JPH10193901A - Wheel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a wheel which is capable of maintaining its water repellency and is hardly stained for a long period. SOLUTION: A wheel comprises a base material and a surface layer including on the surface of the base material, photocatalyst particles, water repellent silicone, and materials for preventing the hydrophilic action of the water repellent silicone due to the luminous excitation of the photocatalyst. Otherwise, a layer including the photocatalyst particles and the water repellent silicone is formed on the surface of the base material. Further, materials for preventing the hydrophilic action of the water repellent silicone due to the luminous excitation of the photocatalyst are fixed to at least a part of the layer surface.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention
About

[0002]

2. Description of the Related Art Wheels of automobiles and motorcycles are contaminated by dirt and oil stains due to combustion products in exhaust gas of automobiles, abrasion powder of tires, dust and soot flying from the road surface and the ground. Moreover, cleaning the wheels is a heavy labor,
It takes time.

[0003]

Therefore, there is a demand for a wheel which is less likely to be soiled.

As a method for preventing the adhesion of dirt, it is known that it is better to impart water repellency to the surface of a substrate. When water repellency is imparted to the surface of the base material, the surface energy is significantly reduced, so that it becomes difficult for dirt components to adhere. As one of the methods, there is a method of forming a surface layer made of a water-repellent silicone on a substrate surface. However, with this structure, the contact angle with water is reduced to about 70 ° due to the adhesion of dirt over time, and the effect of water repellency is not maintained. Therefore, as another method for solving the above-mentioned problem, there is a method of forming a surface layer comprising a photocatalyst and a water-repellent silicone on the surface of a substrate. According to this method, it is possible to decompose the adhered dirt over time based on the oxidative decomposability of the photocatalyst. However, in this configuration, when exposed to sunlight outdoors, the silicone is hydrophilized by photoexcitation of the photocatalyst, so that the water repellency of the surface cannot be maintained. In view of the above circumstances, an object of the present invention is to provide a wheel that can maintain the water repellency of the surface for a long period of time, and to provide a wheel that is less likely to be soiled.

[0005]

According to the present invention, in order to solve the above-mentioned problems, photocatalytic particles, water-repellent silicone, and hydrophilicity of the water-repellent silicone by photoexcitation of the photocatalyst are provided on a substrate surface. Or a layer containing photocatalyst particles and a water-repellent silicone is formed on the surface of the base material, and is further formed on at least a part of the surface of the layer. The present invention provides a wheel characterized in that a substance for preventing the water-repellent silicone from becoming hydrophilic by photoexcitation of the photocatalyst is fixed. Preventing the silicon from becoming hydrophilic by photoexcitation of the photocatalyst by making the surface layer contain a substance such as cobalt or a cobalt compound for preventing the photocatalyst from becoming hydrophilic by photoexcitation. Can be. In addition, since the photocatalyst is contained, it is possible to decompose the dirt adhering with time based on the oxidative decomposability of the photocatalyst. Therefore,
The water repellency of the surface can be maintained, and the wheel can be maintained in a state that is hardly soiled permanently.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a plastic substrate such as polypropylene or urethane or a coated plate thereof, a hard coat plate; a metal substrate such as aluminum or a coated plate thereof, a hard coat plate, etc. The resulting wheel is coated with a surface layer. In one embodiment, as shown in FIG. 1, a surface layer containing a photocatalyst particle, a silicone, and a substance for preventing photocatalyst such as cobalt or a cobalt compound from becoming hydrophilic by photoexcitation is formed. . In another embodiment of the present invention, as shown in FIG. 2, a layer containing photocatalyst particles and a water-repellent silicone is formed, and at least a part of the surface of the layer is made of cobalt or a cobalt compound. A substance for preventing the hydrophilicity of the water-repellent silicone by photoexcitation of the photocatalyst is fixed. A corrosion-resistant intermediate layer may be provided between the substrate and the surface layer. As the material of the corrosion-resistant intermediate layer, silicone resin, amorphous silica,
Acrylic silicone resin or the like can be suitably used.

A photocatalyst has an energy greater than the energy gap between the conduction band and the valence band of the crystal.
A substance capable of generating conduction electrons and holes by excitation of electrons in the valence band (photoexcitation) when irradiated with light (excitation light) having a short wavelength (excitation light).
Oxides such as zeta-type titanium oxide, zinc oxide, tin oxide, ferric oxide, bismuth trioxide, tungsten trioxide and strontium titanate can be suitably used. As a light source used for photoexcitation of the photocatalyst, a light source attached to a vehicle such as sunlight, road lighting, a headlamp, or a dedicated light source can be used. Illumination such as a high-pressure sodium lamp, a low-pressure sodium lamp, a metal halide lamp, a fluorescent lamp, a mercury lamp, a fluorescent mercury lamp, or the like can be used as a light source or a dedicated light source attached to an automobile.

The silicone has an average composition formula R ^p SiO _{(4-p) / 2} (where R is a functional group comprising one or more monovalent organic groups, or a monovalent organic group) A resin represented by the following formula: X is an alkoxy group or a halogen atom, and p is a number satisfying 0 <p <2. Is available.

As the cobalt compound, cobalt alloy, cobalt oxide, cobalt chloride, cobalt sulfate, cobalt iodide, cobalt bromide, cobalt acetate, cobalt chlorate, cobalt nitrate and the like can be suitably used.

The thickness of the surface layer is preferably set to 0.4 μm or less. Then, cloudiness due to irregular reflection of light can be prevented, and the surface layer becomes substantially transparent. More preferably, the thickness of the surface layer is 0.2 μm or less. Then, it is possible to prevent the surface layer from being colored by light interference. Also, the thinner the surface layer, the better its transparency. Further, when the film thickness is reduced, the wear resistance of the surface layer is improved.

A metal such as Ag, Cu and Zn can be added to the surface layer. The surface layer to which the metal is added can kill bacteria and fungi attached to the surface even in a dark place.

Pt, Pd, Ru, Rh, I
A platinum group metal such as r or Os can be added.
The surface layer to which the metal is added can enhance the redox activity of the photocatalyst, and can improve the decomposability of organic contaminants and the decomposability of harmful gases and odors.

Next, a surface layer containing photocatalyst particles, water-repellent silicone, and a substance for preventing the water-repellent silicone from becoming hydrophilic by photoexcitation of the photocatalyst is formed on the surface of the substrate. The method of manufacturing the water-repellent member described above will be described. The production method in this case is basically based on applying a coating composition on the surface of a substrate and curing the coating composition.

Here, the coating composition contains a precursor of silicon as an essential component of a substance for preventing photocatalytic particles, cobalt or a cobalt compound or the like from becoming hydrophilic by photoexcitation of a photocatalyst. Solvents such as ethanol and propanol, catalysts that promote hydrolysis of silicone precursors such as hydrochloric acid, nitric acid, sulfuric acid, acetic acid and maleic acid, and basic compounds such as tributylamine and hexylamine Silicon compounds such as acidic compounds such as aluminum, aluminum triisopropoxide and tetraisopropyl titanate;
And a surfactant for improving the dispersibility of the coating liquid such as a silane coupling agent.

As cobalt or a cobalt compound, a water-soluble cobalt compound is preferably used. As the water-soluble cobalt compound, for example, cobalt chloride, cobalt sulfate, cobalt iodide, cobalt bromide, cobalt acetate, cobalt chlorate, cobalt nitrate and the like can be suitably used.

[0016] Here silicone - The precursor emissions in the average composition formula _{R p SiX q O (4-} pq) / 2 ( wherein, R consists of one or more organic groups monovalent functional X or a functional group comprising two or more selected from a monovalent organic group and a hydrogen group, X is an alkoxy group or a halogen atom, and p and q are 0 <p <2, 0 <
a film-forming element composed of a siloxane represented by the following formula: q <4) or a general formula R _p SiX _4-p (where R is one or more monovalent organic groups) Wherein X is an alkoxy group or a halogen atom, and p is 1 or 2. A film-forming element comprising a hydrolyzable silane derivative to be
Can be suitably used.

Here, as the coating film forming element comprising the hydrolyzable silane derivative, methyltrimethoxysilane,
Methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, Phenyltributoxysilane,
Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldibutoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenyl Methyldipropoxysilane, phenylmethyldibutoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltripropoxysilane, n-propyltributoxysilane, γ-glycoxydoxypropyltrimethoxysilane, γ -Acryloxypropyltrimethoxysilane and the like can be suitably used.

The film-forming element composed of the siloxane includes a partial hydrolysis and dehydration-condensation polymerization of the hydrolyzable silane derivative, or a partial hydrolyzate of the hydrolyzable silane derivative, tetramethoxysilane, tetraethoxysilane and tetraethoxysilane. It can be produced by dehydration polycondensation with a partial hydrolyzate such as silane, tetrapropoxysilane, tetrabutoxysilane, diethoxydimethoxysilane and the like.

The coating method of the coating composition includes spray coating, dip coating, flow coating, spin coating, roll coating, brush coating, and sponge. A method such as coating can be suitably used. As a curing method, it can be carried out by polymerizing by heat treatment, standing at room temperature, ultraviolet irradiation, or the like.

Next, a layer containing photocatalyst particles and a water-repellent silicone is formed on the surface of the base material, and at least a part of the surface of the layer is formed by photoexcitation of the photocatalyst by the water-repellent silicone. A method for manufacturing a water-repellent member to which a substance for preventing hydrophilicity is fixed will be described. The production method in this case is basically based on the photo-excitation of a photocatalyst such as cobalt or a cobalt compound after coating and curing a coating composition containing photocatalyst particles and a water-repellent silicone precursor. By applying a solution containing a substance for preventing hydrophilization and fixing the solution to the surface.

Here, the coating composition has photocatalyst particles and a precursor of a water-repellent silicone as essential components, and in addition, a solvent such as water, ethanol, propanol, hydrochloric acid, nitric acid, and the like. Catalysts that promote the hydrolysis of silica precursors such as sulfuric acid, acetic acid and maleic acid, basic compounds such as tributylamine and hexylamine, and acidic compounds such as aluminum triisopropoxide and tetraisopropyl titanate Such as a catalyst for curing a precursor of silica,
A surfactant such as a silane coupling agent for improving the dispersibility of the coating liquid may be added.

Here, as the precursor of the silicone, in the average composition formula R _p Si _{x q} O _{(4-pq) / 2} , R is a functional group comprising one or more monovalent organic groups. Or two selected from a monovalent organic group and a hydrogen group
X is an alkoxy group or a halogen atom, and p and q are 0 <p <2, 0 <
a film-forming element composed of a siloxane represented by the following formula: q <4) or a general formula R _p SiX _4-p (where R is one or more monovalent organic groups) Wherein X is an alkoxy group or a halogen atom, and p is 1 or 2. A film-forming element comprising a hydrolyzable silane derivative to be
Can be suitably used.

Here, as the coating film forming element comprising the hydrolyzable silane derivative, methyltrimethoxysilane,
Methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, Phenyltributoxysilane,
Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldibutoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenyl Methyldipropoxysilane, phenylmethyldibutoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltripropoxysilane, n-propyltributoxysilane, γ-glycoxydoxypropyltrimethoxysilane, γ -Acryloxypropyltrimethoxysilane and the like can be suitably used.

The film-forming element composed of the siloxane includes partial hydrolysis and dehydration condensation polymerization of the hydrolyzable silane derivative, or partial hydrolyzate of the hydrolyzable silane derivative, tetramethoxysilane, tetraethoxysilane, and the like. It can be produced by dehydration polycondensation with a partial hydrolyzate such as silane, tetrapropoxysilane, tetrabutoxysilane, diethoxydimethoxysilane and the like.

The coating method of the above coating composition includes spray coating, dip coating, flow coating, spin coating, roll coating, brush coating, and sponge. A method such as coating can be suitably used. As a curing method, it can be carried out by polymerizing by heat treatment, standing at room temperature, ultraviolet irradiation, or the like.

The method of applying a solution containing a substance for preventing the photocatalyst such as cobalt or a cobalt compound from being hydrophilized by photoexcitation and fixing it on the surface includes, for example, cobalt chloride, cobalt sulfate, cobalt iodide, bromide, and the like. cobalt,
Spray coating method, dip coating method, flow coating method, spin coating method, roll coating method, brushing water-soluble cobalt compounds such as cobalt acetate, cobalt chlorate and cobalt nitrate Coating, sponge coating, etc., photoreduction, heat treatment, alcohol
This is performed by fixing by a method such as reduction using a sacrificial oxidizing agent such as toluene.

[0027]

【Example】

Reference example. Anatase type titanium oxide sol (Nissan Chemical, TA
-15, nitric acid peptized type, pH = 1), silica sol (Nippon Synthetic Rubber, Glasca A solution, pH = 4), methyltrimethoxysilane (Nippon Synthetic Rubber, Glasca B solution) and ethanol are mixed. The coating liquid obtained by stirring for 2 to 3 hours was applied on a 5 × 10 cm square glazed tile base material (TOTOKIKI, AB02E11) by spray coating.
A heat treatment was performed at 200 ° C. for 15 minutes to obtain a # 1 sample having a surface layer formed of 11 parts by weight of anatase type titanium oxide particles, 6 parts by weight of silica, and 5 parts by weight of silicone. The contact angle of the # 1 sample with water was 92 °. Here, the contact angle with water was evaluated using a contact angle measuring device (Kyowa Interface Science, CA-X150) by the contact angle with water 30 seconds after a water droplet was dropped from the micro syringe. Next, the surface of the # 1 sample was irradiated for one day with an ultraviolet illuminance of 0.3 mW / cm ² using an ultraviolet light source (Sankyo Electric, Black Light Blue (BLB) fluorescent lamp) to obtain a # 2 sample. As a result, the contact angle with water of the # 2 sample was hydrophilized to 0 °. Next, # 1 sample and #
One sample was irradiated with a mercury lamp at an ultraviolet irradiance of 22.8 mW / cm ² for 2 hours, and the surface of each of the # 3 samples obtained was subjected to Raman spectroscopic analysis. As a result, a peak of methyl group observed on the surface of sample # 1 was not observed in sample # 3, but a peak of hydroxyl group was observed instead. From the above,
It can be seen that the organic group bonded to the silicon atom in the silicon molecule on the surface of the film by the photoexcitation of the anatase type titanium oxide which is a photocatalyst is replaced by a hydroxyl group and becomes hydrophilic.

Embodiment 1 FIG. Anatase type titanium oxide sol (Nissan Chemical, TA-15, peptized nitrate, pH = 1),
Silica sol (Nippon Synthetic Rubber, Glasca A solution, pH = 4)
And methyltrimethoxysilane (Nippon Synthetic Rubber, Glasca B solution), cobalt chloride hexahydrate, and ethanol, and stirred for 2-3 hours. -Applied on a silicon-coated aluminum substrate by a coating method and heat-treated at 150 ° C for 10 minutes to give 11 parts by weight of anatase type titanium oxide particles, 6 parts by weight of silica,
A # 4 sample having a surface layer composed of 5 parts by weight of silicon and 0.2 parts by weight of cobalt was obtained. The contact angle of the # 4 sample with water was 98 °. Here, the contact angle with water is measured using a contact angle measuring device (Kyowa Interface Science, CA-X15).
0), and after adding a water drop from the micro syringe, 3
Evaluation was made based on the contact angle with water after 0 seconds. Next, an ultraviolet light source (Sankyo Electric, Black Light Blue- (B
(LB) using a fluorescent lamp) and irradiating with an ultraviolet illuminance of 0.3 mW / cm ² for 1 day to obtain a # 5 sample. As a result, the contact angle of the # 5 sample with water was still 96 °, maintaining water repellency. Therefore, it can be understood from the above that the hydrophilicity of the silicon on the surface of the coating film due to the photoexcitation of the anatase type titanium oxide as a photocatalyst is inhibited by cobalt. this is,
It is considered that the replacement of the organic group bonded to the silicon atom in the silicon molecule on the surface of the coating film with the hydroxyl group is inhibited by cobalt.

Embodiment 2 FIG. Anatase type titanium oxide sol (Nissan Chemical, TA-15, peptized nitrate, pH = 1),
Silica sol (Nippon Synthetic Rubber, Glasca A solution, pH = 4)
, Methyl trimethoxysilane (Nippon Synthetic Rubber, Glasca B solution) and ethanol were mixed, and the coating solution obtained by stirring for 2 to 3 hours was subjected to silicone coating by spray coating. Applied on a coated aluminum substrate, 150
Heat treated at 10 ° C. for 10 minutes to form anatase type titanium oxide particles 1
A surface layer consisting of 1 part by weight, 6 parts by weight of silica and 5 parts by weight of silicone was formed. Further, an aqueous solution of cobalt chloride hexahydrate having a cobalt metal concentration of 50 μmol / g was added to the solution.
After applying 3 g, an ultraviolet illuminance of 0.4 mW was obtained using an ultraviolet light source (Sankyo Electric, Black Light Blue (BLB) fluorescent lamp).
The sample was irradiated with ultraviolet rays of 10 cm / cm ² for 10 minutes to fix cobalt on the substrate to obtain a # 6 sample. The contact angle of the # 6 sample with water is 9
It was 6 ゜. Here, the contact angle with water was evaluated using a contact angle measuring device (Kyowa Interface Science, CA-X150) by the contact angle with water 30 seconds after a water droplet was dropped from the micro syringe. Next, an ultraviolet light source (Sankyo Electric,
Black Light Bull (BLB) fluorescent lamp).
Irradiation was performed at 3 mW / cm ² ultraviolet irradiance for one day to obtain a # 7 sample. As a result, the contact angle of the # 7 sample with water was still 94 °, maintaining water repellency. Therefore, it can be understood from the above that the hydrophilicity of the silicon on the surface of the coating film due to the photoexcitation of the anatase type titanium oxide as a photocatalyst is inhibited by cobalt. This is considered because the substitution of the hydroxyl group for the organic group bonded to the silicon atom in the silicon molecule on the surface of the coating is inhibited by cobalt.

Embodiment 3 FIG. The # 5 sample, the # 7 sample, and a polytetrafluoroethylene plate for comparison were placed under the roofed part of the building as shown in FIG. 3 and left for 4 months. As a result, stains were observed on the polytetrafluoroethylene plate, whereas no stains were observed on the # 5 and # 7 samples.

[0031]

According to the present invention, in the wheel, the photocatalyst particles, the water-repellent silicone, and the substance for preventing the water-repellent silicone from becoming hydrophilic by the photoexcitation of the photocatalyst are provided on the surface of the base material. Or a layer containing photocatalyst particles and a water-repellent silicone is formed on the surface of the substrate, and at least a part of the surface of the layer has the repellent. By fixing a substance for preventing the hydrophilicity of the aqueous silicone by photoexcitation of the photocatalyst, the member surface can maintain the water repellency for a long period of time, and thus is hardly permanently stained.

[Brief description of the drawings]

FIG. 1 is a view showing a surface structure of a wheel according to the present invention.

FIG. 2 is a diagram showing another surface structure of the wheel according to the present invention.

FIG. 3 is a view showing a method of setting a test sample according to the embodiment of the present invention.

Claims (3)

[Claims] 1. A surface layer containing photocatalyst particles, water-repellent silicone, and a substance for preventing the water-repellent silicone from becoming hydrophilic by photoexcitation of the photocatalyst is formed on the surface of a substrate. A wheel. 2. A layer containing photocatalyst particles and a water-repellent silicone is formed on the surface of a base material, and at least a part of the surface of the layer is made hydrophilic by the photoexcitation of the photocatalyst of the water-repellent silicone. A wheel to which a substance for preventing the formation of a wheel is fixed. 3. The wheel according to claim 1, wherein the substance for preventing the photocatalyst from becoming hydrophilic by photoexcitation is cobalt or a cobalt compound.