JPH10203318A - Mirror for vehicle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a mirror for vehicle, which can keep water repellency for a long time. SOLUTION: In a mirror for vehicles, a face layer is formed, which includes photocatalyst particles, repellent silicon and material for preventing the repellent silicon from becoming hydrophilic because of the photo-excitation of the photocatalyst particles is formed in the surface of base material, or a layer is formed, which includes photocatalyst particles and repellent silicon in the surface of base material, and in addition, a material for preventing the repellent silicon from becoming hydrophilic because of the photo-excitation of the photocatalyst particles is fixed in at least a part of the surface of the layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vehicle mirror which can be used for a door mirror, a fender mirror and the like of an automobile.

[0002]

2. Description of the Related Art It is often experienced that a vehicle mirror suffers from rain and splashes in rainy weather, and a large number of discrete water droplets adhere to the surface and lose visibility. If the visibility is lost in this way, it becomes difficult to check the rear of the vehicle while driving, etc., which hinders the safe driving of the traveling vehicle.

[0003]

Therefore, there is a need for a vehicle mirror to which water droplets are unlikely to adhere.

[0004] As a method of preventing the adhesion of water droplets, it is known that it is better to impart water repellency to the surface of a substrate. 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 road mirror capable of maintaining the water repellency of the surface for a long period of time, and to provide a vehicle mirror to which water droplets are unlikely to adhere for a long period of time.

[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 substantially transparent surface layer containing photocatalyst particles and a water-repellent silicone is formed on the surface of the substrate. Further, there is provided a vehicle mirror characterized in that a substance for preventing the water-repellent silicone from becoming hydrophilic by photoexcitation of the photocatalyst is fixed to at least a part of the surface of the layer. 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, it is possible to provide a vehicle mirror in which the water repellency of the surface can be maintained permanently and water droplets hardly adhere to water droplets for a long period of time.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, a surface layer 3 is formed on the surface of a vehicle mirror. In one embodiment, as shown in FIG. 1, a photocatalyst particle, a silicone,
A surface layer containing a substance for preventing hydrophilicity due to photoexcitation of a photocatalyst such as cobalt or a cobalt compound is formed. In another embodiment, as shown in FIG. 2, a layer containing photocatalyst particles and a water-repellent silicone is formed,
Further, a substance for preventing hydrophilicity due to photoexcitation of a photocatalyst of a water-repellent silicone such as cobalt or a cobalt compound is fixed to at least a part of the surface of the layer. Here, a mirror made of a glass substrate provided with a reflective coat on the back surface, a mirror made of a plastic substrate provided with a reflective coat on the back surface, or a substrate surface made of plastic, glass, metal, etc. Mirrors, plastic,
A mirror provided with a reflective coat on a surface of a substrate such as glass or metal and further provided with a transparent hard coat, a mirror made of a mirror-polished metal substrate, and a hard coat formed on a mirror-polished metal substrate surface A well-known mirror substrate such as a mirror provided with a mirror can be used. A transparent intermediate layer made of silicon, amorphous silica, acrylic silicon, or the like may be provided between the substrate and the surface layer.

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 in an environment such as sunlight or road lighting may be used, or a dedicated light source may be used. Illumination such as a fluorescent lamp, an incandescent lamp, a metal halide lamp, a mercury lamp, a xenon lamp, and a germicidal lamp can be used as the dedicated light source. In order for the silicon or amorphous silica on the substrate surface to be hydrophilized by photoexcitation of the photocatalyst,
Illuminance of the excitation light may be at 0.001 mW / cm ² or more, but preferably that it 0.01 mW / cm ² or more, 0.1 m
More preferably, it is W / cm ² or more.

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.

[0022] 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 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 agitated for 2-3 hours. -Applied on a silica-coated 10 cm square soda lime glass substrate by a coating method and heat-treated at 150 ° C for 30 minutes to obtain 11 parts by weight of anatase type titanium oxide particles, 6 parts by weight of silica, A surface layer consisting of 5 parts by weight of cobalt and 0.2 parts by weight of cobalt was formed. Next, a reflective coating of aluminum was formed on the back surface of this plate by vacuum evaporation to obtain a # 4 sample. The contact angle of the # 4 sample with water was 96 °. 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. Then, the surface of the sample # 4 was coated with an ultraviolet light source (Sankyo Electric Co., Ltd., black light bull- (BLB) fluorescent lamp) by 0.3
Irradiation was performed for one day at an ultraviolet irradiance of mW / cm ² to obtain a # 5 sample. As a result, the contact angle of the # 5 sample with water was still 95 °, 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. Further, when the # 5 sample was tilted, the water droplets fell while rolling.

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)
, Methyltrimethoxysilane (Nippon Synthetic Rubber, Glasca B solution) and ethanol were mixed, and the coating solution obtained by stirring for 2 to 3 hours was coated with silica by a spray coating method. A surface layer comprising 11 parts by weight of anatase type titanium oxide particles, 6 parts by weight of silica and 5 parts by weight of silicone, applied on a 10 cm square soda lime glass substrate and heat-treated at 150 ° C. for 30 minutes. Was formed. Further, 0.3 g of an aqueous solution of cobalt chloride hexahydrate having a cobalt metal concentration of 50 μmol / g was applied thereon, and an ultraviolet illuminance of 0.4 mW / was applied using an ultraviolet light source (Sankyo Electric, Black Light Blue (BLB) fluorescent lamp). The cobalt was fixed on the substrate by irradiating the substrate with ultraviolet rays of cm ² for 10 minutes. Next, a reflective coating of aluminum is formed on the back surface of this plate by vacuum evaporation, and #
Six samples were obtained. The contact angle of the # 6 sample with water was 96 °. 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. Then, the surface of the sample # 6 was irradiated with 0.3 mW /
Irradiation was performed for 1 day at an ultraviolet illuminance of cm ² to obtain a # 7 sample. As a result, the contact angle of the # 7 sample with water was still 95 °, 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. When the # 9 sample was tilted, the water drops rolled and fell.

[0030]

According to the present invention, in a vehicle mirror, a photocatalyst particle, a water-repellent silicone and a water-repellent silicone for preventing the photocatalyst from becoming hydrophilic by photoexcitation of the photocatalyst are provided on the surface of the base material. A substantially transparent surface layer containing the substance is formed, or a substantially transparent layer containing the photocatalyst particles and the water-repellent silicone is formed on the surface of the base material; A material for preventing the hydrophilicity of the water repellent silicone by photoexcitation of the photocatalyst is fixed to at least a part of the surface of the layer, so that the surface of the member can maintain the water repellency for a long time. Thus, it is possible to provide a vehicle mirror capable of preventing water droplets from adhering for a long period of time.

[Brief description of the drawings]

FIG. 1 is a diagram showing a surface structure of a vehicle mirror according to the present invention.

FIG. 2 is a diagram showing another surface structure of the vehicle mirror of the present invention.

──────────────────────────────────────────────────の Continued on front page (51) Int.Cl. ⁶ Identification code FI C09D 183/04 C09D 183/04

Claims (3)

[Claims] 1. A substantially transparent material containing photocatalyst particles, a water-repellent silicone, and a substance for preventing the water-repellent silicone from becoming hydrophilic by photoexcitation of the photocatalyst on the surface of a substrate. A mirror for vehicles, wherein a surface layer is formed. 2. A substantially transparent 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 formed of the water-repellent silicone. A mirror for vehicles, wherein a substance for preventing the photocatalyst from becoming hydrophilic by light excitation is fixed. 3. The vehicle mirror according to claim 1, wherein the substance for preventing the photocatalyst from becoming hydrophilic by photoexcitation is cobalt or a cobalt compound.