from room temperature to heating temperature depending on the desired performance of the cured film, the use of a curing catalyst, the heat resistance of the photocatalyst, and the like.

Functional coating material (1) or (2)
The thickness of the cured film formed from is not particularly limited, since the photocatalytic performance is exhibited regardless of the size thereof. In addition, the thickness is preferably 0.05 to 5 μm, in order to stably adhere and hold the cured film over a long period of time and to prevent cracking or peeling.
05 to 2 μm is more preferable.

The thickness of the cured film formed from the acrylic-modified silicone resin coating material is not particularly limited, and may be, for example, about 0.1 to 100 μm. The thickness is preferably 0.5 to 50 μm in order to stably adhere and hold for a long period of time and to prevent cracking or peeling. Coating method (iii) The third coating method (iii) is a coating method using the functional coating material (1) containing the above-mentioned components (E) and (F).

In the third coating method,
Since an inorganic polymer is used as the resin of the coating material, degradation due to photocatalysis is less likely to occur. Further, since it is excellent in durability, hardness and abrasion resistance as a coating material, it can be sufficiently used even when coated on the surface of an aggregate as in the present invention and used for road pavement. Coating method (iv) In the fourth coating method (iv), a photocatalyst is added to an inorganic coating containing silicone resin as a main component in an amount of from 2 to 8 parts by weight based on 100 parts by weight of the total of the solid content in terms of the total condensation compound and the total photocatalytic component.
This is a coating method using an antistatic inorganic paint containing 0 parts by weight as a coating material. .

The paint contained in the antistatic inorganic paint described above
The silicone resin is used as a film-forming component. Silico
As a resin, it deteriorates with time even when mixed with a photocatalyst.
In that the silicone resin contains the following component (A)
(1) is preferable.
In terms of not deteriorating with time and curing at room temperature (normal temperature),
Silicone resin containing (B), (C) and (D) components
(2) is preferable. Component (A): (A₁) General formula R^TwoSi (OR¹)_ThreeSilicon represented by
With respect to 100 parts by weight of the compound, (A_Two) General formula Si (OR
¹)_FourA silicon compound and / or colloidal represented by
20 to 200 parts by weight of silica (A)_Three) General formula R^Two _Two
Si (OR¹) _Two0-60 weight of a silicon compound represented by
And a hydrolyzable mixture (where R ¹, R^TwoIs monovalent
Hydrolyzed polycondensate).
Weight average molecular weight of hydrolyzed polycondensate
Organos adjusted to be over 900 in total
Loxane. Component (B): General formula R^Three _mSix_4-m ... (6) where R is^ThreeAre the same or different substitutions
Represents an unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and m represents
X represents an integer of 0 to 3 and represents a hydrolyzable group. ) Hydrolytic
Dissolve organosilanes in organic solvents, water or their mixtures
In colloidal silica dispersed in a medium, the hydrolyzable
0.001 to 0.5 mole of water per mole equivalent of group (X)
Organosila, partially hydrolyzed under the conditions used
Of silica in oligomers. Component (C): average composition formula R^Four _aSi (OH)_bO_{(4-ab) / 2} ... (7) where R is^FourIs the same or different
Represents an unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms;
And b are 0.2 ≦ a ≦ 2 and 0.0001 ≦ b ≦
3, a number satisfying the relationship of a + b <4. ), In the molecule
Polyorganosiloxane containing silanol groups. Component (D): curing catalyst.

As the component (A) contained in the silicone resin (1), that is, as a raw material of the organosiloxane (A), a hydrolyzable mixture containing the silicon compounds (A ₁ ) to (A ₃ ) is used. Silicon compound (A ₁ )
(A ₃₎ of the general formula ^{_{R 2 p Si (OR 1)}} 4-p ... can be grossly expressed in (8) (wherein R ^1, R ² represents a monovalent hydrocarbon group, p Is an integer of 0 to 2).

R ^{2 in the} formula (8) is not particularly limited. For example, R ² may be substituted or unsubstituted and has 1 carbon atom.
To 8 monovalent hydrocarbon groups. Specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; a 2-phenylethyl group; Aralkyl groups such as 2-phenylpropyl group and 3-phenylpropyl group; aryl groups such as phenyl group and tolyl group; alkenyl groups such as vinyl group and allyl group; chloromethyl group, γ-chloropropyl group, 3,3 and Halogen-substituted hydrocarbon group such as 3-trifluoropropyl group; γ-methacryloxypropyl group, γ
And substituted hydrocarbon groups such as -glycidoxypropyl group, 3,4-epoxycyclohexylethyl group, and γ-mercaptopropyl group. Among these,
An alkyl group having 1 to 4 carbon atoms and a phenyl group are preferable in terms of ease of synthesis or availability.

Further, R ^{1 in the} formula (8) is not particularly limited. For example, R ¹ having an alkyl group having 1 to 4 carbon atoms as a main raw material is used. Particularly, tetramethoxysilane, tetraethoxysilane and the like can be exemplified as the tetraalkoxysilane with p = 0, and as the organotrialkoxysilane with p = 1, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane can be exemplified. Phenyltrimethoxysilane, phenyltriethoxysilane, and 3,3,3-trifluoropropyltrimethoxysilane. Also,
Examples of the diorganodialkoxysilane having p = 2 include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane.

These R ¹ and R ² may be the same or different among the silicon compounds (A ₁ ) to (A ₃ ). The organosiloxane (A) is prepared by, for example, diluting the hydrolyzable mixture with an appropriate solvent, adding water and a catalyst as required in a required amount, and subjecting the mixture to hydrolysis and polycondensation to perform a prepolymer. Can be prepared. At that time, the weight average molecular weight (Mw) of the obtained prepolymer
Is 900 or more in terms of polystyrene, preferably 1000
Adjust so that it is above. When the molecular weight distribution (weight average molecular weight (Mw)) of the prepolymer is smaller than 900, the curing shrinkage at the time of polycondensation of the silicone resin (1) is large, and cracks are easily generated in the coating film after curing. .

The amount of the raw materials (A ₁ ) to (A ₃ ) used for preparing the organosiloxane (A) is preferably 20 to 200 parts by weight of (A ₂ ) per 100 parts by weight of (A ₁ ). Is 40 to 160 parts by weight, more preferably 60 to 120 parts by weight, and (A ₃ ) is 60 parts by weight or less (preferably 40 parts by weight or less, more preferably 30 parts by weight or less). If the amount of (A ₂ ) used is smaller than the above range, or if the amount of (A ₃ ) used is larger than the above range, there is a problem that a desired hardness of the cured film cannot be obtained (hardness is lowered). . On the other hand, if the amount of (A ₂ ) is more than the above range, the cured film has too high a cross-linking density and too high a hardness, so that there is a problem that cracks are easily generated.

The colloidal silica that can be used as the raw material (A ₂ ) is not particularly limited, and for example, water-dispersible or non-aqueous organic solvent-dispersible colloidal silica such as alcohol can be used. Generally, such colloidal silica has a silica content of 20 to 50%.
%, And the silica content can be determined from this value. When water-dispersible colloidal silica is used, water present as a component other than the solid content can be used as a curing agent as described later. The water-dispersible colloidal silica is usually made of water glass, but can be easily obtained as a commercial product. The organic solvent-dispersible colloidal silica can be easily prepared by replacing water of the water-dispersible colloidal silica with an organic solvent. Such an organic solvent-dispersible colloidal silica can be easily obtained as a commercial product similarly to the water-dispersible colloidal silica. In the colloidal silica dispersible in an organic solvent, the type of the organic solvent in which the colloidal silica is dispersed is, for example, lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol, and isobutanol; ethylene glycol, ethylene glycol monobutyl ether And ethylene glycol derivatives such as ethylene glycol monoethyl ether acetate;
And diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; and diacetone alcohol. One or more selected from the group consisting of these can be used. Toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime and the like can also be used in combination with these hydrophilic organic solvents.

When colloidal silica is used as the raw material (A ₂ ), the proportion of (A ₂ ) is part by weight including the dispersion medium. In addition, water is used as a curing agent used in the hydrolysis polycondensation reaction of the hydrolyzable mixture, and the amount of the water is 1 mole equivalent of OR ¹ group contained in the hydrolyzable mixture. Water 0.01-3.0
Mol is preferable, and 0.3 to 1.5 mol is more preferable.

As the diluting solvent used in the hydrolysis polycondensation reaction of the hydrolyzable mixture, the lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol and the like described above as the dispersion solvent for colloidal silica are used. And the like; ethylene glycol derivatives such as ethylene glycol, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether acetate; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; and diacetone alcohol. One or more of them can be used. In combination with these hydrophilic organic solvents, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime and the like can also be mentioned.

It is preferable that the pH of the organosiloxane (A) is adjusted within a range of 3.8 to 6.
If the pH is within this range, within the aforementioned molecular weight range,
The organosiloxane (A) can be used stably. If the pH is out of this range, the stability of the organosiloxane (A) is poor, so that the usable period from the time of preparing the paint is limited. Here, the method of adjusting the pH is not particularly limited. For example, when the pH of the organosiloxane (A) becomes less than 3.8 when the raw materials are mixed, a basic reagent such as ammonia may be used. The pH may be adjusted to a value within the above range, and when the pH exceeds 6, it may be adjusted using, for example, an acidic reagent such as hydrochloric acid. In addition, depending on the pH, when the reaction does not proceed while the molecular weight is small and it takes time to reach the molecular weight range, the organosiloxane (A) may be heated to accelerate the reaction, After the pH is lowered with a reagent to proceed the reaction, the pH may be returned to a predetermined value with a basic reagent.

The silicone resin (1) does not need to contain a curing catalyst when it is cured by heating. However, by promoting the condensation reaction of the organosiloxane (A), it is possible to promote the heat curing of the coating film or to form the coating film. If necessary, the composition may further contain a curing catalyst for the purpose of curing at room temperature. The curing catalyst is not particularly limited,
For example, alkyl titanates; metal carboxylate such as tin octylate, dibutyltin dilaurate, dioctyltin dimaleate; amine salts such as dibutylamine-2-hexoate, dimethylamine acetate, ethanolamine acetate; tetramethylammonium acetate and the like Carboxylic acid quaternary ammonium salts; amines such as tetraethylpentamine, amine silanes such as N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane Coupling agents; acids such as p-toluenesulfonic acid, phthalic acid and hydrochloric acid; aluminum compounds such as aluminum alkoxide and aluminum chelate; lithium acetate, potassium acetate, lithium formate, sodium formate, potassium phosphate; Alkali metal salts such as potassium oxide; tetraisopropyl titanate, tetrabutyl titanate, titanium compounds such as titanium tetra acetyl acetonate; methyltrichlorosilane, dimethyldichlorosilane, halogenated silanes such as trimethyl monochloro silane, and the like. However, other than these, there is no particular limitation as long as it is effective for accelerating the condensation reaction of the organosiloxane (A).

When the silicone resin (1) also contains a curing catalyst, the amount thereof is based on the amount of the organosiloxane (A).
It is preferably at most 10% by weight, more preferably at most 8% by weight. If it exceeds 10% by weight, the storage stability of the inorganic coating material having an antistatic function may be impaired. When the silicone resin contained in the antistatic function inorganic coating is a silicone resin (1), the antistatic function inorganic coating is heated at a low temperature or added with a curing catalyst and left at room temperature to obtain the component (A). The hydrolyzable groups of the above form a condensation reaction to form a cured film. Therefore, such an antistatic inorganic coating is hardly affected by humidity even when it is cured at room temperature. Also, if you perform heat treatment,
The cured film can be formed by promoting the condensation reaction without using a curing catalyst.

The component (B) contained in the silicone resin (2), that is, a silica-dispersed oligomer solution (B)
Is a main component of a base polymer having a hydrolyzable group (X) as a functional group that participates in a curing reaction when forming a cured film of an inorganic coating having an antistatic function. For example, one or two types of the hydrolyzable organosilane represented by the general formula (6) may be added to colloidal silica dispersed in an organic solvent or water (a mixed solvent of an organic solvent and water may be used). In addition to the above, water (water previously contained in the colloidal silica and / or water separately added) is added to the hydrolyzable group (X) in an amount of 0.001 to water per mole equivalent.
It is obtained by partially hydrolyzing the hydrolyzable organosilane under the condition of using 0.5 mol.

The group R ³ in the hydrolyzable organosilane represented by the general formula (6) is the same or different and is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. Although not limited, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group;
Aralkyl groups such as -phenylethyl group, 2-phenylpropyl group and 3-phenylpropyl group; aryl groups such as phenyl group and tolyl group; alkenyl groups such as vinyl group and allyl group; chloromethyl group and γ-chloropropyl group , 3,
Halogen-substituted hydrocarbon groups such as 3,3-trifluoropropyl group; substituted hydrocarbons such as γ-methacryloxypropyl group, γ-glycidoxypropyl group, 3,4-epoxycyclohexylethyl group, γ-mercaptopropyl group And the like. Among these, an alkyl group having 1 to 4 carbon atoms and a phenyl group are preferable from the viewpoint of ease of synthesis or availability.

In the general formula (6), the hydrolyzable group X is not particularly restricted but includes, for example, alkoxy, acetoxy, oxime, enoxy, amino, aminoxy, amide and the like. Can be Among these, an alkoxy group is preferred because of its availability and ease of preparing the silica-dispersed oligomer solution (B).

Specific examples of the hydrolyzable organosilane include mono-, di-, tri- and tetra-functional alkoxysilanes wherein m in the general formula (6) is an integer of 0 to 3. , Acetoxysilanes, oxime silanes,
Examples include enoxysilanes, aminosilanes, aminoxysilanes, amidosilanes and the like. Among these, alkoxysilanes are preferable because they are easily available and the silica-dispersed oligomer solution (B) is easily prepared.

Among the alkoxysilanes, m = 0
Examples of the tetraalkoxysilane include tetramethoxysilane and tetraethoxysilane. Examples of the organotrialkoxysilane having m = 1 include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, and phenyltrimethoxysilane. ,
Examples thereof include phenyltriethoxysilane and 3,3,3-trifluoropropyltrimethoxysilane. Further, as the diorganodialkoxysilane of m = 2,
Examples thereof include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane. Examples of the triorganoalkoxysilane having m = 3 include trimethylmethoxysilane, trimethylethoxysilane, and trimethylisopropoxysilane. And dimethylisobutylmethoxysilane. Further, an organosilane compound generally called a silane coupling agent is also included in the alkoxysilanes.

Of these hydrolyzable organosilanes represented by the general formula (6), 50 mol% or more (preferably 60 mol% or more, more preferably 70 mol% or more)
Is a trifunctional compound represented by m = 1. This is,
If it is less than 50 mol%, sufficient coating film hardness cannot be obtained, and the coating film tends to have poor dry curability. Colloidal silica in the silica-dispersed oligomer solution (B) has the effect of increasing the hardness of a cured coating applied with an inorganic coating having an antistatic function and improving smoothness and crack resistance. The colloidal silica is not particularly limited, and for example, water-dispersible or non-aqueous organic solvent-dispersible colloidal silica such as alcohol can be used. Generally, such colloidal silica contains 20 to 50% by weight of silica as a solid content.
And the silica content can be determined from this value.
When using water-dispersible colloidal silica,
Water present as a component other than the solid content can be used for the hydrolysis of the hydrolyzable organosilane and can be used as a curing agent for the antistatic inorganic coating. The water-dispersible colloidal silica is usually made of water glass, but can be easily obtained as a commercial product. The organic solvent-dispersible colloidal silica can be easily prepared by replacing water of the water-dispersible colloidal silica with an organic solvent. Such an organic solvent-dispersible colloidal silica can be easily obtained as a commercial product similarly to the water-dispersible colloidal silica. In the organic solvent-dispersed colloidal silica, the type of the organic solvent in which the colloidal silica is dispersed is not particularly limited. For example, lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol and isobutanol; ethylene Ethylene glycol derivatives such as glycol, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether acetate; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; and diacetone alcohol. Alternatively, two or more kinds can be used. In combination with these hydrophilic organic solvents, toluene,
Xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime and the like can also be used.

The colloidal silica in the silica-dispersed oligomer solution (B) has the above-mentioned effects. However, if the amount is too large, the cured coating of the inorganic coating having an antistatic function becomes too hard and cracks of the coating may be generated. There is a possibility that it may cause an invite. Therefore, in the silica-dispersed oligomer solution (B), the colloidal silica contains silica as a solid component,
It is contained in the range of 5 to 95% by weight (preferably 10 to 90% by weight, more preferably 20 to 85% by weight). When the content is less than 5% by weight, a desired coating hardness tends to be not obtained. On the other hand, if it exceeds 95% by weight, cracks are likely to occur.

In the present specification, the blending ratio of the component (B) in the silicone resin (2) is a value including the dispersion medium of colloidal silica. As described above, the amount of water used when preparing the silica-dispersed oligomer solution (B) is 0.001 to 0.5 per 1 molar equivalent of the hydrolyzable group (X) of the hydrolyzable organosilane. It is in the range of moles, preferably in the range of 0.01 to 0.4 mole. When the amount of water used is less than 0.001 mol, a sufficient partial hydrolyzate cannot be obtained, and when it exceeds 0.5 mol, the stability of the partial hydrolyzate deteriorates. Here, the amount of water used in the partial hydrolysis reaction of the hydrolyzable organosilane is separately determined when colloidal silica containing no water (for example, colloidal silica using only an organic solvent as a dispersion medium) is used. It is the amount of water added. When colloidal silica containing water (for example, colloidal silica using only water or a mixed solvent of an organic solvent and water as a dispersion medium of colloidal silica) is used, It is the amount of water previously contained in at least the colloidal silica of the water previously contained and the water separately added. If the amount of water was previously contained in the colloidal silica alone and the amount used was sufficient, it was not necessary to separately add water, but the amount of water was previously contained in the colloidal silica. If water alone is not sufficient for the above usage, it is necessary to separately add water until the usage reaches the above usage. In this case, the amount of water used is the total amount of water previously contained in the colloidal silica and water added separately. In addition, even if only the water previously contained in the colloidal silica is sufficient for the amount used, water may be separately added, and in that case, the amount of water used is
It is the total amount of water previously contained in the colloidal silica and water added separately. However, water is separately added so that the total amount does not exceed the upper limit (0.5 mol per 1 mol equivalent of the hydrolyzable group (X)).

The method of partially hydrolyzing the hydrolyzable organosilane is not particularly limited. For example, the hydrolyzable organosilane may be mixed with colloidal silica (whether the colloidal silica contains no water or If the required amount is not contained, add water here. At that time, the partial hydrolysis reaction proceeds at room temperature,
In order to accelerate the partial hydrolysis reaction, if necessary, heating (for example, 60 to 100 ° C.) or a catalyst may be used. Examples of the catalyst include, but are not limited to, hydrochloric acid, acetic acid, halogenated silane, chloroacetic acid, citric acid, benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, maleic acid, and malonic acid. , And one or more of organic acids and inorganic acids such as toluenesulfonic acid and oxalic acid.

The silica-dispersed oligomer solution (B) is prepared by adjusting the pH of the solution in order to stably obtain its performance over a long period of time.
Preferably 2.0 to 7.0, more preferably 2.5 to
6.5, more preferably 3.0-6.0. When the pH is out of this range, the performance continuity of the component (B) is significantly reduced particularly under the condition that the amount of water used is 0.3 mol or more per 1 mol equivalent of the hydrolyzable group (X). When the pH of the component (B) is outside the above range, the pH may be adjusted by adding a basic reagent such as ammonia or ethylenediamine if the pH is more acidic than this range. The pH may be adjusted using an acidic reagent such as hydrochloric acid, nitric acid, and acetic acid. However, the adjustment method is not particularly limited.

The component (C) contained in the silicone resin (2), that is, the silanol group-containing polyorganosiloxane (C) is a base polymer having a hydrolyzable group as a functional group subjected to a curing reaction. ) Is a cross-linking agent for forming a three-dimensional cross-link in the cured film by a condensation reaction with the component.

R ⁴ in the above average composition formula (7) representing the silanol group-containing polyorganosiloxane (C) is
There is no particular limitation, and examples thereof include the same as R ³ in the formula (6). Substituted hydrocarbon groups such as γ-methacryloxypropyl group, γ-aminopropyl group, 3,3,3-trifluoropropyl group, and more preferably methyl group and phenyl group. In the above formula (7), a and b are numbers satisfying the above relation, respectively, and a is less than 0.2 or b
Is more than 3, there are inconveniences such as cracks in the cured coating of the inorganic coating having an antistatic function. When a is more than 2 and 4 or less, or when b is less than 0.0001, curing does not proceed well.

The silanol group-containing polyorganosiloxane (C) is not particularly limited.
Methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane,
Alternatively, it can be obtained by hydrolyzing one or a mixture of two or more of the corresponding alkoxysilanes with a large amount of water by a known method. When a silanol group-containing polyorganosiloxane (C) is hydrolyzed by a known method using alkoxysilane, a small amount of an unhydrolyzed alkoxy group may remain. That is, a polyorganosiloxane in which a silanol group and a trace amount of an alkoxy group coexist may be obtained, but in the present invention, such a polyorganosiloxane may be used.

The component (D), ie, the curing catalyst (D), contained in the silicone resin (2) accelerates the condensation reaction between the components (B) and (C), and forms a coating film of an antistatic inorganic coating. Is a component that cures. Examples of the curing catalyst (D) include, but are not particularly limited to, alkyl titanates; carboxylic acid metal salts such as tin octylate, dibutyltin dilaurate, and dioctyltin dimaleate; dibutylamine-2-hexoate, dimethylamine acetate; Amine salts such as ethanolamine acetate; quaternary ammonium salts of carboxylic acids such as tetramethylammonium acetate; amines such as tetraethylpentamine; N-β-aminoethyl-γ-aminopropyltrimethoxysilane; N-β-amino Amine-based silane coupling agents such as ethyl-γ-aminopropylmethyldimethoxysilane; acids such as p-toluenesulfonic acid, phthalic acid, and hydrochloric acid; aluminum compounds such as aluminum alkoxide and aluminum chelate; lithium acetate, lithium formate; Alkali metal salts such as sodium phosphate, potassium phosphate and potassium hydroxide; Titanium compounds such as tetraisopropyl titanate, tetrabutyl titanate and titanium tetraacetylacetonate; halogenated silanes such as methyltrichlorosilane, dimethyldichlorosilane and trimethylmonochlorosilane And the like.
However, other than these, there is no particular limitation as long as it is effective for promoting the condensation reaction between the component (B) and the component (C).

In the silicone resin (2), the mixing ratio of the component (B) and the component (C) is 1 to 99 parts by weight based on 100 parts by weight of the total of the components (B) and (C). , 99 to 1 parts by weight of component (C) (preferably 5 to 95 parts by weight of component (B), 95 to 5 parts by weight of component (C), more preferably 10 to 90 parts by weight of component (B), ) Component 9
0 to 10 parts by weight). If the amount of the component (B) is less than 1 part by weight (the amount of the component (A) exceeds 99 parts by weight), the curability at room temperature tends to be poor, and sufficient film hardness tends not to be obtained. On the other hand, when the component (B) exceeds 99 parts by weight (the component (A) is less than 1 part by weight), the curability is unstable,
In addition, a good coating film may not be obtained.

In the silicone resin (2), the mixing ratio of the component (D) is 100% in total of the components (B) and (C).
It is in the range of 0.0001 to 10 parts by weight (preferably in the range of 0.0005 to 8 parts by weight, more preferably in the range of 0.0007 to 5 parts by weight) with respect to parts by weight.
When the amount of (D) is less than 0.0001 part by weight, the room-temperature curability tends to decrease, and sufficient coating hardness tends not to be obtained. If the amount exceeds 10 parts by weight, the heat resistance and weather resistance of the cured film may be reduced, and the hardness of the cured film may be too high to cause cracks.

When the silicone resin contained in the antistatic function inorganic coating is the silicone resin (2), the antistatic function inorganic coating contains the hydrolyzable group of the organosilane oligomer contained in the component (B) and ( In the presence of the curing catalyst (D), the silanol group of component (C) undergoes a condensation reaction when left at room temperature or heated at a low temperature to form a cured film. Therefore, such an antistatic inorganic coating is hardly affected by humidity even when it is cured at room temperature. In addition, a heat treatment can promote a condensation reaction to form a cured film.

The photocatalyst contained in the antistatic function inorganic coating material is not particularly limited. For example, titanium oxide, zinc oxide, tin oxide, iron oxide, zirconium oxide, tungsten oxide, chromium oxide, molybdenum oxide, ruthenium oxide, Examples include metal oxides such as germanium oxide, lead oxide, cadmium oxide, copper oxide, vanadium oxide, niobium oxide, tantalum oxide, manganese oxide, cobalt oxide, rhodium oxide, and rhenium oxide, as well as strontium titanate. Among these, the metal oxide is
It is preferable because it can be easily used practically.

When the transparency of the coating film is required, the average primary particle diameter of the photocatalyst is preferably 50 μm or less, more preferably 5 μm or less, and more preferably 0.5 μm or less.
It is more preferred that: One photocatalyst may be used alone, or two or more photocatalysts may be used in combination. The photocatalyst may be in any form as long as it can be dispersed in a paint such as powder, fine particle powder, and solution-dispersed sol particles. Further, the raw material of the photocatalyst is not limited as long as it finally shows the properties of the photocatalyst.

When titanium oxide is used as a photocatalyst, it is preferable to use a titanium oxide having a crystal form showing an anatase in that the antistatic performance is exhibited for a long period of time. When the coating film of the antistatic function inorganic coating material is irradiated with light, the surface resistance of the coating film is reduced by the action of the photocatalyst contained in the coating film, thereby exhibiting an antistatic effect, and the coating film surface is hardly stained. When light is irradiated to the photocatalyst-containing coating film, the mechanism by which the surface resistance value of the coating film decreases is not yet clearly identified, but electrons and holes generated by the light irradiation act. It is considered that this reduces the surface resistance of the coating film.

When the metal is supported on the surface of the photocatalyst,
The antistatic effect of the coating film becomes higher. Although the mechanism has not been clearly confirmed, the fact that a metal is supported on the surface of the photocatalyst promotes the charge separation of the photocatalyst and reduces the probability of disappearance of electrons and holes generated by the charge separation. Is considered to be related. Examples of the metal supported on the surface of the photocatalyst include silver, copper,
Iron, nickel, zinc, platinum, gold, palladium, cadmium, cobalt, rhodium, ruthenium and the like are preferable in that charge separation of the photocatalyst is further promoted. The supported metal may be only one kind or two or more kinds.

The amount of metal carried is not particularly limited, but
For example, the content is preferably 0.1 to 10% by weight, more preferably 0.2 to 5% by weight, based on the photocatalyst. If the loading is less than 0.1% by weight, the loading effect tends not to be sufficiently obtained. Problems tend to occur.

The method for supporting the metal is not particularly limited, and examples thereof include an immersion method, an impregnation method, and a photoreduction method. The amount of the photocatalyst in the antistatic function inorganic paint is not particularly limited. When metal is not supported, it is preferably 5 to 80 parts by weight, more preferably 10 to 50 parts by weight, and when metal is supported on the surface of the photocatalyst, preferably 2 to 75 parts by weight, Preferably it is 5-45 parts by weight. When the amount of the photocatalyst is less than the above range, a sufficient antistatic function tends to be hardly obtained, and when the amount is more than the above range, cracks are likely to occur, and the coating film performance tends to decrease. . The amount of the photocatalyst when the metal is supported on the surface of the photocatalyst does not include the supported metal.

The inorganic coating having an antistatic function can be toned by further containing a coloring agent such as a pigment or a dye, if necessary. Examples of pigments that can be used include, but are not particularly limited to, organic pigments such as carbon black, quinacridone, naphthol red, cyanine blue, cyanine green, and Hansa Yellow; Inorganic pigments are preferred, and one or more selected from these groups may be used in combination. The dispersion of the pigment is not particularly limited, and may be a usual method, for example, a method of directly dispersing the pigment powder using a dyno meal, a paint shaker, or the like. At that time, a dispersant, a dispersing aid, a thickener, a coupling agent, and the like can be used. The amount of the pigment to be added is not particularly limited because the concealing property varies depending on the type of the pigment.
70 parts by weight. When the amount of the pigment is less than 5 parts by weight, the concealing property tends to deteriorate, and when the amount exceeds 80 parts by weight, the smoothness of the coating film may deteriorate.

The dyes that can be used are not particularly limited. For example, azo dyes, anthraquinone dyes, indicoid dyes, sulfide dyes, triphenylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, quinone imine dyes, and the like can be used.
And thiazole, methine, nitro and nitroso dyes. One kind selected from these groups or a combination of two or more kinds may be used. The amount of the dye to be added is not particularly limited because the concealing property varies depending on the type of the dye. For example, the amount is preferably 5 to 80 parts by weight, more preferably 10 to 70 parts by weight, based on 100 parts by weight of the solid content in terms of the total condensed compound. Parts by weight. If the amount of the dye is less than 5 parts by weight, the concealing property tends to be poor,
If the amount exceeds 0 parts by weight, the smoothness of the coating film may deteriorate.

In addition, a leveling agent, metal powder, glass powder,
Antibacterial agents, antioxidants, ultraviolet absorbers and the like may also be included in the antistatic inorganic coating within a range that does not adversely affect the effects of the present invention. The antistatic inorganic coating can be used by diluting it with various organic solvents, if necessary, for ease of handling, or may be diluted with the same organic solvent. The type of the organic solvent can be appropriately selected according to the type of the monovalent hydrocarbon group contained in each component of the silicone resin, the molecular weight of each component of the silicone resin, and the like. Examples of such an organic solvent are not particularly limited. For example, lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol and isobutanol; ethylene glycol, ethylene glycol monobutyl ether, and ethylene glycol monoethyl acetate Ethylene glycol derivatives such as;
Diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; and
Examples thereof include toluene, xylene, hexane, heptane, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime, and diacetone alcohol, and one or more selected from the group consisting of these are used. be able to.
The dilution ratio in the organic solvent is not particularly limited, and the dilution ratio may be appropriately determined as needed.

The method of applying an antistatic inorganic coating is as follows.
There is no particular limitation, and for example, various usual coating methods such as brush coating, spraying, dipping (dipping), roll, flow, curtain, knife coating, and spin coating can be selected. The method of curing the coating film of the antistatic inorganic coating may be a known method, and is not particularly limited. In addition, the temperature at the time of curing is not particularly limited, and can be in a wide range from room temperature to heating temperature depending on the desired performance of the cured film, the use of a curing catalyst, the heat resistance of the photocatalyst, and the like.

The thickness of the cured coating film formed of the inorganic coating having an antistatic function is not particularly limited.
The thickness may be about 5 to 10 μm. However, in order to exert the antistatic function more effectively, the coated cured film is stably adhered and held for a long term, and cracks and peeling do not occur. 0.05-5 μm is preferable, and 0.05
２2 μm is more preferable. Coating Method (v) The fifth coating method (v) is a solution and aggregate containing an additive, ammonium titanium fluoride, and water, which promote the equilibrium of the following reaction formula (4) in an aqueous solution containing ammonium titanium fluoride to the right. To form a photocatalytically active titanium oxide film on the surface of the aggregate.

(NH ₄ ) ₂ TiF ₆ + 2H ₂ O = TiO ₂ + 4HF + 2NH ₄ F (4) Further, in the above method, the concentration of the additive is 0.05 to 0 with respect to the total amount of the solution. It needs to be 0.5 mol / liter. Further, the concentration of titanium ammonium fluoride is 0.01 to 0.2 with respect to the total amount of the solution.
mol / liter. That is,
The concentration of the additive is 0.05 mol with respect to the total amount of the solution.
When the concentration is less than 1 / liter, a titanium oxide film is not formed. When the concentration of titanium ammonium fluoride exceeds 0.2 mol / l with respect to the total amount of the solution, the formed film is not titanium oxide. , NH ₄ TiOF ₃ and TiOF ₂ tend to be mixed. Therefore, the concentration of the additive is 0.1% with respect to the total amount of the solution.
The concentration of 0.5 to 0.5 mol / liter and the concentration of ammonium titanium fluoride are 0.01 to 0.5 mol / l based on the total amount of the solution.
When it is 2 mol / liter, a titanium oxide film is formed on the surface of the aggregate.

In the above method, the titanium oxide film is formed to a thickness of 100 nm to 2 μm, and after the titanium oxide film is formed on the surface of the aggregate, it is fired at 100 to 700 ° C. Thereby, a photocatalytically active titanium oxide film having excellent photocatalytic activity is formed on the surface of the aggregate. That is, when the thickness of the titanium oxide film is less than 100 nm, the photocatalytic performance is reduced.

The additive used here may be any as long as it can make a solution containing ammonium titanium fluoride and water supersaturated with titanium oxide, and is preferably boric acid. Here, if powder acting as a nucleus is present in the solution maintaining equilibrium, it will promote the generation of titanium oxide in the solution, and as a result, the efficiency of forming a titanium oxide film on the aggregate will be reduced. It tends to be worse. In addition, when the aggregate is newly immersed in the solution, the powder of the precipitated titanium oxide precipitated in the solution usually soars, and tends to cause inconvenience in forming the titanium oxide film on the aggregate. .

Therefore, the solution is not miscible with water,
It is also preferable to add a solvent having a specific gravity higher than that of water. Examples of the solvent include benzene chloride and the like. That is, by using a solvent such as benzene chloride which is immiscible with water and has a specific gravity higher than that of water, the titanium oxide powder generated in the liquid during the formation of the titanium oxide film is present on the lower side. Move to the solvent side. For this reason, there is no powder acting as a nucleus in the solution maintaining equilibrium, which can prevent the function of promoting the production of titanium oxide in the solution, and also when the aggregate is newly immersed in the solution. Also,
The formation of the titanium oxide film becomes uniform and efficient.

In the second coating method, since a layer of a component having a photocatalytic function is deposited in a liquid layer, it can be applied regardless of the shape and size of the object to be coated. Applicable to Furthermore, it is very useful because a photocatalytic layer having excellent uniformity can be coated even on a porous aggregate.

When the above two coating methods are applied to an aggregate as a road pavement material as in the present invention, the coating method has a very high coating effect as described above, and is also an economically excellent coating method. is there. [Road pavement method] The road pavement method according to the present invention is characterized by paving the road surface using the above-described aggregate as the road pavement material according to the present invention.

The new pavement method which can be used in the present invention includes open-grain pavement, which has recently increased in pavement rate,
Although the method of construction is not particularly limited, such as conventional general fine-grained pavement, preferably, a neat method having a high anti-slip effect and a roll door asphalt having excellent slip resistance, crack resistance, water tightness, abrasion resistance, etc. It is a construction method. In the neat method, generally, an adhesive such as an epoxy resin is applied to the surface of asphalt or concrete pavement, and the particle size is 1 to 5 mm.
This is a method of bonding aggregates of about mm. According to this pavement method, since it has high slip resistance and can be colored, it is a place where the engine is blown, such as on a steep slope, a sharp curve, near an intersection, and so the exhaust gas concentration is relatively high, and purification is performed. This is where processing is required. In this method, since the aggregate is exposed on the road surface, the photocatalytic activity is always obtained in the present invention. Also, the construction is easy. The aggregate used in the NEET method is 1 as described above.
Since a particle having a particle size of about 5 mm is generally used, the photocatalyst-containing aggregate or the photocatalyst-coated aggregate of the present invention having the particle size can be used. Good.

The roll door asphalt method generally includes:
This is a method of laying asphalt mortar, sprinkling relatively single-grained coarse aggregate, and rolling to finish. Because of its excellent abrasion resistance, the pavement is environmentally friendly and is often used in mountainous areas. Further, since coloring is also possible, it is also used for bus lanes and the like. Even with this construction method,
Since the aggregate is exposed on the road surface, photocatalytic activity is always obtained in the present invention. Also, the construction is easy. Aggregate used in the rolled asphalt method is 5-19mm
Since a particle having a particle size of about the same size is generally used, the photocatalyst-containing aggregate or photocatalyst-coated aggregate of the present invention having the particle size can be used, and these may be used alone or in combination of two or more.

As an existing pavement method that can be used in the present invention, a sand filling method performed on open-grain asphalt pavement is preferable. The sand filling method is a type of water-retentive pavement that has recently been actively developed. This is a method of evaporating the water in the pavement on the surface of the pavement to lower the temperature by utilizing the capillary phenomenon of the pavement. That is, it aims at a "cool road". By using the aggregate of the present invention as the granular material to be filled by this method, the exhaust gas can be purified, and the exhaust gas concentration can be reduced.
Also, to fill the existing road with aggregates by vibration, etc.
The amount used is extremely small compared to other methods, and it is a very economical method considering the porousness of the open particle size. Since the aggregate used in the sand filling method generally has a particle size of about 0.075 to 1 mm, the photocatalyst-containing aggregate or the photocatalyst-coated aggregate of the present invention having the particle size can be used. They may be used alone or in combination of two or more.

[0121]

EXAMPLES Examples of the present invention and comparative examples will be described below, but the present invention is not limited by these examples. [Production Example 1: Production of aggregate (1)] IPA organosilica sol (trade name: OSCAL1432, manufactured by Catalyst Chemicals Co., Ltd.) was mixed with 100 parts by weight of methyltrimethoxysilane, and 100 parts by weight of isopropyl alcohol were mixed. , 60 parts of water were added and stirred. The molecular weight was adjusted to Mw = 950 in a thermostat at 60 ° C. Titanium oxide powder (manufactured by Nippon Aerosil Co., Ltd .:
20 parts of trade name P-25) were added to obtain a photocatalyst-containing coating agent.

Next, 20 parts by weight of crushed stone No. 5 (particle size: 5 to 19 mm) was added to 1000 parts by weight of the above coating agent, and the mixture was charged into a stirring tank and mixed and stirred in an open system. Mixing and stirring were continued until the coating agent was no longer volatile to obtain a photocatalyst-coated aggregate (1). [Production Example 2: Production of aggregate (2)] 62.5 ml of 0.4 mol / liter aqueous solution of ammonium titanium fluoride
And a 0.5 mol / liter aqueous solution of boric acid for 100 m
and mixed with water to make a 250 ml solution.

This solution was heated to 30 ° C.
0 parts by weight, single-grained crushed stone No. 5 (particle size 5 to 19 m
m) was added to a stirring tank, and the mixture was slowly mixed and stirred in a closed system for 48 hours to obtain a photocatalyst-coated aggregate (2). [Production Example 3: Production of aggregate (3)] Except for using a porcelain aggregate (particle size of 1 to 5 mm) instead of single-grained crushed stone No. 5 (particle size of 5 to 19 mm) as an aggregate, The same operation as in Production Example 1 was performed to obtain a photocatalyst-coated aggregate (3). [Production Example 4: Production of aggregate (4)] Except for using porcelain aggregate (particle size 1 to 5 mm) instead of single-grained crushed stone No. 5 (particle size 5 to 19 mm) as an aggregate, The same operation as in Production Example 2 was performed to obtain a photocatalyst-coated aggregate (4). [Production Example 5: Production of aggregate (5)] 90 parts by weight of the soil material shown in Table 1, 10 parts by weight of ST21 (manufactured by Ishihara Techno) as photocatalyst fine particles, and 5 parts by weight of an aqueous sodium hexametaphosphate solution as a dispersant Into a stirring tank, and stirred and mixed to form a suspension, a water content of 200% and a viscosity of 15%.
Adjusted to seconds (P funnel). This was granulated and dried by a spray dryer, and then baked at 1100 ° C. for 60 minutes to obtain a photocatalyst-containing aggregate (5). The particle size of the obtained aggregate (5) was 0.075 to 2.3 mm.

[0124]

[Table 1]

[Production Example 6: Production of aggregate (6)]
90 parts by weight of the soil material shown in FIG.
10 parts by weight of T21 (manufactured by Ishihara Techno) and 5 parts by weight of an aqueous solution of sodium hexametaphosphate as a dispersant were charged into a stirring tank, and mixed to prepare a lump of clay having a water content of 120%. This was dried at 110 ° C. for 5 hours to remove moisture, and formed into a slightly brittle lump. This brittle mass was pulverized with a mallet and then calcined at 1100 ° C. for 60 minutes to obtain a photocatalyst-containing aggregate (6). The particle size of the obtained aggregate (6) is 2.0 to
8.3 mm. [Comparative Production Examples 1 and 2: Preparation of Comparative Aggregates (1) and (2)]
As the comparative aggregate (1), single-crushed crushed stone No. 5 (particle size: 5 to 19 mm) used in Production Examples 1 and 2 was prepared. Also,
As the comparative aggregate (2), the porcelain aggregate (particle size: 1 to 5 mm) used in Production Examples 3 and 4 was prepared. [Comparative Production Example 3: Production of Comparative Aggregate (3)] 100 parts by weight of the soil material shown in Table 1 and 5 parts by weight of an aqueous sodium hexametaphosphate solution as a dispersant were put into a stirring tank.
A suspension was formed by stirring and mixing to prepare a water content of 200% and a viscosity of 15 seconds (P funnel). This was granulated and dried by a spray dryer, and then baked at 1100 ° C. for 60 minutes to obtain a comparative aggregate (3). The particle size of the obtained comparative aggregate (3) was 0.075 to 2.1 mm. [Comparative Production Example 4: Production of Comparative Aggregate (4)] 99.5 parts by weight of the soil material shown in Table 1 and S as photocatalyst fine particles
0.5 parts by weight of T21 (manufactured by Ishihara Techno Co.) and 5 parts by weight of an aqueous solution of sodium hexametaphosphate as a dispersant are put into a stirring tank, and the mixture is stirred and mixed to form a suspension. (P funnel). This is granulated and dried with a spray drier,
A baking treatment was performed at 0 ° C. for 60 minutes to obtain a comparative aggregate (4). The particle size of the obtained aggregate (4) was 0.075 to 2.1 mm. [Comparative Production Example 5: Production of Comparative Aggregate (5)] 100 parts by weight of the soil material shown in Table 1 and 5 parts by weight of an aqueous sodium hexametaphosphate solution as a dispersant were put into a stirring tank.
A suspension was formed by stirring and mixing to prepare a water content of 200% and a viscosity of 15 seconds (P funnel). This at 110 ° C for 1
The water was blown off in the oven for 20 minutes to give a slightly brittle mass. After crushing this brittle mass with a mallet,
It was baked for 0 minutes to obtain a comparative aggregate (5). The particle size of the obtained aggregate (5) was 1.9 to 9.1 mm. [Comparative Production Example 6: Production of Comparative Aggregate (6)] 10 parts by weight of the soil material shown in Table 1 above and ST2 as photocatalyst fine particles.
1 (manufactured by Ishihara Techno) and 5 parts by weight of an aqueous solution of sodium hexametaphosphate as a dispersant were put into a stirring tank, and the mixture was stirred and mixed to form a suspension. As a result, the water content exceeded 400%. The viscosity was 13 seconds (P funnel). When this was granulated using a spray drier, the granulation was not successful. [Example 1] The photocatalyst-coated aggregate (1) obtained in Production Example 1 was paved by a roll door asphalt method with a pavement thickness of 50 mm.

More specifically, the construction was carried out in accordance with the “Asphalt Pavement Guidelines”. Next, the NOx measuring device as shown in FIG. 1 was assembled, the exhaust gas concentration of a sample from which the core was removed from the pavement was measured, and the NOx reduction rate was calculated according to the following equation. NOx reduction rate (%) = 100− (concentration 10 minutes after Light ON / initial concentration) The used gas was NO, the initial concentration was 2 ppm, the gas flow rate was 350 ml / min, and the UV irradiation was 0.61 mW /
cm ² , and the sample size was 10 cmφ × 6 cm.

Table 2 shows the results.

[0128]

[Table 2]

[Example 2] The procedure of Example 1 was repeated, except that the photocatalyst-coated aggregate (2) obtained in Production Example 2 was used instead of the photocatalyst-coated aggregate (1). The results are shown in Table 2. [Example 3] Using the photocatalyst-coated aggregate (3) obtained in Production Example 3 and Tiestop (manufactured by Nisshinsei Co., Ltd.) as an epoxy resin, paving was performed by a neat method with a pavement thickness of 5 mm. .

More specifically, the test was carried out in accordance with the “Resin-based Non-Slip Pavement Guide”. The top coat was set to "none" in order not to hinder the photocatalytic activity. N as in the first embodiment
The Ox reduction rate was calculated. The results are shown in Table 2. Example 4 Instead of the photocatalyst-coated aggregate (3), the photocatalyst-coated aggregate (4) obtained in Production Example 4
Example 3 was carried out except that was used.

Table 2 shows the results. Example 5 Photocatalyst-containing aggregate obtained in Production Example 5 (5)
Was used to pave a drainable pavement road surface (open-grain asphalt pavement) at a filling depth of 50 mm by a sand filling method. Specifically, put out the photocatalyst containing aggregate on the construction surface, spread it evenly using a brush rake or rubber rake, etc., apply vibration to the construction surface using a vibration plate or vibration roller,
The photocatalyst-containing aggregate was filled. The aggregate remaining on the road surface was spread evenly again using a brush rake or the like, vibrated, and this was repeated until the aggregate was not filled. Excess aggregate remaining on the road surface was swept until it was 1-2 mm lower than the aggregate surface of the mother ascon. Incidentally, the topcoat using an airless sprayer, divided 0.2 kg / m ² twice, was uniformly sprayed. At this time, spots appear on the top coat,
If a pool is formed, the effect of water permeability and water retention is reduced.

The NOx reduction rate was calculated in the same manner as in Example 1. The results are shown in Table 2. Example 6 The same procedure as in Example 5 was carried out except that the photocatalyst-containing aggregate (6) obtained in Production Example 6 was used instead of the photocatalyst-containing aggregate (5). The results are shown in Table 2. Comparative Example 1 The same operation as in Example 1 was performed except that the comparative aggregate (1) obtained in Comparative Production Example 1 was used instead of the photocatalyst-coated aggregate (1).

Table 2 shows the results. [Comparative Example 2] The same operation as in Example 3 was carried out except that the comparative aggregate (2) obtained in Comparative Production Example 2 was used instead of the photocatalyst-coated aggregate (3). The results are shown in Table 2. [Comparative Examples 3 to 5] As in Example 5, except that the comparative aggregates (3) to (5) obtained in Comparative Production Examples 3 to 5 were used instead of the photocatalyst-containing aggregate (5). went.

Table 2 shows the results.

[0135]

According to the present invention, regardless of whether it is new or existing,
It can be applied to various types of road pavement and is easy to construct.
Further, it is possible to provide a road pavement material having a high exhaust gas purification processing ability and a photocatalytic function, and a road pavement method using the same.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a NOx measuring device used in the present invention.

[Explanation of symbols]

 1 2L synthetic quartz container 2 sample 3 UV lamp 4 NOx inlet 5 NOx meter

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Koichi Takahama 1048 Kadoma, Kazuma, Osaka Prefecture Matsushita Electric Works Co., Ltd. (72) Inventor Ken Satoru 1-1-5 Nishinomiyahama, Nishinomiya-shi, Hyogo Nisshin Chemical Co., Ltd. Technology Department 2

Claims (9)

[Claims] 1. A photocatalyst-containing aggregate obtained by granulating and firing a soil material, wherein at least 50% by weight of the soil material is silty soil and / or clay soil and a photocatalyst. A photocatalyst-containing aggregate, characterized in that: 2. The aggregate having a particle size of 0.075 to 19.00.
The photocatalyst-containing aggregate according to claim 1, which is 0 mm. 3. The photocatalyst-containing aggregate according to claim 1, wherein 1 to 80 parts by weight of the photocatalyst is contained in 100 parts by weight of the total of the silty soil and / or the clayey soil and the photocatalyst. 4. A photocatalyst-coated aggregate in which a photocatalyst is coated on the surface of a granular aggregate, wherein the coating is at least one selected from the following methods (i) to (v): Photocatalytic coating aggregate. (I) a first coating layer composed of a cured coating of an acrylic-modified silicone resin coating material containing the following components (A), (B), (C) and (D); and a first coating layer formed on the surface of the first coating layer. A coating method for forming a coating layer comprising a second coating layer comprising a cured coating of a functional coating material containing the following components (E) and (F). Component (A): represented by the general formula R ¹ _m SiX _4-m (1) (where R ¹ represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms) , M is an integer of 0 to 3, and X represents a hydrolyzable group.) In a colloidal silica dispersed in an organic solvent, water or a mixed solvent thereof, the hydrolyzable group ( X) A silica-dispersed oligomer solution of an organosilane, which is partially hydrolyzed under the condition of using 0.001 to 0.5 mol of water per 1 mol equivalent. Component (B): represented by the average composition formula R ² _a Si (OH) _b O _{(4-ab) / 2} (2) (where R ² is the same or different, substituted or unsubstituted C 1 -C 1) 8 represents a monovalent hydrocarbon group, wherein a and b are respectively 0.2 ≦ a ≦ 2, 0.0001 ≦ b ≦
3, a number that satisfies the relationship of a + b <4. ), Polyorganosiloxanes containing silanol groups in the molecule. Component (C): curing catalyst. Component (D): a monomer represented by the general formula CH ₂ ＣＲCR ³ (COOR ⁴ ) (where R ³ represents a hydrogen atom and / or a methyl group), wherein R ⁴ is substituted or A group consisting of an unsubstituted first (meth) acrylic acid ester which is a monovalent hydrocarbon group having 1 to 9 carbon atoms, wherein R ⁴ is an epoxy group, a glycidyl group or a hydrocarbon group containing at least one of these groups; A second (meth) acrylate which is at least one group selected from the group consisting of: and a third (meth) acryl wherein R ⁴ is a hydrocarbon group containing an alkoxysilyl group and / or a halogenated silyl group. Acrylic resin which is a copolymer of acid ester and Component (E): 20 to 200 parts by weight of a silicon compound and / or colloidal silica represented by the general formula Si (OR ⁵ ) ₄ and 100 parts by weight of a silicon compound represented by the general formula R ⁶ Si (OR ⁵ ) ₃ When the general formula _{^{R 6 2 Si (OR 5)}} 2
(Wherein R ⁵ and R ^{6 each} represent a monovalent hydrocarbon group) having a weight average molecular weight of 800 or more in terms of polystyrene. An organosiloxane that has been adjusted to be Component (F): photocatalyst. (Ii) a first coating layer comprising an applied cured film of an acrylic-modified silicone resin coating material containing the following components (A), (B), (C) and (D); and a first coating layer formed on the surface of the first coating layer. (A), (B), (C) and (F)
A coating method for forming a coating layer comprising a second coating layer comprising a coated and cured film of a functional coating material containing components. Component (A): represented by the general formula R ¹ _m SiX _4-m (1) (where R ¹ represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms) , M is an integer of 0 to 3, and X represents a hydrolyzable group.) In a colloidal silica dispersed in an organic solvent, water or a mixed solvent thereof, the hydrolyzable group ( X) A silica-dispersed oligomer solution of an organosilane, which is partially hydrolyzed under the condition of using 0.001 to 0.5 mol of water per 1 mol equivalent. Component (B): represented by the average composition formula R ² _a Si (OH) _b O _{(4-ab) / 2} (2) (where R ² is the same or different, substituted or unsubstituted C 1 -C 1) 8 represents a monovalent hydrocarbon group, wherein a and b are respectively 0.2 ≦ a ≦ 2, 0.0001 ≦ b ≦
3, a number that satisfies the relationship of a + b <4. ), Polyorganosiloxanes containing silanol groups in the molecule. Component (C): curing catalyst. Component (D): a monomer represented by the general formula CH ₂ ＣＲCR ³ (COOR ⁴ ) (where R ³ represents a hydrogen atom and / or a methyl group), wherein R ⁴ is substituted or A group consisting of an unsubstituted first (meth) acrylic acid ester which is a monovalent hydrocarbon group having 1 to 9 carbon atoms, wherein R ⁴ is an epoxy group, a glycidyl group or a hydrocarbon group containing at least one of these groups; A second (meth) acrylate which is at least one group selected from the group consisting of: and a third (meth) acryl wherein R ⁴ is a hydrocarbon group containing an alkoxysilyl group and / or a halogenated silyl group. Acrylic resin which is a copolymer of acid ester and Component (F): photocatalyst. (Iii) A coating method using a functional coating material containing the following components (E) and (F). Component (E): 20 to 200 parts by weight of a silicon compound and / or colloidal silica represented by the general formula Si (OR ⁵ ) ₄ and 100 parts by weight of a silicon compound represented by the general formula R ⁶ Si (OR ⁵ ) ₃ When the general formula _{^{R 6 2 Si (OR 5)}} 2
(Wherein R ⁵ and R ^{6 each} represent a monovalent hydrocarbon group) having a weight average molecular weight of 800 or more in terms of polystyrene. An organosiloxane that has been adjusted to be Component (F): photocatalyst. (Iv) An inorganic paint containing a silicone resin as a main component is coated with an antistatic inorganic paint containing a photocatalyst in an amount of 2 to 80 parts by weight based on 100 parts by weight of the total of the solid content in terms of the total condensation compound and the total photocatalytic component. Coating method used as material. (V) A solution containing an additive, ammonium titanium fluoride, and water, which promotes equilibrium of the following reaction formula (4) in an aqueous solution containing ammonium titanium fluoride, is brought into contact with the aggregate, and a photocatalyst is applied to the surface of the aggregate. A photocatalytically active titanium oxide film coating method for forming an active titanium oxide film, wherein the concentration of the additive is 0.05 to the total amount of the solution.
And 0.5 mol / l, and the concentration of titanium ammonium fluoride is 0.01 to 0.
2 mol / l, and a film thickness of 10 on the surface of the aggregate.
After forming a titanium oxide film of 0 nm to 2 μm,
A coating method characterized by firing at 0 to 700 ° C. (NH ₄ ) ₂ TiF ₆ + 2H ₂ O = TiO ₂ + 4HF + 2NH ₄ F (4) 5. The particle size of the aggregate is 0.075 to 26.5 m.
The photocatalyst-coated aggregate according to claim 4, wherein m is m. 6. A road paving method, comprising: paving a road surface using the aggregate according to any one of claims 1 to 5. 7. The road paving method according to claim 6, wherein said paving method is a neat method. 8. The road paving method according to claim 6, wherein said paving method is a roll door asphalt method. 9. The road paving method according to claim 6, wherein said paving method is a sand filling method.