JP2001246265A - Substrate having photocatalyst-containing layer formed on surface, and method for forming the photocatalyst- containing layer on surface of substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a substrate on the surface of which a layer containing a photocatalyst sensitive to visible light is formed, and a method for forming the layer. SOLUTION: As for the substrate, a layer containing two or more kinds of photocatalysts different in a light absorption wavelength is formed on its surface. As for the formation method, the layer is formed by a dry process, such as vapor deposition, a sputtering method, and an ion plating method. The layer is photo-excited in response to photoirradiation to show properties, such as a hydrophilic property, a self cleaning property, an antifouling property, and an organic substance decomposing property. The layer is used for glass, a building material, a material used at a water section, and the like. By this formation method, a photocatalyst film excellent in sensitivity to visible light can be obtained, which can function even when used in a room.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a substrate having a photocatalyst-containing layer formed on the surface thereof and a method for forming a photocatalyst-containing layer on the surface of the substrate, and more particularly to a photocatalyst sensitive to visible light. The present invention relates to a substrate on which a layer containing is formed and a method for forming the same.

[0002]

2. Description of the Related Art It is known that a photocatalyst is coated on a substrate surface to impart antibacterial properties, antifouling properties, deodorant properties, etc. in order to apply the strong oxidizing power of the photocatalyst by photoexcitation possessed by the photocatalyst to organic matter decomposition. In recent years, as a function of a photocatalyst, not only the decomposability by the photoexcitation but also the use of hydrophilicity by photoexcitation have been used. The fields that can utilize the hydrophilicity include, for example, the following.

In cold weather, windshields and glazings of automobiles and other vehicles, glazings of buildings, lenses of eyeglasses, and cover glasses of various instrument panels are often fogged by condensed moisture. In addition, mirrors and eyeglass lenses in bathrooms and washrooms are often fogged by steam. The fogging on the surface of the member is that when the surface is placed at a temperature below the dew point of the atmosphere, the moisture in the atmosphere condenses and condenses on the surface,
This is because they grow like water drops. If the condensed water droplets are sufficiently fine and their diameter is about half the wavelength of visible light, the water droplets will scatter light and the glass or mirror will be apparently opaque, again losing visibility.

If the condensation of moisture further progresses and the fine condensed water droplets fuse with each other and grow into larger discrete water droplets, the refraction of light at the water droplet / surface interface and the water droplet / air interface will cause them to refract. The surface is dark, blurred, mottled, or cloudy. As a result, in a transparent article such as glass, the perspective image is distorted and the transparency is reduced, and the reflected image is disturbed by a mirror.

Further, when a windshield or a window glass of a vehicle, a window glass of a building, a rearview mirror of a vehicle, a lens of eyeglasses, a shield of a mask or a helmet are subjected to rainfall or splashing, and a large number of discrete water droplets adhere to the surface, Their surface may be dark, blurred, mottled, or cloudy, again losing visibility.

Needless to say, the above-mentioned "clouding" has a profound effect on safety and efficiency of various operations. For example, if the windshield or window glass of the vehicle, or the rearview mirror of the vehicle is overcast or cloudy in cold weather or rainy weather, it will be difficult to secure visibility.
Traffic safety is impaired. If the focusing lens of an endoscope lens, a dental mirror, or a dental laser treatment device becomes cloudy, it hinders accurate diagnosis, surgery, and treatment. When the cover glass of the instrument panel becomes cloudy, it becomes difficult to read the data.

On the other hand, in the field of construction and paint,
With environmental pollution, stains on building exterior materials, outdoor buildings, and their coatings have become a problem. Dust and particles suspended in the air accumulate on the roof and outer walls of buildings in fine weather. Sediment is washed away by rainwater as it rains and flows down the building's outer walls. Furthermore, in the rain, the floating dust is carried by the rain and flows down on the outer wall of the building or the surface of the outdoor building. As a result, pollutants adhere to the surface along the path of rainwater. When the surface dries, striped stains appear on the surface.

Further, in the indoor water space, around the bathroom, around the washroom, around the toilet, etc., dirt on the floor, walls, and ceiling due to dew condensation, water contaminants, impurities, slime caused by various microorganisms, stains, etc. Etc. is a problem.

[0009] In order to solve the above problems, various attempts have been made to impart antifogging properties and dropping properties to various substrates. As one of the methods for imparting anti-fogging property and dropping property to the substrate, there is a method for improving the hydrophilicity of the substrate surface, and various methods have been proposed.

For example, in Japanese Utility Model Application Laid-Open No. 3-129357, a polymer layer is provided on the surface of a base material, and this layer is irradiated with ultraviolet rays and then treated with an aqueous alkali solution to generate high-density acidic groups. A method for making a mirror antifogging, which comprises making the surface of the mirror hydrophilic, is disclosed.

Japanese Utility Model Application Laid-Open No. 5-68006 discloses an antifogging film made of a graft polymer of an acrylic monomer having a hydrophilic group and a monomer having a hydrophobic group.

JP-A-55-56177 discloses an antifogging agent comprising an aqueous dispersion containing colloidal silica and a nonionic surfactant and / or an anionic surfactant.

JP-A-10-60665 discloses a hydrophilic film formed by applying a composite solution containing a metal oxide sol to the surface of a base material and then sub-baking it.

Japanese Patent Application Laid-Open No. 57-147525 discloses a synthetic resin excellent in drip-free properties in which inorganic water-based sol particles are deposited on the surface of a base material, and then a drip-free material containing inorganic colloid particles and a surfactant is applied. A method for producing a molded article is disclosed.

However, these methods of imparting hydrophilicity to the surface of a substrate cannot provide a substrate with a high degree of hydrophilicity that imparts anti-fogging properties or dripping properties to the substrate, or do not impart hydrophilicity. It requires complicated processes, high costs and large-scale equipment, cannot be applied to substrates with poor heat resistance due to the necessity of a heat treatment process, or the effect of hydrophilicity lasts only for a short period of time. Problems such as poor durability and abrasion resistance of the coating film provided on the substrate surface for imparting hydrophilicity, and change in the color tone and transparency of the substrate depending on the coating film, giving a sense of incongruity. Was associated with one or more.

To solve these problems, PCT / WO96 / 2
9375 discloses a method for forming a photocatalyst-containing layer on the surface of a base material to impart hydrophilicity to the surface in accordance with photoexcitation of the photocatalyst, using a sol-gel method for the photocatalyst, or using a binder. Thus, a method for forming a photocatalyst-containing layer on the surface of a substrate is disclosed. Another means for forming a photocatalyst layer on the surface of a substrate is disclosed in
No. 226042 and JP-A-9-57911 disclose that a layer containing a photocatalyst is formed on the surface of a substrate of a film to be attached to the substrate.

[0017]

However, in applications utilizing the degradability and hydrophilicity of these photocatalysts, photoexcitation of the photocatalyst is required, and ultraviolet light is required for this photoexcitation. Although this ultraviolet ray is contained abundantly in the sunlight outdoors, it is scarcely contained indoors in sunlight or indoor light. Therefore, in the field where decomposability and hydrophilicity are used by using these photocatalysts, the effect cannot be sufficiently exhibited unless a dedicated ultraviolet lamp or the like is used in indoors where sunlight cannot be used. Uses were limited. Among them, particularly when utilizing hydrophilicity, it is necessary to use stronger ultraviolet rays than in the field utilizing decomposition, and excitation by visible light is less likely to occur,
It was almost impossible to use it indoors. In addition, it has been difficult to form a uniform film having high strength, high durability, and a sol-gel method, a method using a binder, and a method of attaching a film coated with a photocatalyst.

The present invention has been made in view of the above circumstances, and a uniform and high-strength layer containing a photocatalyst that can be photoexcited by visible light and that exhibits decomposability and hydrophilicity by photoexcitation is formed on the surface. An object is to provide a substrate and a method for forming the substrate.

[0019]

According to the present invention, in order to solve the above-mentioned problems, a substrate having a layer containing a plurality of types of photocatalysts having different light absorption wavelengths formed on the surface thereof, and a plurality of types of photocatalysts having different light absorption wavelengths. Provided is a method for imparting functionality to a substrate surface by forming a layer containing a photocatalyst on the surface.

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the components of the present invention will be described. In the present invention, a layer containing a plurality of types of photocatalysts having different light absorption wavelengths is formed on the surface of a base material having a desired function.

[0021] The intended function herein refers to a group consisting of antifogging property, self-cleaning property, antifouling property due to hydrophilicity, antibacterial property, antifouling property, deodorant property, etc. due to organic matter decomposability. The purpose is to express antifogging properties, self-cleaning properties, and antifouling properties due to hydrophilicity.

The above function is realized by photo-excitation of the layer containing the photocatalyst by light irradiation, and the photo-excitation is preferably enabled by irradiation with visible light. Titanium dioxide, which is a commonly used photocatalyst, is photoexcited by light in the ultraviolet region, but hardly responds to light in the visible region. The film containing a photocatalytic film sensitive to light in the visible light region according to the technology of the present invention is effective for indoor use where almost no ultraviolet light is irradiated, whether from sunlight penetrating indoors or from indoor lights. is there.

The layer containing the photocatalyst in the present invention is preferably formed by a dry process. The advantage of the dry process is that firstly, a film with higher filling, higher strength and higher durability can be formed as compared with the wet method such as the sol-gel method or the binder method.The second advantage is that the chemical method is used in the wet method. The point is that a film having a composition that cannot be formed because it is unstable is formed.

As a method of the dry process, it is preferable to use a method selected from the group consisting of a vapor deposition method, a sputtering method, and an ion plating method. Whichever method is used, it is preferable to select film-forming conditions that can satisfy the first and second advantages described above, and can also satisfy each of the advantages.

The photocatalyst in the present invention preferably contains titanium oxide as a main component. Further, it is more preferable that the titanium oxide contains a plurality of types of compounds having different oxygen / titanium ratios, whereby the film containing a photocatalyst contains a plurality of types of photocatalysts having different light absorption wavelengths. Titanium oxide can be doped with a transition metal ion such as Cr or V, or compounded with V2O5, CuO, or the like to improve its activity.

Particularly preferred as the plurality of types of titanium oxides are those containing Ti 2 O 3, and this component is particularly sensitive to visible light. Preferred examples of the photocatalyst component other than Ti2O3 include TiO2, and anatase-type, rutile-type, and brookite-type TiO2 can be used. These titanium oxides are preferably used in a crystalline form as described above, but may further contain amorphous titanium oxide. Titanium oxide, which also has amorphous properties, is often inferior to crystalline ones in photocatalytic activity, but may have other advantages such as being strong in bending.

Other photocatalysts applicable to the present invention include zinc oxide, tin oxide, ferric oxide, bismuth trioxide, tungsten trioxide, and strontium titanate.

In forming such a layer containing a plurality of types of photocatalysts having different light absorption wavelengths, even if the layer containing the photocatalyst has a different composition of the photocatalyst in the thickness direction, the layer may be uniform in the thickness direction. Although a plurality of types of photocatalysts may be mixed with different compositions, it is more preferable that the photocatalysts have different compositions in the thickness direction in order to control their functions. The layer having a different composition in the thickness direction may be composed of a plurality of layers having different compositions, or may have a composition continuously changing in the thickness direction. The formation of layers having different compositions in the thickness direction as described above can be relatively easily achieved by using a dry process. For example, in a sputtering method, film formation conditions such as temperature and atmosphere and a target This can be realized by changing the composition. In these cases, as a means for changing the temperature, atmosphere, and type of target, the temperature, atmosphere, and type of target may be changed over time using a batch-type film forming method.
In addition, it is also possible to use a continuous film forming method and change the temperature, atmosphere, and target type depending on the zone, and take a means for allowing the base material to pass through each zone.

Suitable base materials for forming such films having different compositions in the thickness direction by a continuous film forming method include, for example, roll-shaped base materials such as steel plates. By constructing a production line in which continuous film formation is performed after unwinding the base material and then wound up in a roll shape, a highly efficient film formation process becomes possible.

When a layer containing a photocatalyst containing a plurality of types of titanium oxides having different oxygen / titanium ratios is formed, the layer closer to the surface in the thickness direction has a larger oxygen / titanium ratio, and the photocatalytic activity is Particularly, it is preferable for improving the photocatalytic activity in the visible light region. In this case, for example, TiO and Ti2O3 can be contained as main components in a region near the base material, and TiO2 can be contained as a main component in a region near the surface.

In the dry process, the first means for increasing the oxygen / titanium ratio in a layer closer to the surface in the thickness direction of the layer containing the photocatalyst as described above is to raise the substrate temperature as the layers closer to the surface are stacked. I can give you something to do. This means can be adopted for both batch-type film formation and continuous-type film formation.

The second means for increasing the oxygen / titanium ratio in the dry process as the layer containing the photocatalyst is closer to the surface in the thickness direction is as follows. Increasing the concentration can be mentioned. This means can be adopted for both batch-type film formation and continuous-type film formation.

In the dry process, the third means for increasing the oxygen / titanium ratio as the layer containing the photocatalyst is closer to the surface in the thickness direction as the layer closer to the surface is as follows. The use of a target with a high ratio can be mentioned. This means is mainly used for continuous film formation, and a film having a desired composition can be obtained by continuously passing a substrate through a plurality of coating chambers provided with different targets. In this case, the respective chambers may be completely independent, or may be independent and continuous.

Further, as the layer containing a photocatalyst in the present invention, a plurality of types of layers having different compositions may be alternately or randomly laminated. Such a layer can be formed by, for example, causing a substrate and a target to reciprocate in a chamber having a plurality of targets having different compositions.

It is preferable that the layer containing the photocatalyst in the present invention further contains a substance exhibiting properties selected from the group consisting of hydrophilicity, water storage and binder properties. This is because, as a first reason, although the action of the photocatalyst is strongly sensitive when receiving the excitation light, the expression of the activity is remarkably reduced when the light is not irradiated, so that the substance having hydrophilicity or water storage property is used. It is added to maintain activity even in the dark.

The second reason is that, in particular, a layer made of only a photocatalyst formed by a dry process is superior in strength and durability to a layer formed by a wet method, but the limit is still limited by a photocatalyst alone. Therefore, the strength and durability are improved by adding a substance having a binder property.

A material which exhibits properties selected from the group consisting of hydrophilicity, water storage and binder properties, and which is suitable as a material which can be coated together with a photocatalyst by a dry process, such as silica, zirconia, alumina, tin oxide, etc. But especially hydrophilic
Silica can be used as a suitable substance that imparts a good balance between water storage and binder properties.

It is preferable that the content of the substance exhibiting the property selected from the group consisting of the hydrophilicity, water storage property and binder property is higher in a portion closer to the surface in the thickness direction of the layer containing the photocatalyst, Thereby, the photocatalytic activity and the physical properties of the film can be improved in a well-balanced manner. As a method of controlling the content of the substance that expresses the property selected from the group consisting of hydrophilicity, water storage, and binder property in the thickness direction of the film, a method of forming a film using a dry process is described. For example, two types of targets, a target forming a photocatalyst and a target forming a substance exhibiting properties selected from the group consisting of hydrophilicity, water storage, and binder property, are used, and each film forming ratio is changed. I can give it.

The substance exhibiting the property selected from the group consisting of hydrophilicity, water storage property and binder property can be further contained in the layer containing the photocatalyst as described above. A layer containing a substance exhibiting properties selected from the group consisting of hydrophilicity, water storage properties, and binder properties can also be formed. Also in this case, hydrophilic
Suitable substances that exhibit properties selected from the group consisting of water storage and binder properties include silica, zirconia, alumina, and tin oxide, and among them, hydrophilicity, water storage, and binder are particularly preferable. Silica can be given as a suitable substance imparting a good balance of properties.

The preferred range of the thickness of the layer containing the photocatalyst in the present invention is 10 nm to 10 μm,
More preferably, it is 50 nm to 1 μm. If it exceeds the upper limit of the preferred range, the appearance may be poor, but in applications where the appearance is not so important, it is not necessary to stick to the upper limit. If the value is smaller than the lower limit of the preferable range, the photocatalytic activity may be insufficient.

When a layer containing a substance exhibiting properties selected from the group consisting of hydrophilicity, water storage and binder property is provided on a layer containing a photocatalyst, the thickness of the layer is preferable. The optimal range is 5 nm to 2 μm, and more preferably 10 nm to 200 nm. If it is larger than the upper limit of the preferred range, the photocatalytic activity may not be sufficiently exhibited, and if it is smaller than the lower limit of the preferred range, the property selected from the group consisting of hydrophilicity, water storage, and binder property may not be sufficiently exhibited. is there.

In the present invention, the content of the photocatalyst in the layer containing the photocatalyst is preferably 5 to 100% by weight, more preferably 30 to 95% by weight. If the amount is more than the preferable upper limit, the strength and durability of the layer containing the photocatalyst may not be sufficient, or the photocatalytic activity in a dark place may not be sufficiently maintained.

The substrate to which the present invention can be applied includes, for example, glass for vehicles, window glass for buildings, mirrors for vehicles, road mirrors, instrument panel covers, eyeglass lenses, helmet shields, goggles, heat-insulating showcases, ice and snow Prevention roof,
Icicle formation prevention material, ice and snow prevention antenna, communication obstacle prevention material, ice and snow prevention transmission line, cone discharge prevention material, ceiling material for bathroom, plumbing for toilet bowl, plumbing for water supply, urinal, toilet bowl, trap for toilet bowl, Wash bowl, wash trap, bathtub, bathroom wall material, bathroom flooring, bathroom grating, shower hook, bathtub handgrip, bathtub apron, bathtub drain valve, bathroom window, bathroom window frame, bathroom Window floorboards, bathroom lighting fixtures, drainage plates, drainage pits, bathroom doors, bathroom door frames, bathroom window bars, bathroom door bars, slats, mats, soap holders, tubs,
Bathroom mirrors, bath chairs, transfer boards, water heaters,
Bathroom storage shelves, bathroom handrails, bath lids, bathroom towel rails, shower chairs, basins, etc., bathroom components, kitchen kitchen back, kitchen flooring, sinks, kitchen counters, drain baskets, tableware Dryers, dishwashers, stoves, range hoods, ventilation fans, stove ignition parts, toilet flooring, toilet wall materials, toilet ceilings, ball taps, water stopcocks, cigarette rolls, toilet seats, lifting toilet seats, toilets Toilet members such as doors, toilet bus keys, toilet towel rails, toilet lids, toilet handrails, toilet counters, flush valves, tanks, flushing nozzles for toilet seats with a washing function, wash traps,
Washroom mirrors, washroom storage shelves, drain cocks, toothbrush stands, washbasin mirror lighting equipment, washbasin counters, water soap dispensers, washbasins, mouth washes, hand dryers, washing tubs, washing machine lids, washing machine pans , Dehydration tub, air conditioner filter, touch panel, faucet fitting, cover of human body detection sensor, shower hose, shower head, shower discharge section, sealant, joint, wallpaper, refrigerated case, camera finder , Greenhouse ceiling, car room mirror, dental mirror, wallpaper, steel sheet coil, tent, film, sheet, woven fabric, non-woven fabric,
Fibers, inorganic fibers, SMC, BMC and the like can be mentioned.

[0044]

EXAMPLE In an RF magnetron sputtering apparatus (manufactured by Shimadzu Corporation), the substrate was a SUS304 plate, the targets were Ti2O3 and SiO2, and the outputs were 600 W and 40 W, respectively.
Argon flow rate 40cc / min, oxygen flow rate 5cc / mi
n, the sample holder was rotated at 0.5 Hz under a discharge, and a film was formed at a Ti2O3: SiO2 ratio of 80:20 for 100 minutes. Then, the target was Ti2O3 and SiO2, the output was 600 W and 40 W, respectively, and the argon flow rate was 40 cc /. m
The sample holder was rotated at 0.5 Hz under discharge at an oxygen flow rate of 20 cc / min.
By forming a film at a ratio of 80:20 for 100 minutes, a film thickness of 15
A 0 nm TiO2, Ti2O3 laminated film # 1 was obtained.
The composition ratio of Ti2O3 and SiO2 is Ti2O3 and SiO2.
The film formation speed was calculated based on the single film formation, and the film thickness was roughly estimated as a composition ratio to determine the film formation output. FIG. 1 shows the transition of the contact angle with water when irradiated with 0.5 mW / cm 2 of ultraviolet light by a BLB light. In the figure, C, RT, and H indicate sample positions (substrate temperatures), C is under water cooling, RT is room temperature,
H indicates the position under the heater. Since the heater is not energized in this film formation, it is considered that RT and H indicate the same substrate temperature.

From FIG. 1, it was found that the photocatalytic thin film formed under the sputtering conditions exhibited good photocatalytic hydrophilicity. FIG. 2 shows the transition of the contact angle with water when oleic acid is applied onto the film-formed body # 1 and irradiated with ultraviolet rays at 0.5 mW / cm 2.

FIG. 2 shows that the photocatalytic thin film formed under the sputtering conditions has a high decomposability of oleic acid decomposition, and shows a contact angle with water of 5 ° in 8 hours after irradiation with ultraviolet light. It was revealed that it shows degradability.

FIG. 3 shows the transition of the contact angle with water after the sliding test of the film-formed body # 1. After setting the load to 100 g / cm 2 through the SUS304 material, the film formed body # 1 was slid 1000 times, and the hydrophilicity of the photocatalytic thin film surface when irradiated with ultraviolet rays at 0.5 mW / cm 2 was evaluated. From FIG. 3, it was revealed that the photocatalytic thin film formed under the sputtering conditions had high hydrophilicity after the sliding test and exhibited good characteristics.

[0048]

As described above, the present invention provides a photocatalyst film having excellent sensitivity to visible light by forming a layer containing a plurality of types of photocatalysts having different light absorption wavelengths on a substrate surface. This makes it possible to exhibit functions such as hydrophilicity, antifogging property, self-cleaning property, antifouling property, and organic substance decomposability especially for indoor use.

[Brief description of the drawings]

FIG. 1 is a graph showing a photocatalytic hydrophilicity evaluation result of a film manufactured by the method of the present invention.

FIG. 2 is a graph showing evaluation results of photocatalytic decomposability and hydrophilicity of a film manufactured by the method of the present invention.

FIG. 3 is a graph showing a photocatalytic hydrophilicity evaluation result after a sliding resistance test of a film manufactured by the method of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C23C 14/08 C23C 14/08 E (72) Inventor Kazuhito Hashimoto 2073-2 Iijima-cho, Sakae-ku, Yokohama-shi, Kanagawa 2nd -City Hongodai D Bldg 213 F-term (reference) 4F100 AA20D AA21A AA21C AB04 AR00D AT00B BA02 BA03 BA04 BA08 BA10B BA10D BA41C BA44A CA30A CA30C EH66A EH66C GB07 GB32 JA11A JA11C JA12A JA12C JB05 JBDJ JB05 JBDJ JB05 JBD J AB09 AB11 AC21 AC22 EA04 EA05 EB02 EB03 EB04 GA01 GA02 GA04 GA12 4G069 AA03 AA08 BA02A BA02B BA04A BA04B BA13A BA14A BA14B BA48A CA01 CA11 CD10 EA07 EA09 EA10 EB15X EB15Y EC22 EA02 EC02 EC02 EC02 EC02 EC02 EC04

Claims (58)

[Claims] 1. A substrate having on its surface a layer containing a plurality of types of photocatalysts having different light absorption wavelengths. 2. The photocatalyst-containing layer exhibits properties selected from the group consisting of hydrophilicity, antifogging property, self-cleaning property, antifouling property, and organic substance decomposability by photoexcitation in response to light irradiation. The substrate according to claim 1, which is 3. The substrate according to claim 2, wherein the photoexcitation is possible by irradiation with visible light. 4. The substrate according to claim 1, wherein the layer containing the photocatalyst is formed by a dry process. 5. The substrate according to claim 4, wherein the dry process is selected from the group consisting of a vapor deposition method, a sputtering method, and an ion plating method. 6. The substrate according to claim 1, wherein the photocatalyst contains titanium oxide as a main component. 7. The substrate according to claim 6, wherein the titanium oxide contains a plurality of compounds having different oxygen / titanium ratios. 8. The method according to claim 1, wherein said titanium oxide is mainly composed of Ti2 O3.
8. The substrate according to claim 7, comprising: 9. The method according to claim 1, wherein said titanium oxide is further composed of
9. The substrate according to claim 8, comprising iO2. 10. The substrate according to claim 6, wherein the titanium oxide contains crystalline titanium oxide as a main component. 11. The substrate according to claim 10, wherein the titanium oxide further contains amorphous titanium oxide as a main component. 12. The photocatalyst-containing layer is composed of a plurality of layers having different compositions.
Substrate according to 1 13. The substrate according to claim 1, wherein the layer containing the photocatalyst is a layer whose composition continuously changes in the thickness direction. 14. The substrate according to claim 12, wherein a main component of the photocatalyst is titanium oxide, and the oxygen / titanium ratio of the layer containing the photocatalyst is larger in a layer closer to the surface in the thickness direction. 15. The substrate according to claim 1, wherein the layer containing the photocatalyst is formed by alternately or randomly stacking a plurality of types of layers having different compositions. 16. The substrate according to claim 1, wherein the photocatalyst-containing layer further contains a substance exhibiting properties selected from the group consisting of water storage, hydrophilicity, and binder properties. 17. The substrate according to claim 16, wherein a main component of the substance exhibiting properties selected from the group consisting of water storage, hydrophilicity, and binder properties is silica. 18. The content of a substance that exhibits properties selected from the group consisting of water storage, hydrophilicity, and binder properties is higher in a portion closer to the surface in the thickness direction of the layer containing the photocatalyst. 18. The base material according to 16 to 17. 19. The method according to claim 1, wherein a layer containing a substance exhibiting properties selected from the group consisting of water storage, hydrophilicity, and binder properties is further formed on the photocatalyst-containing layer. Base material. 20. The substrate according to claim 19, wherein a main component of the substance exhibiting properties selected from the group consisting of water storage, hydrophilicity, and binder properties is silica. 21. The thickness of the layer containing the photocatalyst is 10
The base material according to any one of claims 1 to 20, wherein the thickness is from 10 nm to 10 m, more preferably from 50 nm to 1 m. 22. The layer containing a substance exhibiting properties selected from the group consisting of water storage, hydrophilicity and binder properties has a thickness of 5 nm to 2 μm, more preferably 10 nm to 2 μm.
21. The substrate according to claim 19, which has a thickness of 00 nm. 23. The base material may be a vehicle glass, a building window glass, a vehicle mirror, a road mirror, an instrument panel cover, an eyeglass lens, a helmet shield, goggles, a heat-insulating showcase, a snow-prevention roof, an icicle. Building prevention materials, ice and snow prevention antennas, communication obstacle prevention materials, ice and snow prevention transmission lines, cone discharge prevention materials, bathroom ceiling materials, toilet pipes, water supply pipes, urinals, toilet bowls, toilet traps, washbasins Bowl, wash basin, bathtub, bathroom wall material, bathroom flooring, bathroom grating, shower hook, bathtub handgrip, bathtub apron, bathtub drain plug, bathroom window, bathroom window frame, bathroom window Floorboards, bathroom lighting fixtures, drainage plates, drainage pits, bathroom doors, bathroom door frames, bathroom window bars, bathroom door bars, scallops, mats, soap basins, tubs, bathroom mirrors, bath chairs, transfer boxes − Bathroom components such as water heaters, bathroom storage shelves, bathroom handrails, bath lids, bathroom towel rails, shower chairs, basins, kitchen kitchen backs, kitchen flooring, sinks, kitchen counters, drainage Baskets, dish dryers, dishwashers, stoves, range hoods, ventilation fans, stove ignition parts, toilet flooring, toilet wall materials, toilet ceilings, ball taps, water taps, cigarette rolls, toilet seats, elevating Toilet seats, toilet doors, toilet bus keys, toilet towel rails, toilet lids, handrails for toilets, toilet counters, flush valves, tanks, toilet parts such as water spout nozzles for toilet seats with a washing function, sink traps, and sinks Mirrors, storage shelves for sinks, drain cocks, toothbrush stands, lighting equipment for wash mirrors, wash counters, water soap dispensers, wash basins, mouth washer, hand dryers, washing tubs, washing machine lids, washing machine pans, Prolapse Bath, air conditioner filter, touch panel, faucets, human body sensor -
Cover, shower hose, shower head, shower
Water discharge part, sealant, joint, wallpaper, refrigerated case, camera finder, greenhouse ceiling, car interior mirror, dental mirror, wallpaper, steel coil, tent, film, sheet, woven fabric, non-woven fabric, fiber, inorganic fiber, SM
23. The substrate according to claim 1, which is any one of C and BMC. 24. A substrate having on its surface a film containing a plurality of types of titanium oxide compounds having different oxygen / titanium ratios. 25. A method for imparting functionality to a substrate surface by forming a layer containing a plurality of types of photocatalysts having different light absorption wavelengths on the surface. 26. The function is selected from the group consisting of hydrophilicity, antifogging property, self-cleaning property, antifouling property, and organic substance decomposability by photoexcitation of the layer containing the photocatalyst in response to light irradiation. Claim 2 is to exhibit properties.
6. The method for imparting functionality to a substrate surface according to 5. 27. The method for imparting functionality to a substrate surface according to claim 26, wherein the photoexcitation is possible by irradiation with visible light. 28. The method for imparting functionality to a substrate surface according to claim 25, wherein the layer containing the photocatalyst is formed by a dry process. 29. The method according to claim 28, wherein the dry process is selected from the group consisting of a vapor deposition method, a sputtering method, and an ion plating method. 30. The functional material according to claim 28, wherein the plurality of types of photocatalysts are formed on the surface of the substrate by changing film forming conditions of the dry process. How to give. 31. The method according to claim 30, wherein the film forming conditions are selected from the group consisting of a combination of target materials, a film forming atmosphere, and a film forming temperature. 32. The method according to claim 25, wherein the photocatalyst contains titanium oxide as a main component. 33. The method for imparting functionality to a substrate surface according to claim 32, wherein the titanium oxide contains a plurality of compounds having different oxygen / titanium ratios. 34. The method according to claim 34, wherein said titanium oxide is mainly composed of Ti2.
The method for imparting functionality to a substrate surface according to claim 33, comprising O3. 35. The method according to claim 34, wherein the titanium oxide further contains TiO2 as a main component. 36. The method according to claim 32, wherein the titanium oxide contains crystalline titanium oxide as a main component. 37. The method according to claim 36, wherein the titanium oxide further contains amorphous titanium oxide as a main component. 38. The method for imparting functionality to a substrate surface according to claim 25, wherein the layer containing the photocatalyst comprises a plurality of layers having different compositions. 39. The photocatalyst-containing layer is a layer whose composition continuously changes in the thickness direction.
8. The method for imparting functionality to a substrate surface according to 7. 40. The main component of the photocatalyst is titanium oxide, the film forming method is a dry process, and the layer containing the photocatalyst has a higher oxygen / titanium ratio in a layer closer to the surface in the thickness direction. 40. The method for imparting functionality to a substrate surface according to any one of 38 to 39. 41. A means for making the layer containing the photocatalyst a layer closer to the surface in the thickness direction with a higher oxygen / titanium ratio is to increase the substrate temperature as the layers closer to the surface are stacked. 41. The method for imparting functionality to a substrate surface according to claim 40. 42. A means for making the layer containing a photocatalyst a layer closer to the surface in the thickness direction with a higher oxygen / titanium ratio by increasing the oxygen concentration of the atmosphere as the layers closer to the surface are stacked. 41. The method for imparting functionality to a substrate surface according to claim 40, wherein: 43. A means for making the layer containing the photocatalyst a layer closer to the surface in the thickness direction so as to have a higher oxygen / titanium ratio. 41. The method for imparting functionality to a substrate surface according to claim 40, wherein the method is to use. 44. The substrate according to claim 25, wherein the photocatalyst-containing layer is formed by alternately or randomly stacking a plurality of types of layers having different compositions. How to grant. 45. The method according to claim 44, wherein the layer containing the photocatalyst is formed by a physical film forming method using a plurality of targets having different compositions. 46. The substrate surface according to claim 25, wherein the photocatalyst-containing layer further contains a substance exhibiting properties selected from the group consisting of water storage, hydrophilicity, and binder properties. How to give the property. 47. The method for imparting functionality to a substrate surface according to claim 46, wherein a main component of the substance exhibiting properties selected from the group consisting of water storage, hydrophilicity, and binder properties is silica. . 48. The content of a substance exhibiting properties selected from the group consisting of water storage, hydrophilicity, and binder properties, the greater the portion closer to the surface in the thickness direction of the photocatalyst-containing layer. 46. The method for imparting functionality to a substrate surface according to any one of 46 to 47. 49. A method for forming a layer containing the photocatalyst is a dry process, and a target selected from the group consisting of components constituting the photocatalyst and the water storage, hydrophilicity, and binder properties. 49. The method for imparting functionality to a substrate surface according to claim 46, wherein a target containing both components to be expressed is used. 50. The method for forming a layer containing a photocatalyst is a dry process, and the target is selected from the group consisting of a target containing a component constituting the photocatalyst and the water storage, hydrophilicity, and binder properties. 47. Both of the targets containing a component that expresses the properties of the target are used.
49. The method for imparting functionality to a substrate surface according to any one of items 48 to 48. 51. A layer containing a substance exhibiting properties selected from the group consisting of water storage, hydrophilicity, and binder properties is further formed on the photocatalyst-containing layer.
50. A method for imparting functionality to the surface of a substrate according to any one of Items 50 to 50. 52. The method for imparting functionality to a substrate surface according to claim 51, wherein a main component of the substance exhibiting properties selected from the group consisting of water storage, hydrophilicity, and binder properties is silica. . 53. Both the layer containing the photocatalyst and the layer containing a substance exhibiting properties selected from the group consisting of water storage, hydrophilicity and binder properties are formed by a dry process. 53. The method for imparting functionality to a substrate surface according to any one of the above items. 54. The photocatalyst-containing layer having a thickness of 10
The method for imparting functionality to a substrate surface according to any one of claims 25 to 50, wherein the thickness is from 10 nm to 10 µm, more preferably from 50 nm to 1 µm. 55. A layer containing a substance exhibiting properties selected from the group consisting of water storage, hydrophilicity, and binder properties, has a thickness of 5 nm to 2 μm, more preferably 10 nm to 2 μm.
55. The method for imparting functionality to a substrate surface according to claim 51, wherein the thickness is 00 nm. 56. The base material is a vehicle glass, a building window glass, a vehicle mirror, a road mirror, an instrument panel cover, an eyeglass lens, a helmet shield, goggles, a heat-insulating showcase, an ice-covered snow-proofing roof, and an icicle. Building prevention materials, ice and snow prevention antennas, communication obstacle prevention materials, ice and snow prevention transmission lines, cone discharge prevention materials, bathroom ceiling materials, toilet pipes, water supply pipes, urinals, toilet bowls, toilet traps, washbasins Bowl, wash basin, bathtub, bathroom wall material, bathroom flooring, bathroom grating, shower hook, bathtub handgrip, bathtub apron, bathtub drain plug, bathroom window, bathroom window frame, bathroom window Floorboards, bathroom lighting fixtures, drainage plates, drainage pits, bathroom doors, bathroom door frames, bathroom window bars, bathroom door bars, scallops, mats, soap basins, tubs, bathroom mirrors, bath chairs, transfer boxes − Bathroom components such as water heaters, bathroom storage shelves, bathroom handrails, bath lids, bathroom towel rails, shower chairs, basins, kitchen kitchen backs, kitchen flooring, sinks, kitchen counters, drainage Baskets, dish dryers, dishwashers, stoves, range hoods, ventilation fans, stove ignition parts, toilet flooring, toilet wall materials, toilet ceilings, ball taps, water taps, cigarette rolls, toilet seats, elevating Toilet seats, toilet doors, toilet bus keys, toilet towel rails, toilet lids, handrails for toilets, toilet counters, flush valves, tanks, toilet parts such as water spout nozzles for toilet seats with a washing function, sink traps, and sinks Mirrors, storage shelves for sinks, drain cocks, toothbrush stands, lighting equipment for wash mirrors, wash counters, water soap dispensers, wash basins, mouth washer, hand dryers, washing tubs, washing machine lids, washing machine pans, Prolapse Bath, air conditioner filter, touch panel, faucets, human body sensor -
Cover, shower hose, shower head, shower
Water discharge part, sealant, joint, wallpaper, refrigerated case, camera finder, greenhouse ceiling, car interior mirror, dental mirror, wallpaper, steel coil, tent, film, sheet, woven fabric, non-woven fabric, fiber, inorganic fiber, SM
The method for imparting functionality to a substrate surface according to any one of claims 25 to 55, wherein the method is one of C and BMC. 57. A film containing a plurality of types of titanium oxide compounds having different oxygen / titanium ratios is formed on the surface,
A method for imparting functionality to a substrate surface. 58. An apparatus for imparting functionality to a substrate surface, comprising a dry process means for forming a layer containing a plurality of types of photocatalysts having different light absorption wavelengths on the substrate surface.