Photocatalytic hydrophilic coating compsn.

Photocatalytic hydrophilic coating composition

BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a composition that can form a high hydrophilicity on the surface of the part to which it is applied and can maintain it for a long time. In more detail, it is about making the surface of mirrors, glass, lenses, and other parts highly hydrophilized, which can prevent the surface of the part from being hazy and the formation of water droplets on the surface of the part, or to purify the surface, or to promote it The surface water drops dry.

Background technique

In cold weather, the windshield and window glass of automobiles or other vehicles, the window glass of buildings, the lenses of glasses, and the glass covers of various instrument dials are foggy due to moisture condensation. This phenomenon It happens often. In addition, it is common for mirrors and glasses in bathrooms and washrooms to produce haze in the steam. Moisture occurs on the surface of the component because when the surface is at a temperature below the dew point of the ambient atmosphere, the moisture in the ambient atmosphere condenses and condenses on the surface, which grows into water droplets. Condensed water droplets are very small. If their diameter is 1/2 of the wavelength of visible light, the water droplets will scatter the light, making the glass and mirror opaque in appearance and losing visibility.

When the moisture continues to condense and the small condensed water droplets fuse together to form larger scattered water droplets, the surface becomes dirty and blurred due to the refraction of light at the interface between the water droplet and the surface and the interface between the water droplet and the air. , Form spots, or foggy. As a result, on transparent objects such as glass, the perspective image is skewed, reducing the perspective, and scattered reflection images are formed in the mirror.

In addition, the windshield and window glass of the vehicle, the window glass of the building, the rear view mirror of the vehicle, the lens of the glasses, the baffle of the mask and the mask, are subjected to rainfall and splashing, and a large number of discrete water droplets are attached to the surface. When the surface is dirty, fuzzy, spotted, or hazy, the visibility is lost.

Needless to say, the above-mentioned "fogging and unclear" has a serious impact on safety and the efficiency of various operations. For example, when the windshield and window glass of a vehicle, and the rearview mirror of a vehicle become dirty or foggy in cold or rainy weather, it is difficult to guarantee the vision and traffic safety is threatened. When the endoscope lens, dental mirror, and the cluster lens of the dental laser treatment device are hazy, it will cause obstacles to correct diagnosis, surgery, and treatment. When the glass cover of the measuring instrument panel is cloudy, it is difficult to accurately read the data.

On the other hand, in the field of construction and coatings, there are problems with environmental pollution, exterior decorative materials and outdoor structures and their coatings and pollution. Coal dust and particles floating in the atmosphere accumulate on the floor and outer walls of buildings on sunny days. Accumulation flows along with rainwater and flows down from the outer wall of the building. In addition, when it rains, the floating coal dust moves continuously with the rain and flows downward along the outer wall of the building and the surface of the outdoor structure. As a result, a lot of pollutants adhere to the surface along the rainwater channel marks. When the surface is dry, the surface shows streak-like contamination.

The pollution of decoration materials and coatings outside the building is formed by the burning products such as carbon black and the pollutants of inorganic substances such as urban dust and clay particles. It can be said that the diversity of such pollutants makes pollution countermeasures more complicated and difficult. (Original Kikko, "Test Methods for Promoting Pollution of Materials on External Walls", Paper Report Collection of the Department of Construction of the Architectural Society of Japan, No. 404, October 1989, p.15-24).

According to the general concept in the past, in order to prevent the pollution of the exterior decoration of the above-mentioned building, it is considered that it is best to use a waterproof coating such as polytetrafluoroethylene (PTFE). However, recently, for urban coal dust containing a large amount of hydrophobic components, it is enough to make the surface of the coating film hydrophilic (Polymer, Vol. 44, May 1995, p.307). Therefore, some people have proposed a proposal to coat buildings with hydrophilic graft polymers (News "Chemical Industry Daily", January 30, 1995). It is reported that this coating film exhibits a hydrophilicity that is converted into a contact angle with water of 30-40°.

However, inorganic dust represented by clay minerals has a contact angle of 20-50° with water, which is hydrophilic compared to graft polymers with a contact angle of 30-40° with water, and is easy to Attached to its surface. Therefore, we believe that the use of such graft polymer coatings cannot adequately prevent pollution caused by inorganic dust.

SUMMARY OF THE INVENTION The present inventors have obtained the knowledge that the use of a specific composition containing photocatalytic particles formed of metal oxides can easily form strong hydrophilicity on the surface of parts using this composition, and It can also maintain this hydrophilicity for a long time. Based on this knowledge, the present invention has been completed.

Therefore, the object of the present invention is to provide a composition capable of imparting anti-fogging properties to the surface of a part.

Another object of the present invention is to provide a composition capable of imparting anti-fogging properties to the surface of the member without impairing the transparency of the member.

Another object of the present invention is to provide a composition capable of promoting the drying of water droplets adhering to the surface of a part using this composition.

Another object of the present invention is to provide a composition that is difficult to contaminate the surface of the part on which the composition is used, and once the contaminant adheres to it, the contaminant can be easily detached.

According to the present invention, the composition for hydrophilizing the surface of the applied part contains at least: (a) photocatalytic particles formed of metal oxide; (b) silica fine particles, a silicone resin capable of forming a silicone resin film At least one selected from a precursor of a film and a precursor of a silica film capable of forming a silica film, and (c) a solvent. In the composition, the photocatalytic particles and the silica fine particles or the precursor The total concentration of solid content is 0.01 to 5% by weight.

Brief Description of the Drawings Fig. 1 is a schematic diagram of a form of a preferred spray container for packaging the composition according to the present invention.

Fig. 2 is a schematic diagram of a preferred cover of the spraying container shown in Fig. 1.

Figure 3 is a schematic view of another preferred spray container for packaging the composition according to the present invention.

Fig. 4 is a schematic diagram of a form of another preferred spray container for packaging the composition according to the present invention.

Figures 5 (a) and (b) are respectively schematic views of the cross-sectional shape of a spherical bottle for encapsulating the spray container constructed according to the composition of the present invention.

Fig. 6 is a schematic diagram showing changes in the anti-fogging properties of the hydrophilic surface prepared in Example A4 with respect to ultraviolet irradiation time.

Fig. 7 is a schematic diagram showing changes in the anti-fogging properties of the hydrophilic surface prepared in Example B1 with respect to ultraviolet irradiation time.

Detailed Description of the Invention Definitions The term "anti-fogging" used in this specification broadly refers to the prevention of surface haze, the growth of condensed water droplets on the surface, and the optical obstacles caused by the adhesion of water droplets on the surface.

Hydrophilic surface When the composition of the present invention is applied to the surface of a part according to the following method, the surface of the part can be made hydrophilic. Such a hydrophilized surface means that it exhibits a water wettability state with a contact angle with water of 10° or less, preferably 5° or less.

Furthermore, the composition according to the present invention has the advantage that the surface of the transparent member can maintain the original degree of transparency and be highly hydrophilized. The greatest advantage of the present invention is that it is possible to impart hydrophilicity to the following parts requiring original transparency, specifically, to impart anti-fogging properties without impairing the transparency and appearance. Furthermore, the addition of hydrophilicity is to apply the composition of the present invention to a surface, and when it is dried or heated, it can be carried out with an extremely simple operation, which is also the greatest advantage of the present invention. The thickness of the film can be changed according to the formulation of the composition applied to the surface of the part. Of course, it is expected that uneven application may occur. However, the composition of the present invention appropriately controls the amount of film thickness to form the following pattern, and selects the application to form a uniform film. The method can form an excellent hydrophilic surface extremely simply as described above.

In order to make the surface of the obtained part hydrophilic, light is irradiated to the surface. Although it can be considered that this hydrophilization phenomenon is carried out by the mechanism shown below, this is a hypothesis after all, and the present invention is not limited to this mechanism. When light having energy above the energy gap band at the upper end of the photocatalytic valence electron band and the lower end of the conduction band irradiates the photocatalyst, the electrons in the valence electron band of the photocatalyst can be excited to generate conduction electrons and holes. In this way, the effect of either or both of them imparts polarity to the surface (usually called electron attraction). As a result, the above amount of water in equilibrium with the ambient atmosphere is chemically adsorbed on the surface. In this way, the surface free energy based on the hydrogen bonds of the surface increases, and the water molecules according to the increase in the surface free energy are physically adsorbed and fixed on the surface. Generally speaking, since substances with close surface free energy are easy to adhere to each other, the surface of water molecules is physically adsorbed, forming a water-like condition. That is, such a surface is hydrophilized. It is found that the degree of hydrophilization of the surface obtained by using the composition of the present invention does not depend on the thickness of the film formed by the composition of the present invention. The inventors believe that the photocatalyst has the effect of oxidative decomposition, and the film with the photocatalyst can obtain the effects of antifouling, antibacterial, and deodorization according to its effect. This has long been known, but this oxidative decomposition effect depends on In the film thickness of the contained photocatalyst. The present inventors confirmed that the hydrophilicity obtained by the composition of the present invention can fully exhibit the hydrophilicity even if the oxidative decomposition effect is extremely weak or at a film thickness that is not exhibited at all. In addition, the inventors can also confirm that the oxidative decomposition effect is extremely limited in the thickness of the film formed from the composition of the present invention that does not affect the transparency of the transparent member. In this case, it is completely If the hydrophilicity cannot be exerted, once the hydrophilicity of the surface is hydrophilized, it can be maintained for several weeks even in a dark place.

In order to make the surface highly hydrophilized by the light excitation of the photocatalyst, the illuminance of the excitation light is preferably 0.001 mW/cm2 or more, more preferably 0.01 mW/cm2 or more, and particularly preferably 0.1 mW/cm2 or more.

When the photocatalytic oxide is anatase-type titanium oxide, rutile-type titanium oxide, zinc oxide, or strontium titanate, as a light source for light excitation of the photocatalyst, sunlight, indoor lighting, fluorescent lamps, mercury lamps, and incandescent lamps can be used , Xenon lamp, high pressure sodium lamp, metal halide lamp, BLB lamp, etc. When the photocatalytic oxide is tin oxide, germicidal lamps, BLB lamps, etc. can be used.

The film thickness of the surface layer of a part formed using the composition of the present invention is preferably 0.4 μm or less. When the film thickness is less than this, white turbidity caused by random reflection of light can be prevented, the surface layer is substantially transparent, and the thickness of the surface film layer is preferably less than 0.2 μm. This can effectively prevent light interference from causing the surface layer to develop color. The thinner the surface layer is, the more its transparency can be improved, and the abrasion resistance can also be improved.

According to a preferred embodiment of the present invention, the amount of photocatalyst in the surface layer formed in this way is preferably 1×10-7 to 1×10-3 g/cm2, more preferably 5×10-7 to 5×10-4 g/cm2 , 1×10-6 to 1×10-4g/cm2 is particularly preferred.

On the highly hydrophilized surface obtained by using the composition of the present invention, even if moisture and steam in the air form condensation, the condensed water does not form one drop of water, but forms a water film, which is very obvious. Therefore, it is also very obvious that no light scattering haze is generated on the surface. Similarly, window glass, vehicle rearview mirrors, vehicle windshields, spectacle lenses and masks will not form water droplets that disperse the field of view when it rains or is splashed, thus ensuring a high degree of field of vision and visibility. In order to improve the safety of vehicle traffic, the efficiency of work activities in all walks of life has been greatly improved.

Similarly, on the highly hydrophilized surface obtained with the composition of the present invention, it is difficult to adhere to municipal soot, carbon black and other combustion products contained in the exhaust gas of automobiles, and hydrophobic pollutants such as grease and seal eluted components. Even if it adheres to inorganic clay pollutants, it can be washed away by rainfall and washing.

Furthermore, the highly hydrophilized surface obtained by the composition of the present invention can spread the attached water droplets uniformly on the surface. As a result, the drying of the attached water droplets can be promoted.

Furthermore, the highly hydrophilized surface obtained by the composition of the present invention has antistatic effect (effect of preventing dust adhesion), heat insulation effect, bubble adhesion effect in waterproofing, effect of improving heat exchanger efficiency, and biological improvement. The effect of physical affinity.

When it is desired to use the composition of the present invention to obtain an anti-fogging effect, the parts using the composition should generally be transparent objects, and the material thereof is not particularly limited, such as glass, plastic, etc. As specific examples of applicable parts, there are mirrors such as vehicle rearview mirrors, bathroom mirrors, washroom mirrors, dental mirrors, road mirrors, spectacle lenses, optical lenses, lighting lenses, semiconductor lenses, Lenses for photocopiers and TV lenses for vehicle rearview; prisms; window glass for buildings and observation towers; baskets for cars, trains, airplanes, ships, submarines, snow supports, and rope cars; cranes in amusement parks Window glass of vehicles such as baskets, spaceships, etc.; cars, motorcycles, trains, airplanes, ships, submarines, snow supports, snowmobiles, ropeway baskets, amusement park baskets, spaceships, etc. Windshield of the first class of passenger equipment; protective goggles, sports goggles, baffles of protective masks, baffles of sports masks, baffles of face masks, glass of frozen food display windows, Chinese steamed buns and other insulated food displays Window glass; cover surfaces of measuring instruments, cover surfaces of vehicle rear-view TV mirrors, cluster lenses such as dental laser treatment devices, cover surfaces of laser detection detectors such as vehicle distance detectors, cover surfaces of infrared detectors, and cameras Use filters and films, sheets, seals, etc. attached to the surface of the above items.

When it is desired to use the composition of the present invention to obtain a surface purification effect, the material is not particularly limited. For example, there are metals, ceramics, glass, plastics, wood, stone, cement, concrete, fibers, fabrics, their combinations, and their laminates. Wait. As specific examples of applicable parts, there are building materials, exterior decoration of buildings, interior decoration of buildings, window frames, window glass, structural parts, exterior decoration and coating decoration of passenger vehicles, exterior decoration of mechanical devices and articles, and dust cover And coating decoration, traffic signs, various display devices, billboards, road soundproof walls, railway soundproof walls, bridges, barrier exterior decoration and coating decoration, tunnel interior decoration and coating decoration, insulators, solar cells Cover, solar water heater heat collection cover, vinyl hose, vehicle lighting lampshade, residential equipment, toilets, bathtubs, washstands, lighting appliances, lighting covers, kitchen supplies, food appliances, food appliances washer, food appliance dryers, laundry tubs , Conditioning areas, kitchen fume hoods, ventilation fans, and films, sheets, seals, etc. attached to the surface of the above items.

When it is desired to use the composition of the present invention to obtain the effect of promoting the drying of water droplets, the material is not particularly limited. For example, there are metals, ceramics, glass, plastics, wood, stone, cement, concrete, fibers, fabrics, their combinations, and their laminates. body. As specific examples of applicable parts, there are films, sheets, seals, etc. attached to the surfaces of automobile bodies, windows, roads, and the above-mentioned articles.

When it is desired to use the composition of the present invention to obtain the antistatic effect, the material is not particularly limited. For example, there are metals, ceramics, glass, plastics, wood, stone, cement, concrete, fibers, fabrics, their compositions, and their laminates. . As specific examples of applicable parts, there are cathode ray tubes, magnetic recording devices, optical recording devices, magneto-optical recording devices, audio tapes, video tapes, analog recorders, housing parts and exterior decorations and coating decorations of household electrical appliances. , Outer shell parts and exterior decoration and coating decoration of OA machine products, building materials, exterior decoration of buildings, interior decoration of buildings, window frames, window glass, structural parts, exterior decoration and coating decoration of vehicles, mechanical devices and articles The exterior decoration, dust cover and coating decoration, as well as the film, sheet, seal, etc. attached to the surface of the above-mentioned articles.

Surface hydrophilization composition The composition of the present invention basically includes: (a) photocatalytic particles formed of metal oxide; (b) a silicone resin film precursor that can form a silicone resin film from silica fine particles, And at least one selected from silica film precursors that can form a silica film; (c) a solvent.

In addition, the composition of the present invention may contain other ingredients according to the situation.

Photocatalyst particles The photocatalyst particles contained in the composition of the present invention are basically formed of a metal oxide. Specifically, the so-called photocatalyst in the present invention refers to the light (excitation light) in the valence electron band when it is irradiated with light (excitation light) of greater energy (ie, short wavelength) than the energy gap between the crystalline conduction band and the valence electron band. The electrons are excited to generate substances that conduct electrons and holes. Examples of the photocatalytic oxide include anatase-type titanium oxide, rutile-type titanium oxide, zinc oxide, tin oxide, iron oxide, bismuth trioxide, tungsten trioxide, and strontium titanate oxides.

The average crystallite diameter of these photocatalyst particles is preferably 100 nm or less. The upper limit thereof is preferably 20 nm or less, and more preferably 10 nm or less. The lower limit is preferably 1 nm or more, more preferably 3 nm or more. The average crystallite diameter of the photocatalyst particles can fully exhibit the hydrophilic effect in the above-mentioned range, and the surface using the composition can prevent the particles from scattering visible light and losing transparency.

In addition, the average crystallite diameter of the photocatalyst particles can be obtained from the integrated width of the strongest peak in the vicinity of 2θ=25.3° of the particle powder X-ray diffraction according to the Scherrer method.

Silica fine particles, silicone resin film precursor, and silica film precursor.

The composition according to the present invention may contain silica microparticles. It is believed that the silica fine particles can effectively fix the photocatalyst particles on the surface of the part. According to a preferred embodiment of the present invention, the average particle size of the silica microparticles is preferably 1-100 nm, more preferably 5-50 nm, and most preferably 8-20 nm. The average particle diameter of the silica fine particles can be obtained by, for example, a dynamic laser scattering method.

As a preferable example of a silica film precursor capable of forming a silica film that can be used in the composition of the present invention, there is a silicate represented by the average composition formula SiXqO(4-q)/2.

(In the formula, X is an alkoxy group or a halogen atom, and q is a number satisfying 0<q<4).

As an example of another preferable film precursor capable of forming a silica film, there is a tetrafunctional water-decomposable silane derivative represented by the general formula SiX4 (where X is an alkoxy group or a halogen atom).

As preferred examples of the above-mentioned tetrafunctional water-decomposable silane derivatives, there are tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, diethoxydimethoxysilane, tetramethoxysilane, Chlorosilane, tetrabromosilane, silanol, dimethoxydiethoxysilane, etc.

As preferred examples of the above-mentioned silicate, there are partial water-decomposition products and dehydration polycondensation products of the above-mentioned tetrafunctional water-decomposable silane derivatives.

As a preferred example of a silicone film precursor that can form a silicone film that can be used in the composition of the present invention, there is a siloxane represented by the average composition formula RpSiXqO(4-pq)/2, (where R is from hydrogen A group selected from one or two or more groups of atoms and organic groups, X is an alkoxy group or a halogen atom, and p and q are numbers satisfying 0<p<2, 0<q<4, respectively).

As a preferred example of a silicone film precursor that can form a silicone film that can be used in the composition of the present invention, there is a hydrolyzable silane derivative represented by the general formula RpSiX4-p, (where R is the same as defined above, X Is an alkoxy group or a halogen atom, and p is 1 or 2).

The organic group represented by R means an alkyl group (more preferably a non-substituted alkyl group of 1 to 18 carbon atoms, and an alkyl group of 3 to 18 carbon atoms is particularly preferred) or an aryl group (preferably a phenyl group).

As preferred examples of the above-mentioned hydrolyzable silane derivatives, there are methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, and ethyltrimethoxysilane. , Ethyltriethoxysilane, Ethyltripropoxysilane, Ethyltributoxysilane, Phenyltrimethoxysilane, Phenyltriethoxysilane, Phenyltripropoxysilane, Phenyl Tributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane , Diethyldiethoxysilane, diethyldipropoxysilane, diethyldibutoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenyl Methyldipropoxysilane, phenylmethyldibutoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltripropoxysilane, n-propyl Tributoxysilane, γ-glycoside propyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, etc.

As the above-mentioned siloxane, it is possible to use partial hydrolysis and dehydration polycondensation of the above-mentioned water-decomposable silane derivative, or a partial water-decomposition product of the above-mentioned water-decomposable silane derivative, Tetrapropoxysilane, tetrabutoxysilane, diethoxydimethoxysilane and other products prepared by dehydration polycondensation of partially hydrolyzed products.

The silicone resin prepared by partial hydrolysis or dehydration polycondensation of the precursor by the following method is represented by the following average composition formula: RpSiO(4-p)/2 (where R is the same as defined above, X is an alkoxy group or a halogen atom, and p is a number satisfying 0<p<2).

The amount of the precursor contained in the composition of the present invention can be appropriately determined, but, for example, 1 part by weight of photocatalyst particles, converted to the weight of silica, is preferably 10 parts by weight or less, more preferably 5 parts by weight. Parts or less, 1 part by weight or less is particularly preferred, and more preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, and particularly preferably 0.2 parts by weight or more.

Solvent The solvent contained in the composition of the present invention, as long as it can stably disperse the photocatalyst particles and the precursor, and finally obtain a hydrophilic surface. There is no particular limitation on this. Examples thereof include water or organic Solvents, or their mixed solvents. Water, alcohol, or a mixed solvent of these are particularly preferred.

The amount of solvent in the composition of the present invention is the total weight (hereinafter also referred to as the "solid content concentration") that can convert the aforementioned photocatalyst particles and precursor into the weight of silica. The concentration in the composition is 0.01 When the amount is between ~5% by weight, the solid content concentration here can be simply expressed by heating the composition at 400-500°C for 3 hours, and dividing the weight of the remaining solid content by the weight of the composition after the liquid component has evaporated Multiply the weight by one hundred. When the solid content concentration exceeds 5% by weight, the surface on which the composition is used has a cloudy appearance, or interference stripes appear, which is very undesirable. A more preferable upper limit is 1% by weight. When the solid content concentration is less than 0.01% by weight, a sufficient hydrophilic surface cannot be effectively formed. A more preferable lower limit is 0.05% by weight, and 0.1% by weight is particularly preferred. In the composition of the present invention, the photocatalyst particles are solid For the component concentration, the amount of solvent can be determined in the above range.

According to a preferred embodiment of the present invention, it is preferable to use alcohols with a molecular weight of 60 to 300, preferably a molecular weight of 60 to 100, and which are liquid at room temperature.

As the best examples of alcohols, there are methanol, ethanol, n-propanol, isopropanol, t-butanol, isobutanol, n-butanol 2-methylpropanol, pentanol, ethylene glycol, mono Acetone alcohol, diacetone alcohol, ethylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone, dipropylene glycol, propylene glycol, tripropylene glycol, 1-ethoxy-2-propanol, 1- Butoxy-2-propanol, 1-propoxy-2-propanol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, 2-butane Oxyethanol and so on.

The addition of water as a solvent is preferable from the viewpoint of promoting the hydrolysis of the silica precursor. For example, when tetraethoxysilane, tetramethoxysilane, tetrabutoxysilane, tetrapropoxysilane, tetrachlorosilane, and tetrabromosilane are used as the silica precursor, the composition of the present invention described below In the application method, the presence of water promotes hydrolysis.

Other Components The composition of the present invention may contain other optional components in addition to the above-mentioned components.

According to a preferred embodiment of the present invention, the composition of the present invention may contain substances with a refractive index of 2 or less. By adding a substance with a refractive index below 2, the benefit obtained is that it can effectively prevent the reflection of visible light on the applicable surface.

As substances with a refractive index of 2 or less that can be added to the composition of the present invention, there are silica (refractive index of 1.5), tin oxide (refractive index of 1.9), calcium carbonate (refractive index of 1.6), calcium hydroxide (refractive index of 1.6) ), magnesium carbonate (refractive index 1.5), strontium carbonate (refractive index 1.5), dolomite (refractive index 1.7), calcium fluoride (refractive index 1.4), magnesium fluoride (refractive index 1.4), alumina (refractive index 1.6) ), silica sand (refractive index 1.6), zeolite (refractive index 1.5), montmorillonite (refractive index 1.5), kaolin (refractive index 1.6), mica (refractive index 1.6), iron oxide (refractive index 1.8), yttrium oxide ( Refractive index 1.9) and so on.

According to another preferred aspect of the present invention, the composition of the present invention may also contain a surfactant. By adding a surfactant, even after the composition of the present invention is used immediately, the surface to be used can be strongly hydrophilic. And anti-fogging. Especially when the composition of the present invention contains alcohol, its addition is preferable. When the surface using the composition of the present invention becomes hydrophilic due to light irradiation, it may take several hours depending on the situation. At this time, when the alcohol derived from the composition of the present invention remains on the surface, the hydrophilicity of the surface is unsatisfactory until the hydrophilicity is generated by the photocatalyst. However, by adding a surfactant, the surface of the composition immediately exhibits strong hydrophilicity even after the composition is used, and the anti-fogging property can be imparted, which is the most preferable. Furthermore, by adding a surfactant, there is an advantage that the composition of the present invention can be uniformly applied to the surface of a part.

In a preferred embodiment of the present invention, the preferred addition amount of the surfactant is less than 10 parts by weight, more preferably 0.1 to 2 parts by weight, based on 1 part by weight of the photocatalyst particles.

Examples of surfactants that can be added to the composition of the present invention include sulfonic acid polyoxyethylene alkyl phenyl ether ammonium salt, sulfonic acid polyoxyethylene alkyl phenyl ether sodium salt, fatty acid sodium soap, fatty acid potassium soap, two Sodium octyl sulfosuccinate, alkyl sulfate, alkyl ether sulfate, alkyl sodium sulfate, alkyl ether sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl ether sulfate , Alkyl sulfate TEA salt, polyoxyethylene alkyl ether sulfate TEA salt, 2-ethylhexyl alkyl sulfate sodium salt, sodium acyl methyl taurate, sodium lauroyl methyl taurate, twelve Sodium alkyl phenyl sulfonate, sodium lauryl sulfosuccinate 2 sodium, polyoxyethylene sulfosuccinate lauryl 2 sodium, polycarboxylic acid, oleoyl sarcosine, amide ether sulfate, lauroyl sarcosinate , Sulfo FA ester sodium salt and other anionic surfactants; polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene Polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkylphenol ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene laurate, polyoxyethylene hard Fatty acid ester, polyoxyethylene alkyl phenyl ether, polyoxyethylene oleate, sorbitol alkyl ester, polyoxyethylene sorbitol alkyl ester, polyether modified silicone, polyester modified silicone, sorbitan Sugar alcohol laurate, sorbitol stearate, sorbitol palmitate, sorbitol oleate, sorbitol sesquioleate, polyoxyethylene sorbitol laurate, polyoxyethylene Sorbitol stearate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan oleate, glycerol stearate, polyglyceryl fatty acid ester, alkyl alcohol amide, lauric acid diethanolamide , Oleic acid diethanolamide, ethylene oxide dodecyl ammonia, polyoxyethylene dodecyl ammonia, polyoxyethylene alkyl ammonia, polyoxyethylene stearyl ammonia, polyoxyethylene alkyl propylene diamine , Polyoxyethylene propylene oxide block polymer, polyoxyethylene stearate and other nonionic surfactants; dimethyl alkyl betaine, alkyl glycine, amide betaine, imidazoline and other amphoteric surfactants, Octadecyl dimethyl benzyl ammonium chloride, alkyl dimethyl benzyl ammonium chloride, tetradecyl dimethyl benzyl ammonium chloride, dioleyl dimethyl ammonium chloride, 1-hydroxy Ethyl-2-alkylimidazoline quaternary salt, alkyl isoquinoline bromide, polymer amine, octadecyl trimethyl ammonium chloride, alkyl trimethyl ammonium chloride, dodecyl tri Methyl ammonium chloride, cetyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, alkyl imidazoline quaternary salt, dialkyl dimethyl ammonium chloride, octadecane Base amine acetate, fourteenAnionic surfactants such as alkyl amine acetate, alkyl propylene diamine acetate, didecyl dimethyl ammonium chloride, etc.

According to a preferred embodiment of the present invention, the composition of the present invention may contain an acid. By adding acid, the surface polarity to which the composition of the present invention is applied can be increased, and good hydrophilicity can be maintained even in dark places.

As the acid that can be added to the composition of the present invention, nitric acid, sulfuric acid, hydrochloric acid, acetic acid, propionic acid, maleic acid, adipic acid, fumaric acid, phthalic acid, and valeric acid can be added to the surface polarity. , Lactic acid, butyric acid, citric acid, malic acid, picric acid, formic acid, carbonic acid, phenol, etc. Nitric acid, hydrochloric acid and sulfuric acid are particularly good.

According to another preferred aspect of the present invention, the composition of the present invention may contain a silane hydrolysis catalyst. Due to the presence of the catalyst, the method of using the composition of the present invention described later can promote the silane compound as the precursor Of hydrolysis. As examples of preferred catalysts, there are nitric acid, sulfuric acid, hydrochloric acid, acetic acid, propionic acid, maleic acid, adipic acid, fumaric acid, phthalic acid, valeric acid, lactic acid, butyric acid, citric acid, and apples of pH 2-5. Acid, picric acid, formic acid, carbonic acid, phenol, etc.

According to another preferred embodiment of the present invention, when the silica precursor is silanol, the composition of the present invention may contain a polymerization curing catalyst for silanol. Due to the presence of this catalyst, in the method of using the composition of the present invention described later, the polymerization reaction of silanol can be promoted. As preferred examples of catalysts, there are aluminum chelate, aluminum acetylacetonate, aluminum perchlorate, aluminum chloride, aluminum isobutoxide, aluminum isopropoxide and other aluminum compounds; tetraisopropyl titanate, Titanium compounds such as tetrabutyl titanate; lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methylation products, sodium acetate, sodium formate, potassium acetate, potassium formate, potassium propionate, four Basic compounds such as methyl ammonium chloride and tetramethyl ammonium hydroxide; n-hexylamine, tributylamine, diazabicycloundecene, ethylene diamine, hexamethylene diamine, diethylene triamine , Tetraethylenepentamine, triethylenetetramine, ethanolamines, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)- Amine compounds such as aminopropyltrimethoxysilane, γ-(2-aminoethyl)-aminopropylmethyldimethoxysilane; tin compounds such as tin acetylacetonate, tin dibutyl octoate, cobalt octoate, Metal-containing compounds such as cobalt acetylacetonate and iron acetylacetonate; acidic compounds such as phosphoric acid, nitric acid, phthalic acid, p-toluenesulfonic acid, and trichloroacetic acid.

According to a preferred aspect of the present invention, the composition of the present invention may contain a leveling agent so that it can form a smooth surface when used on the surface of a part. The addition of the leveling agent is very beneficial to the application of the composition of the present invention to large parts. As examples of preferred leveling agents, there are diacetone alcohol, ethylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone, dipropylene glycol, tripropylene glycol, 1-ethyl-2-propanol , 1-butoxy-2-propanol, propylene glycol monomethyl ether, 1-propoxy-2-propanol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monoethyl ether, etc. .

According to a preferred embodiment of the present invention, the composition of the present invention may also contain antibacterial metals (for example, Ag, Cu, Zn) or their compounds. By adding these metals, when using the composition of the present invention, bacteria present on the surface can be killed, and after further use, the growth of microorganisms such as mold, algae, and moss on the surface can be inhibited.

According to another preferred embodiment of the present invention, the composition of the present invention may contain at least one platinum group metal selected from Pt, Pd, Rh, Ru, Os, and Ir. It has the surface of the photocatalyst formed by the metal oxide. Due to the oxidative decomposition of the photocatalyst, it has the functions of anti-fouling, antibacterial and anti-odor. This has been known for a long time. We believe that the surface of the part using the composition of the present invention Above, this effect can be maintained. It is also believed that the above-mentioned metals can enhance the oxidative decomposition of the photocatalyst, and can improve the antibacterial properties, deodorization properties, gas decomposition properties, and organic decomposition properties of the surface.

When the composition of the present invention is stored in a tin container or a metal-lined container, or when applied to a metal part, it is preferably weakly acidic, neutral or alkaline. Especially when adding the above-mentioned acid, it is preferable to add a pH adjuster.

The composition of the present invention may appropriately contain an acid or a base in order to improve the dispersibility of the contained solid content and improve the storage properties. Furthermore, depending on the situation, pigments, dyes, storage stabilizers, etc. may be contained.

Application of the composition of the present invention to the surface of a part In order to make the surface hydrophilic or anti-fogging, the composition of the present invention is applied to the surface of the part, followed by drying or curing to form a film.

As in the above-mentioned composition of the present invention, a film having a thickness of 0.4 μm or less, preferably a film having a thickness of 0.2 μm or less, is formed on the final part. In order to form such a thin film, it is preferable to use the composition of the present invention in the range of about 1×10-4 to 20 mg/cm2 on the surface of the part, and more preferably in the range of 5×10-4 to 1 mg/cm2.

Although the method of applying the composition of the present invention to the surface of a part can be appropriately selected, it is preferable to use spray coating, dip coating, flow coating, spin coating, roller coating, brush coating, and sponge coating.

The composition after application to the surface is dried or cured to form a film. The so-called drying or curing in the present invention means that the silica precursor or silicone precursor contained in the composition of the present invention forms silica or silicone. Therefore, drying can be carried out by either natural drying or heating. Furthermore, when the precursor is formed into silica or silicone, it is also possible to cause a polymerization reaction by irradiation with ultraviolet rays or the like.

Furthermore, a preferred aspect of the present invention is to encapsulate the composition of the present invention in a spray container, and the user can freely apply the composition of the present invention to the surface of any part.

A spray container suitable for encapsulating the composition of the present invention is shown in FIG. 1. The container shell 1 is preferably made of aluminum, which is light in quantity, easy to process, and durable. Duralumin, copper-aluminum alloy, titanium alloy, stainless steel, etc. can also be used.

When the composition of the present invention is acidic, in order to avoid direct contact between the metal container shell and the acidic composition, it is preferable to coat the acid-resistant resin liner 2. As an acid-resistant resin liner, ABS resin, polycarbonate, methylpentene resin, polyvinyl chloride, polypropylene, polyethylene, tetrafluoroethylene resin, fluoroethylene propylene and trifluorochloroethylene resin, vinylidene fluoride can be used Vinyl resin, perfluoroalkoxy resin, phenol resin, epoxy resin, acrylic resin, chlorinated polyether, polysulfone, polystyrene, polyphenylene ether, polyphenylene sulfide, polyimide, nylon, ion Polymer and so on. As shown in Fig. 2, a removable cover can be installed on the upper part of the container of Fig. 1. The structure of this cover includes: a pipe 3 for introducing the composition of the present invention into the spraying part, a nozzle 4, and the uppermost part of the housing 12 for finger pressing The pressure rod 5, the coil spring 6, the rubber pad 9, the fixed cover 10, the gasket 11 provided on the connecting part of the fixed cover 10 and the upper part of the container shell 1, and the outer shell 12. The pressure rod 5 has a hole for introducing the composition of the present invention into the injection part, a communication port 7 communicating with the nozzle 4 at the upper part, and a communication port 8 communicating with a certain position of the rubber pad.

In this way, before pressing the plunger 5, the communication port 7 does not communicate with the nozzle 4, and the communication port 8 is sealed by the rubber gasket 9, so that the composition will not be ejected. When the pressing rod 5 is pressed, the communication port 8 is located in the space between the pressing rod 5 and the housing 12, and the composition introduced from the tube 3 into the space between the pressing rod 5 and the housing 12 is further introduced into the inner cavity of the pressing rod 5 in. At the same time, the communication port 7 communicates with the nozzle 4, and the composition introduced into the internal cavity of the plunger 5 is ejected from the nozzle 4.

The inside of the pipe 3, the plunger 5, the nozzle 4, and the housing 12 that are in direct contact with the composition preferably uses the above-mentioned acid-resistant resin.

The rubber pad 9 is preferably also made of acid-resistant rubber, such as ethylene rubber, propylene rubber, and silicone rubber.

The nozzle 4 is preferably formed with a slightly inclined ejection port upward.

The cavity part of the pressure rod 5 connected with the nozzle should be easy to introduce the composition into the nozzle, and it can also be in the shape of a cross groove or spiral groove.

As for other forms of the aerosol container, the double-structured container shown in Figs. 3 and 4 can also be used.

In the structure shown in FIG. 3, an inner container 13 is installed inside the container of FIG. 1, and the coating liquid sample D11 and spray gas such as nitrogen, DME, LPG, etc. are filled in the inner container 13. Through this type of structure, Even if there are pinholes in the resin liner, the composition of the present invention will not directly contact the metal container shell 1, which is more desirable.

In the structure shown in FIG. 4, a pressure-resistant and pressure-transmitting pneumatic inner container 14 is provided in the container of FIG. 1, and a hole is provided in the lower part of the container. With this structure, the composition of the present invention is put into the inner gas pressure vessel 14 (part A in the figure), and nitrogen gas is put between the outer container and the gas pressure vessel (part B in the figure) to separate the gas and liquid. Therefore, it is possible to prevent such undesirable phenomena as gas slowly dissolving into the liquid and reducing the pressure in the container.

Nitrogen is filled in the lower hole of the container, and then sealed with a rubber plug 15. In this way, even if there is residual pressure after use, the rubber plug 15 can be easily pulled out, which is very safe.

For the air pressure vessel 14, it is better to use polyethylene, polyvinyl chloride, etc. that have pressure resistance and have very good pressure transmission properties. In order to improve the pressure transmission properties, it is best to make the unevenness as shown in Figure 5(a) or (b). Multi-patterned cross-sectional shape.

In addition to nitrogen, ether gases such as dimethylene ether or inert gases such as argon and helium can also be used as the gas to be charged.

Examples The following examples illustrate the present invention in more detail, but the present invention is not limited to these examples.

The composition and acquisition of the titanium oxide sol used in the following examples are as follows.

Titanium oxide sol ST-K01: is a composition formed by 8 parts by weight of anatase-type titanium oxide particles, 2 parts by weight of alkyl silicate, 54.8 parts by weight of aqueous nitric acid, 28 parts by weight of methanol and 7.2 parts by weight of propanol, Available from Ishihara Sangyo Co., Ltd.

Titanium oxide sol ST-K03: is a composition formed by 5 parts by weight of anatase-type titanium oxide particles, 5 parts by weight of alkyl silicate, 54.8 parts by weight of aqueous nitric acid, 28 parts by weight of methanol and 7.2 parts by weight of propanol, Available from Ishihara Sangyo Co., Ltd.

Titanium oxide sol TA-15: It is formed from 15 parts by weight of anatase-type titanium oxide particles and 85 parts by weight of an aqueous nitric acid solution, and is available from Nissan Chemical Co., Ltd.

Example A1: Silica Coating Precursor and Solvent Amount The titanium oxide sol (ST-K01) was diluted 10 times, 100 times or 1000 times with ethanol to obtain samples A1, A2, and A3, respectively. The solid content concentrations of the samples A1 to A3 were 1% by weight, 0.1% by weight, and 0.01% by weight, respectively.

No aggregation was found in these samples after being left for 3 days.

The samples A1 to A3 were coated on a 10 cm square soda lime glass base material, and dried at room temperature for 18 hours.

As a result, all samples were able to obtain transparent and uniform coating films. However, in the coating film obtained with sample A1, interference fringes were observed.

Next, each coating film was irradiated with an ultraviolet light source (Sankyo Electric, BLB (Belastober) fluorescent lamp) with an illuminance of 0.25 mW/cm2 for 1 hour, and then the anti-fogging properties of the coating film were measured. The evaluation and measurement criteria are as follows: : No haze even if it breathes.

: When breathing, there is a slight haze, but a transparent image is clearly seen.

: When breathing, although it is not the glass matrix material in the whole process, there is a haze phenomenon in which the degree of transparent image cannot be clearly seen.

×: When suffocating, the haze phenomenon spreads over the matrix material glass.

As a result, the evaluation of the anti-fogging property was that the samples A1 and A2 were , and the sample A3 was ×.

For sample A1, the adhesion of the coating film to the base material and the ease of peeling from the base material were evaluated. The adhesion to the matrix material was evaluated by wiping with a water-containing wiping cloth () until peeling occurred. On the other hand, the evaluation of the ease of peeling from the base material is the number of wiping times until the coating film is completely peeled off when the plastic is wiped off with rubber. Each test was carried out 3 times.

As a result, the adhesion to the matrix material did not peel off even if it was wiped 20 times. On the other hand, due to the ease of peeling on the base material, the coating film can be completely peeled off only by wiping 2 to 3 times.

Example A2: Adding copper In 10 g of titanium oxide sol (ST-K01), 100 μl of copper sulfate aqueous solution with a copper concentration of 1 g/l was added, and then diluted 100 times with ethanol. After this diluted solution was left for 3 days, no agglomeration was found, showing good dispersibility. Therefore, even if the antibacterial metallic copper is added, there is no change in the performance as a coating liquid, and we think it can be used in the same manner as in Example 1.

Example A3: Adding silica and diluting the titanium oxide sol (TA-15) with ethanol to obtain a coating solution having a titanium oxide particle concentration of 0.5% by weight.

On the other hand, in the titanium oxide sol (TA-15), silica sol (Nippon Synthetic Rubber Geraska A liquid) was mixed and diluted with ethanol to obtain a titanium oxide particle concentration of 0.5% by weight and a silica particle concentration of 0.5% by weight coating liquid.

Each coating solution was coated on a 10 cm square soda lime glass base material, kept at 50°C for 1 hour, and allowed to cool for 15 minutes to obtain samples A4 and A5.

When observing the coating films of samples A4 and A5, sample A4 strongly reflected visible light and gave a dazzling feeling. In contrast, sample 5 hardly reflected visible light. It shows good visible light transmittance.

The samples A4 and A5 were irradiated with an ultraviolet light source (BLB fluorescent lamp) with an illuminance of 0.25 mW/cm2 for 2 hours, and then the anti-fogging properties of the coating film were measured. The anti-fogging properties were evaluated according to Example A1, and as a result, any sample showed good anti-fogging properties .

It can be seen from the above that the addition of silica having a lower refractive index than titanium dioxide maintains the transmittance of visible light on the surface while exhibiting good anti-fogging properties.

Example A4: Adding a non-ionic surfactant, mixing silica sol (Nippon Synthetic Rubber, Ceraska A solution, average particle size 10nm) in titanium oxide sol (TA-15), and then diluting with ethanol to obtain titanium oxide particles A coating liquid having a concentration of 0.5% by weight and a concentration of silica particles of 0.5% by weight.

The titanium oxide sol (TA-15) was mixed with silica sol (Geraska A solution) and polyethylene glycol (molecular weight 3000) as a surfactant, and then diluted with ethanol to obtain a titanium oxide particle concentration of 0.5% by weight. A coating liquid having a silica particle concentration of 0.5% by weight and a polyethylene glycol concentration of 0.2% by weight.

After mixing silica sol (Glaska A liquid) and denatured silicone (Shin-Etsu Chemical, KF-351, polyether type) as a surfactant in titanium oxide sol (TA-15), dilute with ethanol to obtain titanium oxide particles A coating solution having a concentration of 0.5% by weight, a concentration of silica particles of 0.5% by weight, and a concentration of denatured silicone of 0.2% by weight.

On the other hand, the titania sol (TA-15) was mixed with silica sol (Glaska A liquid) and modified silicone as a surfactant (Shin-Etsu Chemical, KF-945, polyether type), and then diluted with ethanol A coating solution having a titanium oxide particle concentration of 0.5% by weight, a silica particle concentration of 0.5% by weight, and a modified silicone concentration of 0.2% by weight was obtained.

Various coating liquids were coated on a 10 cm square soda lime glass substrate material, kept at 50°C for 1 hour, and cooled for 15 minutes to obtain samples A6-9, respectively.

The samples A6 to 9 were irradiated with an ultraviolet light source (BLB fluorescent lamp) with an illuminance of 0.25 mW/cm 2, and the change in the anti-fogging property of the coating film with respect to the irradiation time was measured. The results are shown in FIG. 6.

That is, the sample A6 showed good anti-fogging property within 2 hours, until it showed the anti-fogging property of , the sample A7 used 3 hours, the sample A8 used 4 hours, and the sample A9 used 20 hours. From the above, it can be seen that the addition of a surfactant that has a strong influence on the hydrophobic site requires ultraviolet light to be irradiated in order to exhibit anti-fogging properties.

Example B1: The amount of surfactant added was titanium oxide sol (TA-15), silica sol (ceraska A liquid), and a nonionic surfactant (Matsumoto Oils and fats, -, NP-95) and ethanol were mixed to obtain coating liquid samples B1 to 4 in which titanium oxide particles, silica particles, and surfactants were dispersed in a solvent.

Table 1 Sample Titanium Oxide Silica Particle Surfactant (Parts by Weight) (Parts by Weight) (Parts by Weight) B1 50 25 0B2 50 25 20B3 50 25 50B4 50 25 100 After drying, the soda lime glass substrate was irradiated with an ultraviolet light source (Sankyo Electric, BLB fluorescent lamp) with an illuminance of 0.25 mW/cm2, and the change of the anti-fogging property on the irradiation time was studied. The results are shown in Fig. 7, and the anti-fogging properties were evaluated in accordance with the same evaluation criteria as in Example A1.

For the evaluation of anti-fogging properties, as shown in Fig. 7, regardless of whether the substrate glass was irradiated with ultraviolet rays or not, samples of coating liquid samples B1 to 4 were coated on the surface of the substrate glass. After 50 hours, All are show good anti-fogging properties.

The samples coated with the coating liquid sample B1 did not show anti-fogging properties at all before irradiation. On the contrary, the samples coated with the coating liquid samples B2 to 4 also showed anti-fogging before irradiation. Sex.

We believe that the sample coated with the coating liquid sample B1 does not exhibit anti-fogging properties in the initial stage due to the influence of residual ethanol. It can also be considered that the anti-fogging properties shown over time are due to the decomposition of ethanol due to the light excitation of the photocatalyst.

In response to this, the coating liquid samples B2 to 4 in which the surfactant was mixed were applied. Since ethanol and the surfactant coexisted, the anti-fogging properties were initially obtained. Although this initial anti-fogging performance is temporarily lost, the anti-fogging performance is restored. This is because the photocatalyst is excited by light to decompose ethanol and surfactants, and loses hydrophilicity due to intermediate products produced in the decomposition process, so it temporarily loses its anti-fogging properties. When the surfactant is completely decomposed, it becomes hydrophilic. The performance is restored again, and the anti-fogging performance is also restored.

Therefore, it can be seen that when other surfactants are added in addition to the photocatalytic titanium oxide particles, silica, and ethanol, the permanent anti-fogging properties can be exhibited, and the initial anti-fogging properties can be obtained.

The more surfactants, the longer the temporary loss of anti-fogging properties. That is, for 1 part by weight of the photocatalytic titanium oxide particles, the sample coated with only 0.4 parts by weight of the surfactant coating solution sample B2 was coated with 1 part by weight of the surfactant for about 2 hours. The sample of cloth liquid sample B3 did not exceed 5 hours, and the sample coated with 2 parts by weight of surfactant coating liquid sample B4 reached 24 hours. Furthermore, when 1 part by weight of the photocatalytic titanium oxide particles were coated with a sample containing 10 parts by weight of a surfactant coating liquid, the time for the temporary loss of anti-fogging properties was 200 hours or more.

For the temporary loss of anti-fogging properties, for example, when it is provided in the form of a spray, it is best within 1 day. It is known that the amount of surfactant added is preferably less than 10 weight for 1 part by weight of photocatalytic titanium oxide particles. Parts, less than 2 parts by weight is better.

For the substrate glass irradiated with BLB for 50 hours and the sample coated with the coating liquid sample B1-4 on the surface of the substrate glass, the contact angle between the surface and water and the contact angle with water were investigated using a contact angle measuring device ( Concord Interface Science, CA-X150). The measurement was performed after 30 seconds of dripping water droplets on the surface of the sample from a micro syringe.

As a result, the substrate glass was 30°, and the coating liquid sample B1-4 was coated on the surface of the substrate glass. All the samples showed good results, and any contact angle with water was 0°.

With respect to the sample in which the coating liquid sample B1-4 whose contact angle with water was evaluated was coated on the surface of the base material glass, the oil pollution purification performance was evaluated. That is, oleic acid was applied to the surface of each sample, and each sample was immersed in a water tank filled with water while keeping the surface of the sample in a horizontal posture.

As a result, oleic acid coalesce to form oil droplets, which will be released from the surface of the sample after gentle rubbing.

Example B2: Polishing by adding cationic and nonionic surfactants. After mixing titanium oxide sol (ST-K01) and titanium oxide sol (ST-K03) at a ratio of 1:1, they were diluted 20 times with propanol to obtain The mixed solution was designated as the photocatalytic coating sample B5. To this sample B5, 0.05% by weight (that is, 0.325% by weight for titanium oxide) sorbitan monocaprylate (nonionic surfactant) was added to obtain sample B6, and 0.1% by weight was added to sample B5 % (That is, 0.65% by weight for titanium oxide) of sorbitan monocaprylate to obtain sample B7, and for sample B5, 0.05% by weight of quaternary ammonium salt (cationic surfactant) is added to obtain sample B8 . Furthermore, 0.1% by weight of quaternary ammonium salt was added to sample B5 to obtain sample B9.

Use the flow coating method to coat samples B5 to 9 on a dark gray painted steel plate sprayed with ethanol, and leave it at room temperature (20°C) for 18 hours. For this sample, it was measured in accordance with the Japanese Industrial Standards (JIS) Z8741 Gloss. As a result, compared to the gloss of the coated steel plate being 94, the gloss of sample B5 was 96, and the samples B6-9 with surfactant added were 102, 110, 106, and 112, respectively, which was larger, showing luster.

Samples B5 to 9 were coated on a glass plate sprayed with ethanol by the flow coating method, and left for 18 hours at room temperature (20°C). The sample was irradiated with an ultraviolet light source (Sankyo Electric, BLB fluorescent lamp) with an illuminance of 0.5 mW/cm2, and the change in the anti-fogging property with respect to the irradiation time was studied. As a result, the anti-fogging properties were seen. Samples B5 to 7 showed the characteristics of at the beginning, and the sample B8 showed the characteristics of after 1.5 hours, and the sample B9 showed the characteristics of after 5 hours.

Example C1: Addition of anionic surfactants. 2450 parts by weight of water and 0.025 parts by weight of anionic surfactants (Nippon Oil and Fats, -A-80) were added to titanium oxide sol (ST-K01) to obtain sample C1 .

A titanium oxide sol (ST-K01) was added with 2450 parts by weight of water and 0.25 parts by weight of an anionic surfactant (Nippon Oil & Fats, - A-80) to obtain sample C2.

The samples C1 and C2 were left for 3 days, and it was not considered that agglomeration occurred.

Samples C1 and C2 were coated on a 10 cm square soda lime glass plate by the flow coating method, and dried at room temperature for 1 hour to obtain samples C3 and C4.

For samples C3 and C4, it was not considered that white turbidity and interference lines appeared, and a uniform and transparent coating film was obtained.

Next, samples C3 and C4 were irradiated with an ultraviolet light source (Sankyo Electric, BLB fluorescent lamp) with an illuminance of 0.25mW/cm2 for 1 day, and the contact angle with water, anti-fogging, and Purification of oil-contaminated water.

The contact angle with water was measured using a contact angle measuring device (Kyowa Interface Science, CA-X150), and water droplets were dropped from a micro-syringe to evaluate the contact angle with water 30 seconds after the drop. As a result, both samples C3 and C4 Yes, it shows a high degree of hydrophilization when the contact angle with water reaches approximately 0°. The contact angle with water of the soda lime glass plate measured for comparison reached 30°.

The anti-fogging properties were evaluated according to the same evaluation criteria as in Example A1. As a result, the anti-fogging properties of sample C3 and C4 showed good results of .

Furthermore, the purification performance of oil pollution was evaluated for samples C3 and C4. That is, oleic acid was coated on the surface of each sample, and while keeping the surface of the sample in a horizontal posture, each sample was immersed in a water tank filled with water.

As a result, the oleic acid on any sample coalesce to form oil droplets, which can be released from the surface of the sample by gently rubbing it.

Example D1: Addition of alcohol-small molded product coating film The titanium oxide sol (ST-K01) was diluted 25 times with 2-propanol to obtain coating solution sample D1.

The above-mentioned coating liquid was coated on a 10 cm square soda lime glass base material by a spray coating method, and dried at room temperature (20° C.) for 20 minutes to cure the coating film to obtain sample D2.

On the other hand, the titanium oxide sol (ST-K01) was diluted 25 times with ethanol to obtain a coating solution sample D3.

The coating solution was coated on a 10 cm square soda lime glass base material by a flow coating method, and then dried at room temperature (20° C.) for 20 minutes to cure the coating film to obtain a comparative sample D4.

Next, the contact angle and appearance of samples D2 and D4 with water were studied.

The surface of samples D2 and D4 was irradiated with an ultraviolet light source (Sankyo Electric, BLB fluorescent lamp) with an illuminance of 0.5 mW/cm2 for 24 hours. Using a contact angle measuring device (Kyowa Interface Science, CA-X150), water droplets were dropped on the sample surface from a micro syringe, and 30 seconds later, the contact angle with water after irradiation was measured.

As a result, the sample D2, like D4, showed superhydrophilization when the contact angle with water reached 0°. Sample D2 is the same as D4, and its appearance is transparent, and no unevenness is observed.

Example D2: Adding alcohol-coating film of large-sized molded product. The coating solution sample D1 of Example D1 was coated on a 50cm square soda-lime glass substrate material by flow coating, and then dried at room temperature (20°C) for 20 Minutes, the coating film was cured, and sample D5 was obtained.

On the other hand, the coating solution sample D3 of Example D1 was coated on a 50 cm square soda-lime glass substrate material by the flow coating method, and dried at room temperature (20°C) for 20 minutes to cure the coating film to obtain a sample D6.

For samples D5 and D6, the contact angle and appearance with water were studied.

The surfaces of the samples D5 and D6 were irradiated with an ultraviolet light source (Sankyo Electric, BLB fluorescent lamp) with an illuminance of 0.5 mW/cm2 for 24 hours. Using a contact angle measuring device (Kyowa Interface Science, CA-X150), water droplets were dropped on the surface of the sample from a micro syringe. After 30 seconds, the contact angle with water after irradiation was measured.

As a result, the sample D5, like D6, showed superhydrophilization when the contact angle with water reached 0°.

However, in sample D6, white turbidity was seen at the starting point of the free flow coating, while in sample D5, the appearance was transparent, and no unevenness was observed.

Therefore, it can be shown that propanol is preferably used for large-sized molded products.

Example D3: Adding alcohol-large molded product coating. After mixing titanium oxide sol (ST-K01) and titanium oxide sol (ST-K03) at a ratio of 1:1, they were diluted 25 times with 2-propanol to obtain a coating liquid Sample D7.

The coating solution sample D7 was coated on a 50 cm square soda lime glass base material by the flow coating method, and dried at room temperature (20° C.) for 20 minutes to cure the coating film to obtain sample D8.

With respect to sample D8, the contact angle with water and the appearance were investigated in the same manner as in Example D1.

As a result, the sample D8 exhibited superhydrophilization when the contact angle with water reached 0°. The appearance is transparent, and no unevenness is observed.

Example D4: Adding alcohol-large molded product coating. After mixing titanium oxide sol (ST-K01) and titanium oxide sol (ST-K03) at a ratio of 1:1, the mixture was mixed with 8:2 2-propanol and The propylene glycol monopropyl ether mixture was diluted 25 times to obtain coating solution sample D9.

The coating solution sample D9 was coated on a 50 cm square soda lime glass base material by a flow coating method, and dried at room temperature (20° C.) for 20 minutes to cure the coating film to obtain sample D10.

For the sample D10, the contact angle with water and the appearance were investigated in the same manner as in Example D1.

As a result, the sample D10 exhibited superhydrophilization when the contact angle with water reached 0°. The appearance is transparent, and no unevenness is observed.

Example D5: Adding Alcohol-Large-sized molded product coating. After mixing titanium oxide sol (ST-K01) and titanium oxide sol (ST-K03) at 1:1, use 9:1 2-propanol and diacetone alcohol ( The 4-hydroxy-4-methyl-pentan-2-one) mixed solution was diluted 25 times to obtain a coating solution sample D11 (pH 4).

The coating solution sample D11 was coated on a 50 cm square soda lime glass base material by a flow coating method, and dried at room temperature (20° C.) for 20 minutes to cure the coating film to obtain sample D12.

For the sample D12, the contact angle with water and the appearance were investigated in the same manner as in Example D1.

As a result, when the contact angle between sample D12 and water reached 0°, it exhibited superhydrophilization. The appearance is transparent, and no unevenness is observed.

Example D6: Application to automobile body After mixing titanium oxide sol (ST-K01) and titanium oxide sol (ST-K03) at 1:1, use a 9:1 mixture of ethanol and diacetone alcohol for the mixture Diluted 25 times to obtain coating solution sample D13.

The coating solution sample D13 was coated on the car shell by the flow coating method, and dried at room temperature (20° C.) for 20 minutes to cure the coating film to obtain sample D14.

Regarding sample D14, the contact angle with water and the appearance were investigated in the same manner as in Example D1.

As a result, the sample D14 exhibited superhydrophilization when the contact angle with water reached 0°. The surface is smooth, the appearance is transparent, and no unevenness is observed.

Example D7: Application to automobile body After mixing titanium oxide sol (ST-K01) and titanium oxide sol (ST-K03) at a ratio of 1:1, use the mixture with 8:1:1 ethanol and 2- The mixed solution of propanol and diacetone alcohol was diluted 25 times to obtain coating solution sample D15.

The coating solution sample D15 was coated on the car shell by a spray method, and dried at room temperature (20° C.) for 20 minutes to cure the coating film to obtain sample D16.

For the sample D16, the contact angle with water and the appearance were investigated in the same manner as in Example D1.

As a result, the sample D16 exhibited superhydrophilization when the contact angle with water reached 0°. The appearance is transparent, and no unevenness is observed.

Example D8: After adding ethanol and a leveling agent to mix the titanium oxide sol (ST-K01) and the titanium oxide sol (ST-K03) at 1:1, the mixture was mixed with 8:2 ethanol and propylene glycol monopropyl The ether mixture was diluted 25 times to obtain coating solution sample D17.

The coating solution sample D17 was coated on a 50 cm square soda lime glass base material by the flow coating method, and dried at room temperature (20° C.) for 20 minutes to cure the coating film to obtain sample D18.

With regard to sample D18, the contact angle with water and the appearance were investigated in the same manner as in Example D1.

As a result, the sample D18 exhibited superhydrophilization when the contact angle with water reached 0°. The appearance is transparent, and no unevenness is observed.

Example D9: Add ethanol and leveling agent to mix titanium oxide sol (ST-K01) and titanium oxide sol (ST-K03) at a ratio of 1:1, and then use 9:1 ethanol and butyl cellosolve ( The 2-butoxyethanol) mixed solution was diluted 25 times to obtain coating solution sample D19.

The coating solution sample D19 was coated on the outer shell of an automobile by the flow coating method, and dried at room temperature (20° C.) for 20 minutes to cure the coating film to obtain sample D20.

For the sample D20, the contact angle with water and the appearance were investigated in the same manner as in Example D1.

As a result, the sample D20 exhibited superhydrophilization when the contact angle with water reached 0°. The appearance is transparent, and no unevenness is observed.

Example D10: Aerosol composition The coating solution sample D11 of Example D5 and nitrogen gas were charged into the spray container shown in FIG. 1 at a volume ratio of 6:4. The coating liquid sample D11 was sprayed on the smooth glass base material from the spray container, and it was left at room temperature for 30 minutes to obtain the sample D13.

The contact angle with water and the appearance of the sample D13 were examined in the same manner as in Example D1.

As a result, when the contact angle of the sample D13 with water reached 0°, it was superhydrophilized. In addition, its appearance was transparent, and no unevenness was observed.

Example E1: Solid content concentration and transparency The soda lime glass plate (size 40×100×2mm) was immersed in a solution of titanium oxide sol (ST-K01) diluted with ethanol and immersed at a lifting speed of 24 cm/min After coating, ethanol is diluted to form the following solid content concentration. After that, heating was performed at 50°C or 150°C to obtain samples E1 to E8. With respect to these samples, the haze value (haze value) was measured using a haze meter (manufactured by Gardener Co., Ltd., Beige-duplas).

The results are shown in the table below.

Sample Solid content concentration Heat treatment temperature Haze value (weight%) (°C) (%) E1 10 50 12E2 5 50 0.25E3 1 50 0.12E4 0.1 50 0.23E5 10 150 10E6 5 150 0.22E7 1 150 0.12E8 0.1 150 0.27

Example E2: Solid content concentration and film hardness were the same as Example E1 except that titanium oxide sol ST-K03 was used, and samples E9-16 were obtained.

For these samples, a pencil hardness test was performed in accordance with the Japanese Industrial Standards (JIS) H8602, and the results are shown in the table below.

Sample Solid content concentration Heat treatment temperature Haze value (wt%) (°C) (%) E9 10 50 5BE10 5 50 6BE11 1 50 9HE12 0.1 50 9HE13 10 150 6BE14 5 150 6BE15 1 150 8HE16 0.1 150 9H