JP2000135755A - Hydrophilic composite material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composite material excellent in durability and having high-degree hydrophilicity by forming an uneven structure on the surface of a base material so that the height and width of unevenness of the surface of the base material at an arbitrary position and the center line average surface roughness of the base material measured by an atomic force microscope are set to specific values. SOLUTION: A composite material is obtained by forming an uneven surface to a base material and forming a surface layer comprising metal oxide on the uneven surface so that the average height and average width of the unevenness of the surface layer at an arbitrary position measured by an atomic force microscope are 0.4-200 nm and the center line average surface roughness Ra thereof is 0.1-50 nm. Pref., the average height of the unevenness is 0.8-40 nm and the average width thereof is 9-100 nm and the center line average surface roughness Ra is 0.1-10 nm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a bathroom mirror, a bathroom window, a bathroom lighting fixture, a bathroom mirror, a vehicle glass, a building window glass, a vehicle mirror, a road mirror, an instrument panel cover,
Glasses lenses, helmet shields, goggles, heat-insulating showcases, sinks, system kitchens or part thereof, such as sinks, traps, countertops, ventilation fans, cutting boards, tableware, kitchen components, washbasins, washbasins, Toilet members such as sinks, traps, faucet equipment, accessory storage shelves such as toothbrushes, toilet members such as toilet bowls, toilet seats, toilet lids, urinals, bathrooms, unit baths, saunas or inside Anti-fogging property and dew-proofing that can be suitably used in a so-called water environment such as a bathtub, a washing place, a water heater, a faucet device, a shower, a soap dish, a bath lid, a mirror, etc., and a washing machine. The present invention relates to a member having excellent properties, antifouling properties and self-purifying properties.

[0002]

2. Description of the Related Art As a method for preventing fogging, dew condensation, dirt, and the like, it has been conventionally performed to impart hydrophilicity to a substrate surface. As a method for imparting hydrophilicity, a method of coating a surface with a polymer having hydrophilicity, a method of applying a surfactant, and the like are known.

According to the method of forming a film having hydrophilicity, polyamides and polyacrylic acids, which are widely known hydrophilic polymers, are soft and have a drawback that the film strength is low when the film is formed. Was. In addition, since the surfactant flows down with water, there is a drawback that the surfactant is not durable in an environment where water is used.

[0004]

SUMMARY OF THE INVENTION In view of the above circumstances, an object of the present invention is to provide a hydrophilic composite material having excellent durability and a high degree of hydrophilicity.

[0005]

According to the present invention, in order to solve the above-mentioned problems, the height and width of irregularities at an arbitrary position on the substrate surface measured by an atomic force microscope are 0.4 n.
m or more and 200 nm or less, and the center line average surface roughness Ra
Provided a hydrophilic composite material having an uneven structure having a thickness of 0.1 nm or more and 50 nm or less. By forming such an uneven structure on the substrate surface, it exhibits high hydrophilicity without deteriorating the texture of the substrate, exhibits sufficient anti-fogging and water droplet preventing effects, adheres contaminants, It has become possible to provide articles with improved cleanliness.

The height, width and surface roughness of the irregularities on the substrate surface can be determined by using an atomic force microscope. When measuring a complex and fine uneven surface, the adsorbed water on the surface and the gas entering the surface interfere with each other, and accurate values cannot be obtained with a contact-type surface roughness meter. The measurement is preferably performed using a force microscope. It is preferable that the height and width of the unevenness be の of the wavelength of visible light, that is, 200 nm or less. This is because coloration of the surface layer due to light interference can be prevented, and the texture of the substrate is not impaired. The height and width of the unevenness are preferably 0.4 nm or more. If the height and width of the unevenness are smaller than this, mechanical strength cannot be secured. The surface roughness is mainly determined by the height of the unevenness, and the surface roughness (Ra) = height / 4 in the schematic surface cross section shown in FIG.
Here, since the height of the unevenness is preferably 0.4 nm or more and 200 nm or less, the surface roughness is preferably 0.1 nm or more and 50 nm or less.

In a preferred embodiment of the present invention, the average height of the unevenness at an arbitrary position on the surface of the substrate is 0.8 nm or more and 40 nm or less, and the average width of the unevenness is 9 nm or more and 100 nm or less.
m or less, and the center line average surface roughness Ra is 0.1 nm.
At least 10 nm or less. By forming the uneven structure in this range, antifogging and antifouling properties required for high hydrophilicity can be obtained.

According to the present invention, there is further provided a hydrophilic composite material characterized in that the uneven structure is a fractal structure. The fractal structure is a multi-level uneven structure including a large-period uneven structure on the surface of the base material and a small-period uneven structure in the structure. By using a fractal structure, that is, a complex structure having finer irregularities in the irregularities, it is possible to increase the water retention ability of the substrate surface and to express a higher degree of hydrophilicity.

[0009] In a preferred aspect of the present invention, the concavo-convex structure is formed of a layer containing one or more metal oxides, which is bonded to the surface of the substrate. By including one or more oxides, desired irregularities exhibiting high hydrophilicity can be easily formed.

In a preferred aspect of the present invention, the thickness of the layer is set to 400 nm or less. By setting the thickness as described above, a transparent film having excellent anti-fogging property and free from light interference and white turbidity can be formed.

In a preferred embodiment of the present invention, the layer is formed by a sol coating method. According to the sol coating method, there is no restriction on equipment depending on the size and shape of the base material, so that a film can be easily formed on the base material surface without requiring special equipment.

In a preferred embodiment of the present invention, the layer is formed by vacuum deposition. According to the vacuum evaporation, a transparent film having uniform and excellent antifogging properties can be formed regardless of the type of the base material and the type of the oxide used.

In a preferred embodiment of the present invention, the layer is formed by sputtering. According to sputtering, a uniform and strong film can be formed.

In a preferred aspect of the present invention, the layer is formed by CVD. According to CVD, a film having better durability can be formed.

In a preferred embodiment of the present invention, the metal oxide is selected from the group consisting of silica, alumina, zirconia, titania, tin oxide and zinc oxide. By using these oxides, a highly hydrophilic surface having excellent water resistance and chemical resistance can be obtained. Among these metal oxides, it is preferable to use zirconia, titania, tin oxide, and zinc oxide having photocatalytic activity.
By doing so, a higher degree of hydrophilicity can be obtained by indoor lighting or ultraviolet rays from windows.

In a preferred aspect of the present invention, the uneven structure is formed by chemical etching. According to chemical etching, a hydrophilic surface which also has antireflection is obtained.

In a preferred embodiment of the present invention, after forming a concavo-convex structure by any of the above methods, a surface layer made of a metal oxide is further formed on the concavo-convex surface, and the surface of the layer is measured by an atomic force microscope. The average height and average width of the unevenness at any drop are 0.4 nm or more and 200 nm or less, and the center line average roughness Ra is 0.1 nm or more and 50 nm or less.
Make sure that: By forming further irregularities on the surface having the predetermined irregular structure, the surface becomes finer irregularities, and the hydrophilicity is further improved by increasing the surface area.

In a preferred aspect of the present invention, the average height and average width of the irregularities are 0.4 nm or more and 200 nm or less, and the center line average surface roughness Ra is 0.1 nm or more and 5 nm or more.
It is preferably 0 nm or less. By making the surface of the substrate on which the fine irregularities are formed more irregular, the surface structure becomes complicated and the hydrophilicity is further improved.

In a preferred embodiment of the present invention, a surface having irregularities and a surface layer made of a metal oxide are further formed on the irregular surface, and the irregularities at arbitrary positions on the surface layer measured by an atomic force microscope. And a layer having a center line average surface roughness Ra of 0.1 nm or more and 50 nm or less. A hydrophilic surface can be obtained by further forming irregularities on the surface on which the irregularities have been formed in advance. Further, even if the surface has interference fringes and cloudiness, there is also an effect of eliminating these and making the surface transparent.

In a preferred embodiment of the present invention, the average height and average width of the irregularities are 0.4 nm or more and 200 nm or less, and the center line average surface roughness Ra is 0.1 nm or more and 5 nm or more.
0 nm or less.

In a preferred aspect of the present invention, the uneven surface is formed by vacuum evaporation. As described above, according to the vacuum deposition, a transparent film having a uniform and excellent antifogging property can be formed regardless of the type of the base material and the type of the oxide used.

In a preferred aspect of the present invention, the uneven surface is formed by sputtering. According to sputtering, a uniform and strong film can be formed.

In a preferred aspect of the present invention, the uneven surface is formed by CVD. According to CVD, a film having better durability can be formed.

In a preferred aspect of the present invention, the uneven surface is formed by chemical etching. Chemical etching is suitable for forming irregularities on the surface of an inorganic base material such as a mirror or glass. In the case of a mirror or glass, a hydrophilic surface also having antireflection can be obtained.

In a preferred embodiment of the present invention, it is formed by a sol coating method. This is because sols of metal oxides having various particle diameters and properties can be obtained, so that an appropriate sol can be selected according to the unevenness of the substrate formed in advance.

In a preferred embodiment of the present invention, the metal oxide film is preferably formed by sputtering. According to sputtering, a uniform and strong film can be formed.

In a preferred aspect of the present invention, the metal oxide film is formed by CVD. According to CVD, a film having better durability can be formed.

In a preferred embodiment of the present invention, the metal oxide is preferably selected from the group consisting of silica, alumina, zirconia, titania, tin oxide and zinc oxide.
By using these metal oxides, it is easy to obtain unevenness having good hydrophilicity. Among these metal oxides, it is preferable to use zirconia, titania, tin oxide, and zinc oxide having photocatalytic activity. By doing so, a higher degree of hydrophilicity can be obtained by indoor lighting or ultraviolet rays from windows.

[0029]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The composite material that can be used in the present invention is not limited to articles used around water in a house, but can be widely used for those used in an environment with water. For example,
Bathroom mirrors, bathroom windows, bathroom lighting fixtures, toilet mirrors, vehicle glass, building window glass, vehicle mirrors, road mirrors, instrument panel covers, eyeglass lenses, helmet shields,
Goggles, thermal showcases, bathroom wall materials, bathroom flooring, bathtubs, bathroom gratings, bathroom ceilings, showers
Hook, bathtub handgrip, bathtub apron part, bathtub drain plug, bathroom window, bathroom window frame, bathroom window floorboard, bathroom lighting fixture, drainage plate, drain pit, bathroom door, bathroom door frame, bathroom window rail , Bathroom door bar, sink, mat, soap box, tub, bathroom mirror, bath chair, transfer board, water heater, bathroom storage shelf, bathroom railing, bath lid, bathroom towel rail, shower Bathroom materials such as chairs and basins, kitchen kitchen backs, kitchen flooring, sinks, kitchen counters, drain baskets, dish dryers, dishwashers, stoves, range hoods, ventilation fans, stove ignition Parts, kitchen components such as stove knobs, urinals, urinals, toilet traps, toilet plumbing, toilet flooring, toilet wall materials,
Ceiling for toilet, ball tap, water stopcock, cigarette, toilet seat, elevating toilet seat, toilet door, toilet key, toilet towel rail, toilet lid, toilet railing, toilet counter, flash valve, tank , Toilet parts such as water spout nozzles for toilet seats with wash functions, wash basins, wash basins, toilet mirrors, wash basins, drain plugs, toothbrush stands, wash mirror luminaires, wash counters, water soap dispensers,
Covers for washbasins, mouth washers, hand dryers, washing towels such as rotating towels, washing tubs, washing machine lids, washing machine pans, dehydration tubs, air conditioner filters, touch panels, faucet fittings, human body detection sensors , Shower hoses, shower heads, shower spouts, sealants, joints, etc.

In the present invention, the material of the substrate may be basically any material such as ceramic, ceramic material, metal, glass, plastic, decorative plywood, calcium silicate, mortar or a composite thereof. The shape of the substrate may be any shape, for example, a mirror, a tile, a wall material, a plate-like material such as a floor material, a sphere, a cylinder, a cylinder, a rod, a prism,
Even simple shapes such as hollow prisms, sanitary ware,
Complex shapes such as wash basins, bathtubs, sinks, and their accessories may be used.

In the present invention, the method of forming the irregularities on the surface of the substrate is not limited, and may be selected from known methods, such as a sol coating method, a plating method, and a CVD method.
Method, a method of forming a film having fine irregularities on the substrate surface by a method such as sputtering, vacuum deposition, a method of forming irregularities directly on the substrate, such as sandblasting, etching, etc. There is a method of forming unevenness and transferring the unevenness to the substrate.

In the present invention, it is preferable to coat a layer containing at least one metal oxide on the surface of the substrate.
According to this, desired irregularities exhibiting high hydrophilicity can be easily formed. As a method of coating the oxide, a sol coating method, vacuum deposition, sputtering,
The method may be selected from known methods such as a CVD method and a plating method, and may be other methods. According to the sol coating method, since there is no restriction on the equipment depending on the size and shape of the base material, the sol coating method can be easily performed without requiring special equipment. According to the CVD method, sputtering, and vacuum deposition, application to a large base material is restricted by equipment, but a uniform and stable thin film can be formed. By increasing the treatment temperature in these methods, it is possible to further improve the durability such as alkali resistance and hot water resistance.

In the present invention, the thickness of the oxide film is set to 400 nm or less. In particular, when a film having a thickness of more than 400 nm is formed using one kind of oxide, interference fringes, turbidity, and the like due to light interference occur, and defects in appearance are likely to occur. Also, as the film thickness increases, the abrasion resistance decreases, and it is inevitable that the film is easily damaged.

Here, as the metal oxide, silica, alumina, zirconia, ceria, yttria, boronia,
Magnesia, calcia, ferrite, hafnia, titanium oxide, zinc oxide, tungsten trioxide, ferric oxide, cuprous oxide, cupric oxide, bismuth trioxide, tin oxide,
Single oxides such as nickel oxide, cobalt oxide, barium oxide, strontium oxide, and vanadium oxide, and barium titanate, calcium silicate, water glass, aluminosilicate, calcium phosphate, strontium titanate,
Composite oxides such as potassium titanate, barium titanate, calcium titanate, and aluminosilicate can be suitably used. Among them, it is preferable to use any of silica, alumina, zirconia, titania, tin oxide, and zinc oxide. Silica and alumina are preferred for forming small and fine irregularities, and zirconia and
Titania, tin oxide and zinc oxide are preferred. In the sol coating method, silica, from which various things can be obtained regarding the particle diameter and the sol properties described below, is preferable. Silica is the cheapest and very practical.

In the present invention, the metal oxide particles are preferably in the form of a sol dispersed in water or a hydrophilic solvent in a colloidal state. The hydrophilic solvent is not particularly limited as long as it can stably disperse the metal oxide and form a uniform and smooth film on the substrate, but is preferably an organic solvent having a boiling point of 200 ° C. or lower. Solvents can be mentioned. Examples of preferred organic solvents include methanol, ethanol, n-propanol, isopropanol, t-butanol, isobutanol, and n-butanol.
2-methylpropanol, pentanol, ethylene glycol, monoacetone 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,
Alcohol solvents such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether and 2-butoxyethanol, and hydrocarbon solvents such as n-hexane, toluene, xylene and mineral spirits Examples of the solvent include ester solvents such as methyl acetate, ethyl acetate, and butyl acetate.

In the present invention, when a film is formed on the surface of the base material by the sol coating method, the metal oxide is used in an amount of 0.0
It is preferable to use a coating composition containing 5 to 20 parts by weight and 99.95 to 80 parts by weight of a solvent. By coating the coating solution on the surface of the base material, a transparent film having excellent antifogging properties and free from light interference and white turbidity can be formed.

In the case of the sol coating method, a granular metal oxide having an average particle diameter of 1 to 100 nm, an average diameter of 1 to 50 n
m, a chain metal oxide having an average length of 10 to 1000 nm, and a feather or rod-shaped metal oxide having an average diameter of 1 to 50 nm and an average length of 10 to 500 nm are preferably used. Examples of the granular metal oxide having an average particle diameter of 1 to 100 nm include silica and zirconia, and an average diameter of 1 to 50 n.
m, as the chain metal oxide having an average length of 10 to 1000 nm, silica, alumina, etc., an average diameter of 1 to 50 nm,
Examples of the feather-like or rod-like metal oxide having an average length of 10 to 500 nm include alumina and titania. If a chain-like, feather-like, or rod-like metal oxide is used, the durability of the film formed on the substrate surface can be improved. Also,
When a granular inorganic oxide is used, a film having desired unevenness and higher smoothness can be formed.

In the present invention, the base material surface layer preferably contains a binder for fixing the metal oxide on the base material surface. This is because the binder improves the adhesion to the substrate surface, and provides higher durability and abrasion resistance. As the binder, an inorganic binder such as glaze or silicone, an organic binder such as a thermosetting resin, a photocurable resin, or a thermoplastic resin can be used.

In the present invention, the coating liquid may contain a surfactant. Examples of surfactants that can be added include polyoxyethylene alkylphenyl ether ammonium sulfonate, sodium polyoxyethylene alkylphenyl ether sodium sulfonate, fatty acid soap, fatty acid sodium soap, dioctyl sodium sulfosuccinate, Alkyl sulfate, alkyl ether sulfate, alkyl sulfate soda salt, alkyl ether sulfate soda salt, polyoxyethylene alkyl ether tersulfate, polyoxyethylene alkyl ether tersulfate Da salt,
Alkyl sulfate TEA salt, polyoxyethylene alkyl ether sulfate TEA salt, 2-ethylhexyl alkyl sulfate sodium salt, sodium acylmethyltaurate, sodium lauroylmethyltaurate, sodium dodecylbenzenesulfonate, lauryl sulfosuccinate Disodium, disodium lauryl polyoxyethylene sulfosuccinate, polycarboxylic acid, oleoyl sarcosine, amide ether sulphate
Anionic surfactants such as sodium, lauroyl sarcosine and sodium sulfo FA ester; polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene acetyl ether, polyoxyethylene stearyl Ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether
Ter, polyoxyethylene alkyl ester, polyoxyethylene alkyl phenol ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene laura
Polyoxyethylene stearate, polyoxyethylene alkylphenyl ether, polyoxyethylene oleate, sorbitan alkyl ester, polyoxyethylene sorbitan alkyl ester, polyether-modified silicone, polyester-modified silicone Sorbitan laurate, sorbitan stearate, sorbitan palmitate, sorbitan sesquioleate, sorbitan oleate, polyoxyethylene sorbitan laurate,
Polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan oleate, glycerol stearate,
Polyglycerin fatty acid ester, alkyl alkylamide, lauric acid diethanolamide, oleic acid diethanolamine, oxyethylene dodecylamine, polyoxyethylene dodecylamine, polyoxyethylene alkylamine, polyoxyethylene octadecylamine, polyoxyethylene alkyl Propylene diamine,
Nonionic surfactants such as polyoxyethylene oxypropylene block polymer and polyoxyethylene stearate; amphoteric surfactants such as dimethyl alkyl betaine, alkyl glycine, amido betaine and imidazoline; octadecyl dimethyl benzyl ammonium chloride, alkyl dimethyl Benzyl ammonium chloride, tetradecyl dimethyl benzyl ammonium chloride, dioleyl dimethyl ammonium chloride, 1
-Hydroxy-2-alkylimidazoline quaternary salt, alkylisoquinolinium bromide, polymer amine, octadecyltrimethylammonium chloride, alkyltrimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, behenyltrimethylammonium chloride, alkylimidazoline Cationic surfactants such as quaternary salts, dialkyldimethylammonium chloride, octadecylamine acetate, tetradecylamine acetate, alkylpropylenediamine acetate, and didecyldimethylammonium chloride.

In the present invention, the method of applying the coating solution on the surface of the substrate may be appropriately selected from known methods.
Spray coating method using air gun, airless gun, aerosol spray, etc., spin coating method,
Examples include, but are not limited to, dip coating, flow coating, roll coating, brush coating, and sponge coating. In addition, various shampoos, primers, detergents, compounds, antistatic agents, and the like can be used as a treatment before applying the coating liquid to the substrate surface.

The heat treatment after applying the coating solution to the surface of the substrate may be appropriately performed according to the type and properties of the coating solution and the substrate, and may be any method such as natural drying, heating, and infrared / ultraviolet irradiation. In some cases, the solvent may simply be evaporated and dried. As a method of performing the heat treatment, the surface treatment agent is applied to the surface of the article and then the heat treatment is performed. The number of times of the application and the heat treatment may be two or more. There are various methods such as performing heat treatment at once after repeating application only a plurality of times and performing a series of operations of coating and heat treatment a plurality of times.

In the present invention, it is preferable to form irregularities on the substrate surface by chemical etching. Chemical etching is a method in which a substrate is immersed in a solution of, for example, an acid, an alkali, or a peroxide or brought into contact with steam generated when the solution is heated, and a surface treatment is performed by a chemical reaction. Examples of the solution to be used include aqueous solutions of hydrochloric acid, sulfuric acid, ammonium sulfide, hydrofluoric acid, boron fluoride, hydrofluoric acid and the like.

It is also possible to further form a coating with a metal oxide on the surface of the substrate having the irregularities formed by a method such as vacuum deposition, sputtering, CVD, or etching. In particular, it is preferable to use silica, alumina, zirconia, titania, tin oxide, and zinc oxide. Among these metal oxides, those having photocatalytic activity such as zirconia, titania, tin oxide, and zinc oxide are preferably used. The hydrophilicity of the photocatalyst makes it possible to further enhance the hydrophilicity in the presence of ultraviolet light obtained from indoor lighting, incident light from windows, and the like. Further, the effect of decomposing and deodorizing can be expected by the decomposition function of the photocatalyst. It is preferable to use these oxide sols and form them by a sol coating method. Sols having various particle diameters and properties are available, and an optimum sol can be selected so as to enter the concave portions formed on the surface. The oxide sol includes the various metal oxides described above.
m or less is preferable. This is because the surface of the base material surface is increased because of entering the unevenness formed in advance, and the hydrophilicity is further enhanced. Also, sputtering or CVD
The method of forming the oxide film by the above method is also preferable.
According to the sputtering or the CVD, it is possible to form a film utilizing the unevenness of the hydrophilic composite material before forming the film. By increasing the processing temperature in CVD or sputtering, it is possible to further improve durability such as alkali resistance and hot water resistance.

Further, metal particles can be fixed to the outermost surface of the substrate by a photoreduction method. In this case, the hydrophilic function can be enhanced by adding a metal having an electron capturing effect. Metals having an electron trapping effect include Pt, Pd, Au, Ag, Cu, Ni, Fe, C
It refers to metals such as o and Zn which have a small ionization tendency and are easily reduced. These metals may be used in combination. In this case, the average particle diameter of the metal is preferably 200 nm or less. This is to prevent color formation and white turbidity due to light interference and irregular reflection.

It is also possible to fill the gaps between the metal oxide layer particles formed on the substrate surface with particles having a smaller particle size than the gaps. By filling the gaps with particles, the surface area of the substrate surface can be increased, which leads to improvement in hydrophilicity. In addition, the particles filled in the gaps can bind the metal oxide layer particles, and the adhesion to the base material is improved. As particles having a particle size smaller than the gap,
Sn, Ti, Ag, Cu, Zn, Fe, Pt, Co, P
d, Ni and the like. If the metal having the electron capturing effect is filled, further improvement in hydrophilicity can be expected.

[0046]

EXAMPLES Example 1 Chain Colloidal Silica 1% Chain colloidal silica (solids concentration 15-16%, pH
(2-4, particle diameter 40-100 nm) was diluted with ethanol to prepare a 1% by weight coating solution. The coating solution was contained in a cloth, applied to a 10 cm square mirror, and dried naturally to obtain a sample. The following five items were evaluated using the above samples.
Table 1 shows the results.

Example 2: Chain colloidal silica 20% Chain colloidal silica (solid content: 15 to 16%, pH
(2-4, particle diameter 40-100 nm) as it was in a stock solution, contained in a cloth, applied to a 10 cm square mirror, and dried naturally to obtain a sample. The following five items were evaluated using the above samples. Table 1 shows the results.

Example 3: Spherical colloidal silica 1% Spherical colloidal silica (solid content: 30 to 31%, particle diameter: 8 to 11 nm);
g was added and diluted with water to prepare a 1% by weight coating solution. The coating solution was contained in a cloth, applied to a 10 cm square mirror, and dried naturally to obtain a sample. The following five items were evaluated using the above samples. Table 1 shows the results.

Example 4 Spherical Colloidal Silica 1% Spherical colloidal silica (solid content: 30 to 31%, particle size: 8 to 11 nm) was diluted with water to prepare a 1% by weight coating solution. The coating solution was contained in a cloth, applied to a 10 cm square mirror, and dried naturally to obtain a sample. Using the above sample,
The following five items were evaluated. Table 1 shows the results.

Example 5: Alumina sol 1% rod-shaped alumina sol (solids concentration 20 to 22%, particle size 1
(0 to 20 nm) was diluted with ethanol to prepare a 1% by weight coating solution. The coating solution was contained in a cloth, applied to a 10 cm square mirror, and dried naturally to obtain a sample. The following five items were evaluated using the above samples. Table 1 shows the results.

Example 6 Zirconia Sol 1% A spherical zirconia sol (solid content 30 to 31%, particle diameter 60 to 70 nm) was diluted with ethanol to prepare a 1% by weight coating solution. The coating solution was contained in a cloth, applied to a 10 cm square mirror, and dried naturally to obtain a sample. The following five items were evaluated using the above samples. Table 1 shows the results.

Example 7: 1% titania sol Anatase type titania sol (solid content: 10%) was diluted 10 times with water to prepare a coating solution. The coating solution was contained in a cloth, applied to a 10 cm square mirror, and dried naturally to obtain a sample. The following five items were evaluated using the above samples. Table 1 shows the results.

Example 8: Lithium silicate Lithium silicate (SiO ₂ solid concentration: 20 to 21)
%, Li ₂ O solid content concentration of _{2 to} 3.5%)
The sample was applied to a 10 cm square mirror by being included in a cloth, and was naturally dried to obtain a sample. The following five items were evaluated using the above samples. Table 1 shows the results.

Example 9: Addition of a binder Spherical colloidal silica (solid content: 30 to 31%, particle size: 8 to 11 nm); 10 g, polyvinyl alcohol 5%
Aqueous solution (manufactured by Nippon Synthetic Chemical Co., Ltd., NH26); 2 g, silane coupling agent (manufactured by Nippon Unicar Co., Ltd., A110
0); 0.02 g, surfactant; 0.4 g, water; 90 g
Was mixed to prepare a coating solution. The coating solution was contained in a cloth, applied to a 10 cm square mirror, and dried naturally to obtain a sample. The following five items were evaluated using the above samples. Table 1 shows the results.

Comparative Example 1: Mirror For comparison with the above embodiment, no treatment was performed.
A 0 cm square mirror was prepared, and the following five items were evaluated. Table 1 shows the results.

Evaluation Items 1. Surface roughness (Ra), average height of unevenness (H), average width of unevenness (L): Measured in an AFM (atomic force microscope) mode of a scanning probe microscope (D3000 manufactured by Digital Instruments). 2. Anti-fogging property: Stored in a refrigerator (about 0 ° C.) for 5 minutes, and then left in an atmosphere of 28 ° C. and 81% humidity to check the surface for fogging. ◎: Not fogged at all and does not affect the reflected image, ：: No fogging, but slightly reflected image, Δ: Slightly fogged, X: Clearly fogged. 3. Dropping property: Place the sample on a vertical surface, pour water on it, and visually check the state of water wetting after 1 minute. ◎: 100% wet area, ○: 80% or more wet area 1
Less than 00%, Δ: 60% or more and less than 80% of water-wetted surface, ×:
Evaluated in 4 steps of less than 60% water wet area. 4. Abrasion resistance: Sliding with a sponge and checking for abnormalities in appearance. ◎: No abnormality at all, ：: Slight scratches that can be seen when exposed to light, △: Shallow scratches, X: Deep scratches reaching the substrate, evaluated on four levels. 5. Cleanability: After applying artificial grime to the sample, spray it with water by spraying to check the dirt removal. ◎: The dirt is completely removed by one spraying of water, ○: The dirt is completely removed by three to four sprays of water, Δ: 3 to 4 spraying
The dirt is slightly left with the water, but the dirt remains.

[0057]

[Table 1]

As can be seen from Table 1, it was confirmed that by applying various sols to the surface of the base material, good antifogging property, drip property and cleaning property were exhibited. In addition, regarding the particle shape, it was confirmed that the chain sol had better wear resistance than the spherical sol. Further, when a spherical sol was used, it was confirmed that the abrasion resistance was improved by adding a binder.

Example 10: Evaluation at Various Solid Concentrations Chain colloidal silica (solid content 20%, particle diameter 40)
-100 nm) with a silica solids concentration of 20% (no dilution)
Coating solutions having various concentrations of 0.01% were prepared. Each of the coating solutions having various concentrations was contained in each sponge of 10 g / m ² and applied to a transparent glass plate to obtain a sample. The various samples prepared as described above were evaluated for transparency, anti-fogging property, and dropping property. The antifogging property and the dropping property were evaluated in the same manner as in Examples 1 to 9. Regarding the transparency, ：: no interference fringes can be seen in any way, ○: interference fringes can be seen slightly by applying light, Δ: interference fringes, ×: interference fringes
There was white turbidity. In addition, workability for coating was evaluated so as to satisfy the above three items.
Table 2 shows the evaluation results.

[0060]

[Table 2]

As can be seen from Table 2, in the case of the sol coating method, it can be confirmed that the solid content concentration for satisfying all of the transparency, anti-fogging property and dropping property is 20% to 0.05%. Was.

Example 11 Evaluation of Antifogging and Antifouling of Various Films Silica was coated on a polyethylene terephthalate (PET) film by DC reactive sputtering. This film was adhered to a mirror to obtain Sample 1. Similarly, silica was coated on the PET film by EB evaporation. This film was adhered to a mirror to obtain Sample 2. Similarly, alumina was coated on a PET film by EB evaporation. This film was adhered to a mirror to obtain Sample 3. For comparison, the PET films as the substrates of Samples 1 to 3 were also adhered to a mirror to obtain comparative samples.

The following evaluation was performed on these samples. 1. Surface roughness (Ra), average height of unevenness (H), average width of unevenness (L): Measured in an AFM (atomic force microscope) mode of a scanning probe microscope (D3000 manufactured by Digital Instruments). 2. Anti-fogging property: Stored in a refrigerator (about 0 ° C.) for 5 minutes, and then left in an atmosphere of 28 ° C. and 81% humidity to check the surface for fogging. The initial antifogging property and the antifogging property after one week exposure were evaluated. ◎: Not fogged at all and does not affect the reflected image, ：: No fogging, but slightly reflected image, Δ: Slightly fogged, X: Clearly fogged. 3. Antifouling property: Stain adhesion after exposure for one week was visually checked. ：: No contamination was observed, and the initial cleanliness was maintained.
：: Slightly adhered, but does not affect use. △: Dirty adhered and there is a part where the mirror is difficult to see. ×: Surface is cloudy with dirt. Rated on a scale. The sample was exposed for one week under a mirror in an 80 cm square shower booth, and repeated bathing of four persons per day was performed. Table 3 shows the evaluation results.

[0064]

[Table 3]

As can be seen from Table 3, the comparative sample had no antifogging property at all. On the other hand, all of Samples 1 to 3 showed good antifogging properties without affecting the reflection image both after the initial exposure for one week. Further, regarding the antifouling property, the surface of the comparative sample became cloudy due to adhesion of dirt. On the other hand, sample 1
No contamination was observed in any of Nos. 1 to 3, and the initial cleanliness was maintained. It was confirmed that good antifogging and antifouling properties can be obtained by coating the substrate with an inorganic oxide of silica or alumina by DC reactive sputtering or EB vapor deposition to form irregularities.

Example 12: Hydrofluoric acid treatment (chemical etching) A 20 cm square mirror surface was chemically etched with hydrofluoric acid to form fine irregularities to obtain a sample. The same evaluation as in Example 11 was performed using this sample. Table 3 shows the evaluation results.

As can be seen from Table 3, good anti-fogging properties which did not affect the reflection image were exhibited at the initial stage and after exposure for one week. Further, no stain was attached, and the initial cleanliness was maintained. From this, it was confirmed that good antifogging property and antifouling property can be obtained by forming irregularities on the surface by hydrofluoric acid treatment.

Example 13 Treatment with Hydrofluoric Acid Solution (Chemical Etching) A 20 cm square mirror was treated with a hydrofluoric acid solution to form fine irregularities to obtain a sample. The same evaluation as in Example 11 was performed using this sample. Table 3 shows the evaluation results.

As can be seen from Table 3, good anti-fogging properties which did not affect the reflection image were exhibited at the initial stage and after exposure for one week. Further, no stain was attached, and the initial cleanliness was maintained. From this, it was confirmed that good antifogging property and antifouling property can be obtained by forming irregularities on the surface by treatment with hydrofluoric acid solution.

Example 14: CVD method (tin oxide) A 20 cm square mirror surface was coated with tin oxide by a CVD method to obtain a sample. This sample was divided into three equal parts, and the same evaluation as in Example 11 was performed using one sheet. The remaining two sheets were evaluated for warm water resistance and alkali resistance. Warm water resistance was evaluated by immersing in 95 ° C. warm water for 12 hours and then visually checking for abnormal appearance. Alkali resistance was evaluated by immersing in 5% NaOH for 12 hours. It was performed by a method of visually confirming the presence or absence of an abnormality. Warm water resistance,
The same evaluation as in Example 11 was performed using the sample for which the alkali resistance was evaluated. Table 3 shows the evaluation results.

As can be seen from Table 3, both in the initial stage and after one week of exposure, good antifogging properties without affecting the reflected image were exhibited. Further, no stain was attached, and the initial cleanliness was maintained. No abnormality due to warm water or alkali was observed,
It was confirmed that the antifouling property was not affected. From this, it was confirmed that by forming tin oxide by coating the tin oxide by the CVD method, the anti-fogging property and anti-fouling property resistant to hot water and alkali can be obtained.

Example 15: Treatment of Uneven Surface with Inorganic Oxide Sol By treating with a hydrofluoric acid solution, a mirror surface having fine unevenness was formed on the surface of the spherical colloidal silica (solid concentration: 30 to 31%, particle size: 8-11 nm), lithium silicate, and a mixture of the above-mentioned spherical colloidal silica and the above-mentioned lithium silicate were coated with three types of sols, respectively, to obtain three types of samples. At the time when the irregularities were formed on the mirror surface, slight turbidity was observed,
By coating the sols of any kind, no interference fringes or white turbidity were observed even when the surface was exposed to light. The same evaluation as in Example 11 was performed using this sample. Table 3 shows the evaluation results.

As can be seen from Table 3, both in the initial stage and after exposure for one week, good antifogging properties without affecting the reflected image were exhibited. Further, no stain was attached, and the initial cleanliness was maintained. From this, by forming a coating with a metal oxide on the surface of the substrate on which the unevenness has been formed in advance, and making the unevenness,
It was confirmed that good antifogging and antifouling properties were obtained.

Example 16: Treatment of uneven surface with titanium oxide sol Anatase-type titania sol (solid content: 15%) was diluted 15 times with ethanol to prepare a coating solution. The coating solution was applied by a flow coating method to a mirror surface having fine irregularities formed by a hydrosilicofluoric acid solution treatment, and naturally dried to obtain a sample. The same evaluation as in Example 11 was performed using this sample. Table 3 shows the evaluation results.

As can be seen from Table 3, both the initial and after one week exposure exhibited good antifogging properties without affecting the reflected image. Further, no stain was attached, and the initial cleanliness was maintained. From these results, it was confirmed that good antifogging and antifouling properties can be obtained by further applying a metal oxide sol to the surface of the substrate on which the unevenness has been formed in advance to form the unevenness.

Example 17: Treatment of uneven surface with alkoxide Titanium alkoxide solution (NDH510, manufactured by Nippon Soda)
C, solid content concentration 5%) was diluted twice with ethanol to prepare a coating solution. The coating solution was applied by a flow coating method to a mirror surface having fine irregularities formed by hydrofluoric acid solution treatment, and baked at 500 ° C. for 30 minutes to obtain a sample. Using this sample, the same evaluation and abrasion resistance as in Example 11 were performed. Evaluation of abrasion resistance was performed in Example 1.
-9 was performed in the same manner. Table 3 shows the evaluation results.

As can be seen from Table 3, both in the initial stage and after one week of exposure, good antifogging properties without affecting the reflected image were exhibited. Further, no stain was attached, and the initial cleanliness was maintained. In the wear resistance evaluation, no damage was found. From this, it was confirmed that the surface of the substrate on which the irregularities had been formed in advance was further coated with a metal oxide and fired to form the irregularities having good wear resistance. It was also confirmed that good antifogging and antifouling properties were obtained.

Example 18: Sputter treatment of uneven surface A silica sample was coated by a vacuum evaporation method, and a 20 cm square mirror surface on which unevenness was previously formed was further coated with titania by sputtering to obtain a sample. The same evaluation as in Example 11 was performed using this sample. Table 3 shows the evaluation results.

As can be seen from Table 3, both in the initial stage and after exposure for one week, good antifogging properties without affecting the reflected image were exhibited. Further, no stain was attached, and the initial cleanliness was maintained. From these results, it was confirmed that more excellent antifogging property and antifouling property can be obtained by further providing irregularities on the substrate surface having irregularities formed by vacuum deposition.

Example 19: Sputtering treatment 2 for uneven surface The silica was coated by sputtering, and a mirror surface of 20 cm square in which unevenness was previously formed was further coated with titania by sputtering to obtain a sample. The same evaluation as in Example 11 was performed using this sample. Table 3 shows the evaluation results.

As can be seen from Table 3, both in the initial stage and after exposure for one week, good antifogging properties without affecting the reflected image were exhibited. Further, no stain was attached, and the initial cleanliness was maintained. From these results, it was confirmed that more favorable anti-fogging property and anti-fouling property could be obtained by further providing irregularities on the surface of the base material having irregularities formed by sputtering.

Example 20: Sputtering treatment 3 of uneven surface The sample was obtained by coating tin oxide by a CVD method, and further coating silica by sputtering on a 20 cm square mirror surface on which predetermined unevenness was formed. The same evaluation as in Example 11 was performed using this sample. Table 3 shows the evaluation results.

As can be seen from Table 3, both in the initial stage and after one week of exposure, good antifogging properties without affecting the reflected image were exhibited. Further, no stain was attached, and the initial cleanliness was maintained. From these results, it was confirmed that more excellent antifogging property and antifouling property can be obtained by further providing irregularities on the surface of the substrate on which irregularities were formed by the CVD method.

Example 20: Relationship between Film Thickness and Antifogging and Antifouling Properties A 20 cm square mirror surface was coated with titania in various thicknesses by sputtering to obtain samples. Using this sample, antifogging and antifouling properties were evaluated in the same manner as in Example 11. The appearance was also evaluated. The method is described in Example 1
Same as 9. Table 4 shows the evaluation results.

[0085]

[Table 4]

As can be seen from Table 4, there is no difference in the antifogging and antifouling properties due to the difference in the film thickness within the range of this experiment. However, when the film thickness is 500 nm, interference fringes are observed and there is a problem in appearance. Was. From this, it was confirmed that the film thickness was preferably 400 nm or less.

[0087]

According to the present invention, the antifogging property, the antifogging property, the antifouling property, and the self-cleaning property are excellent in durability, have high hydrophilicity, and can be suitably used in an environment with water. It has become possible to provide an excellent composite material.

[Brief description of the drawings]

FIG. 1 shows a schematic diagram of a cross section of a substrate surface.

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Claims (28)

[Claims] 1. A composite material having a hydrophilic surface, wherein an average height and an average width of irregularities at an arbitrary position on a substrate surface measured by an atomic force microscope are 0.4 nm or more and 200 nm or more.
nm or less, and the center line average surface roughness Ra is 0.1 nm.
A hydrophilic composite material comprising a substrate having a concavo-convex structure having a thickness of at least 50 nm or less. 2. The uneven structure has an average height of 0.8 nm or more and 40 nm or less and an average width of the unevenness of 9 nm or more and 100 nm.
Hereinafter, the center line average surface roughness Ra is 0.1 nm or more and 10 n
The hydrophilic composite material according to claim 1, wherein m is equal to or less than m. 3. The hydrophilic composite according to claim 1, wherein the uneven structure is a fractal structure. 4. The hydrophilic material according to claim 1, wherein the composite material comprises a substrate and a layer bonded to the surface of the substrate and containing at least one metal oxide. Composite. 5. The hydrophilic composite according to claim 4, wherein the thickness of the layer is 400 nm or less. 6. The hydrophilic composite material according to claim 4, wherein the layer is formed by a sol coating method. 7. The hydrophilic composite material according to claim 4, wherein the layer is formed by vacuum evaporation. 8. The hydrophilic composite material according to claim 4, wherein the layer is formed by sputtering. 9. The hydrophilic composite according to claim 4, wherein the layer is formed by CVD. 10. The method according to claim 4, wherein the metal oxide is selected from the group consisting of silica, alumina, zirconia, titania, tin oxide, and zinc oxide.
10. The hydrophilic composite material according to any one of items 9 to 9. 11. Zirconia among the metal oxides,
The hydrophilic composite material according to claim 10, wherein the titania, tin oxide, and zinc oxide are photocatalysts. 12. The hydrophilic composite material according to claim 1, wherein the composite material is formed of a substrate having an uneven structure, and the uneven structure is formed by chemical etching. 13. After forming the concavo-convex structure according to any one of claims 1 to 12, a surface layer made of a metal oxide is further formed on the surface of the concavo-convex structure, and measured by an atomic force microscope. The average height and average width of the concavities and convexities at an arbitrary position on the surface layer are 0.4 nm or more and 200 nm or less, and the center line average surface roughness Ra is 0.1 nm or more and 50 nm or more.
A hydrophilic composite material comprising: 14. An average height of the irregularities is 0.8 nm or more and 40 nm or less, an average width of the irregularities is 9 nm or more and 100 nm or less, and a center line average surface roughness Ra is 0.1 nm or more and 10 nm.
The hydrophilic composite material according to claim 13, wherein: 15. A composite having a hydrophilic surface, comprising:
A substrate having a concavo-convex structure, further forming a surface layer made of a metal oxide on the substrate surface, the average height and average width of the concavities and convexities at any position of the surface layer measured by an atomic force microscope. , 0.4 nm or more and 200 nm or less,
A layer having a center line average surface roughness Ra of 0.1 nm or more and 50 nm or less. 16. The surface layer has an average height of irregularities of 0.8.
nm to 40 nm, average width of unevenness is 9 nm to 10
The hydrophilic composite material according to claim 15, wherein the hydrophilic composite material has a center line average surface roughness Ra of 0.1 nm or more and 10 nm or less. 17. The structure according to claim 15, wherein the uneven structure is formed by vacuum evaporation.
3. The hydrophilic composite material according to item 1. 18. The hydrophilic composite according to claim 15, wherein the uneven structure is formed by sputtering. 19. The hydrophilic composite material according to claim 15, wherein the uneven structure is formed by CVD. 20. The uneven structure according to claim 15, wherein the uneven structure is formed by chemical etching.
3. The hydrophilic composite material according to item 1. 21. The hydrophilic composite material according to claim 15, wherein the surface layer is formed by a sol coating method. 22. The hydrophilic composite material according to claim 15, wherein the surface layer is formed by sputtering. 23. The hydrophilic composite material according to claim 15, wherein the surface layer is formed by CVD. 24. The method according to claim 1, wherein the metal oxide is selected from the group consisting of silica, alumina, zirconia, titania, tin oxide, and zinc oxide.
24. The hydrophilic composite material according to 5 to 23. 25. Among the metal oxides, zirconia;
25. The hydrophilic composite according to claim 24, wherein titania, tin oxide, and zinc oxide are photocatalysts. 26. The hydrophilic composite material according to claim 1, wherein the hydrophilic composite material is any one of a bathroom mirror, a bathroom window, a bathroom lighting fixture, and a toilet mirror. 27. The hydrophilic composite 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,
The hydrophilic composite material according to any one of claims 1 to 25, wherein the hydrophilic composite material is any one of a heat insulating showcase. 28. The hydrophilic composite material, comprising: a bathtub, a bathroom wall material, a bathroom flooring, a bathroom grating, a bathroom ceiling, a shower hook, a bathtub handgrip, a bathtub apron,
Bathtub drain plugs, bathroom windows, bathroom window frames, bathroom window floor boards, bathroom lighting fixtures, drainage plates, drainage pits, bathroom doors, bathroom door frames, bathroom window bars, bathroom door bars, floorboards, mats, Soap rest, pail, bathroom mirror, bath chair, transfer box
Bathroom equipment, bathroom shelves, bathroom handrails, bathroom lids, bathroom towel rails, shower chairs, basins, etc. Kitchen counter, drainage basket, dish dryer,
Dishwashers, stoves, range hoods, ventilation fans, stove ignition parts, kitchen components such as stove knobs, urinals, urinals, toilet traps, toilet plumbing, toilet flooring, toilet wall materials, toilets Ceilings, ball taps, water stopcocks, cigarettes, toilet seats, lifting toilet seats, toilet doors, toilet bus keys, toilet towel rails, toilet lids, toilet railings, toilet counters, flush valves, tanks, Toilet components such as water nozzles on toilet seats with wash functions, wash bowls, wash traps, wash mirrors, wash shelves, drain plugs, toothbrush stands, wash mirror lighting fixtures, wash counters, water soap dispensers, wash basins , Mouth washers, hand dryers, washing parts such as rotating tiles, washing tubs, washing machine lids, washing machine pans, dehydration tubs, air conditioner filters, touch panels, faucet fittings, covers for human body detection sensors, Wa - E - scan, shower - head, shower - water discharger, shea - Holland, hydrophilic material according to claim 1 to 25, characterized in that either joint.