JP2008246968A - Water-repellent and oil-repellent anti-staining reflecting plate, its manufacturing method and tunnel, road sign, display plate, signboard, vehicle and building using water-repellent and oil-repellent anti-staining reflecting plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-repellent and oil-repellent anti-staining reflecting plate enhanced in water-repellent and oil-repellent anti-staining properties, water-repellent droplet separation properties (also said as water-repellent sliding properties) and durability such as abrasion resistance or weatherability, its manufacturing method and a tunnel, a road sign, a signboard, a vehicle and a building all of which use the water-repellent and oil-repellent anti-staining reflecting plate. <P>SOLUTION: The water-repellent and oil-repellent anti-staining reflecting plate 10 is manufactured by coating the surface of a base material 11 with a fine particle dispersion in which transparent fine particles 18 are dispersed, drying the coated base material to heat-treat the same in an oxygen-containing atmosphere to obtain a fine particle welded base material 19 and forming a water-repellent and oil-repellent anti-staining film 14 on the surface of the fine particle welded base material 19. The tunnel, the road sign, the signboard, the vehicle and the building all of which use the water-repellent and oil-repellent anti-staining reflecting plate are also disclosed. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a reflector having a highly durable and water-repellent / oil-repellent antifouling film formed on the surface thereof, and a method for producing the same, and more specifically, a tunnel that requires a water / oil repellent / antifouling function. The present invention relates to a water- and oil-repellent and antifouling reflector used for road signs, display boards, signs, vehicles such as automobiles, and outer walls in buildings such as buildings, and a method for manufacturing the same.

In general, a chemical adsorption solution consisting of a fluorocarbon group-containing chlorosilane-based adsorbent and a non-aqueous organic solvent can be used for chemical adsorption in the liquid phase to form a monomolecular film-like water / oil repellent / antifouling chemical adsorption film. Is already well known (see, for example, Patent Document 1).

The principle of production of a chemisorbed monolayer in such a solution is to form a monolayer using a dehydrochlorination reaction between active hydrogen such as hydroxyl groups on the substrate surface and chlorosilyl groups of chlorosilane-based adsorbents. It is in.

JP-A-4-132737

However, since the conventional chemical adsorption film uses only the chemical bond between the adsorbent and the flat substrate surface, the contact angle of the water droplet is only about 120 degrees, and the water droplets and dirt are naturally removed. Has the problem of poor water and oil repellency and antifouling properties and water separation. Moreover, the subject that durability, such as abrasion resistance and a weather resistance, was also scarce occurred.

The present invention relates to a water- and oil-repellent and water-repellent (water-sliding property) water-repellent and oil-repellent and water-repellent (water-sliding property) It is also intended to improve durability such as wear resistance and weather resistance.

The water / oil repellent / antifouling reflective plate according to the first invention provided as means for solving the above-mentioned problems is a plate-like base material and a water / oil / oil repellent preventive material fused to the surface of the base material. It has a dirty transparent fine particle and a water / oil repellent / antifouling coating covering a portion of the surface of the substrate where the transparent fine particle is not fused.

In the water / oil repellent / antifouling reflective plate according to the first aspect of the present invention, the transparent fine particles have a part of the surface fused to the surface of the substrate, and the other exposed part is the water repellent / repellent. It is preferably covered with an oil antifouling film.

In the water / oil repellent / antifouling reflective plate according to the first aspect of the present invention, it is preferable that the water / oil repellent / antifouling coating is covalently bonded to the surface of the transparent fine particles and the substrate.

In the water- and oil-repellent and antifouling reflective plate according to the first invention, the transparent fine particles having different particle diameters may be mixed and used.

In the water / oil repellent / antifouling reflective plate according to the first invention, the water / oil repellent / antifouling coating preferably contains —CF ₃ groups.

In the water / oil repellent / antifouling reflective plate according to the first invention, any one of silica, alumina, and zirconia, wherein the transparent fine particles are translucent and the softening temperature thereof is higher than the softening temperature of the substrate surface. It is preferable.

In the water- and oil-repellent and antifouling reflective plate according to the first invention, it is preferable that the transparent fine particles have a particle size of less than 400 nm.

In the water- and oil-repellent and antifouling reflective plate according to the first aspect of the invention, the contact angle with respect to water is preferably 130 degrees or more.

In the water / oil repellent / antifouling reflective plate according to the first aspect of the present invention, the transparent fine particles are melted on the surface of the base material through a film made of any one of a resin film, a silica glass film, and a coating film. It is preferable that the water / oil repellent / antifouling coating covers a portion where the transparent fine particles are not fused via the transparent coating.

In the water / oil repellent / antifouling reflective plate according to the first aspect of the present invention, it is preferable that the substrate is a light reflective stainless steel plate or an aluminum plate, and the coating is transparent.

In the water- and oil-repellent and antifouling reflective plate according to the first invention, the substrate is any one of paper, cloth, resin, glass plate, metal plate, and ceramic plate, and the coating is a dye, pigment, It is preferable to include one or more of metal fine particles and mica fine particles.

The tunnel according to the second invention is equipped with the water / oil repellent / antifouling reflecting plate according to the first invention on the wall surface.

The road sign according to the third invention uses the water / oil repellent antifouling reflector according to the first invention.

The display plate according to the fourth invention uses the water / oil repellent / antifouling reflective plate according to the first invention.

The signboard according to the fifth invention uses the water / oil repellent / antifouling reflecting plate according to the first invention.

A vehicle according to a sixth aspect uses the water / oil repellent / antifouling reflecting plate according to the first aspect inside and outside the vehicle body.

The building according to the seventh invention uses the water and oil repellent antifouling reflecting plate according to the first invention for the outer wall and the inner wall.

The method for producing a water- and oil-repellent and antifouling reflecting plate according to the eighth invention comprises a step C of preparing a fine particle dispersion in which transparent fine particles are dispersed, and applying and drying the fine particle dispersion on the surface of the substrate. The process D for attaching the transparent fine particles to the surface of the base material and the base material with the transparent fine particles attached to the surface are heat-treated at a temperature lower than the softening temperature of the transparent fine particles, A step E of fusing the transparent fine particles to the surface; a step F of washing and removing the transparent fine particles that have not been fused to the surface of the substrate; and a surface of the fine particle fused substrate to which the transparent fine particles are fused. And a step G of forming a water and oil repellent antifouling film.

In the method for producing a water- and oil-repellent and antifouling reflective plate according to the eighth invention, before the step D, the surface of the base material does not dissolve in the fine particle dispersion and has a temperature lower than that of the base material. The method may further include a step B of forming a film to be fused with the transparent fine particles.

In the method for producing a water- and oil-repellent and antifouling reflective plate according to the eighth aspect of the invention, it is preferable that the base material is a light-reflective stainless steel plate or an aluminum plate, and the coating is transparent.

In the method for producing a water / oil repellent / antifouling reflective plate according to the eighth invention, the substrate is any one of paper, cloth, resin, glass plate, metal plate and ceramic plate, and the coating is a dye. And any one or more of pigments, metal fine particles, and mica fine particles.

In the method for producing a water- and oil-repellent and antifouling reflective plate according to the eighth invention, the coating film may be silica-based glass formed by a sol-gel method.

In the method for producing a water / oil repellent / antifouling reflective plate according to the eighth invention, the heat treatment temperature in the step E is preferably lower than either the softening temperature of the substrate or the transparent fine particles.

In the method for producing a water- and oil-repellent and antifouling reflective plate according to the eighth invention, before the step C, the first silane compound containing a linear group and a non-aqueous organic solvent are included. The surface of the monomolecular film of the first silane compound is dispersed by the reaction of the silyl group of the first silane compound and the reactive group on the surface of the transparent microparticle a. It is preferable to include the step A for manufacturing the covered transparent fine particles, and the heat treatment in the step E is performed in an atmosphere containing oxygen.

In the method for producing a water- and oil-repellent and antifouling reflective plate according to the eighth invention, an organic solvent is used for the fine particle dispersion, and the linear group may be a fluorocarbon group.

In the method for producing a water- and oil-repellent and antifouling reflective plate according to the eighth aspect of the invention, the fine particle dispersion uses one or both of water and alcohol, and the linear group is carbonized. It may be a hydrogen group.

In the method for producing a water- and oil-repellent and antifouling reflective plate according to the eighth invention, the formation of the water and oil and oil repellent and antifouling coating in the step G is performed with a second silane compound containing a fluorocarbon group. A second chemical adsorption liquid containing an aqueous organic solvent is brought into contact with the fine particle fused glass substrate, and a silyl group of the second silane compound and a reactive group on the surface of the fine particle fused glass substrate are obtained. It is preferable to carry out by this reaction.

In the method for producing a water- and oil-repellent and antifouling reflective plate according to the eighth invention, after the reaction between the silyl group and the reactive group in the step G, the unreacted second silane compound is washed away. May be.

In the method for producing a water- and oil-repellent and antifouling reflective plate according to the eighth invention, either one or both of the first and second silane compounds contained in the first and second chemical adsorption liquids, respectively. An alkoxysilane compound may be used.

In the method for producing a water- and oil-repellent and antifouling reflective plate according to the eighth invention, either one or both of the first and second silane compounds contained in the first and second chemical adsorption liquids, respectively. It may be a halosilane compound.

In the method for producing a water- and oil-repellent and antifouling reflective plate according to the eighth invention, either one or both of the first and second silane compounds contained in the first and second chemical adsorption liquids, respectively. It may be an isocyanate silane compound.

In the method for producing a water- and oil-repellent and antifouling reflective plate according to the eighth invention, the first and second chemical adsorption liquids containing the alkoxysilane compound further include a metal carboxylate as a condensation catalyst. 1 or 2 or more compounds selected from the group consisting of a carboxylate metal salt, a carboxylate metal salt polymer, a carboxylate metal salt chelate, a titanate ester, and a titanate ester chelate may be included.

In the method for producing a water- and oil-repellent and antifouling reflecting plate according to the eighth invention, the first and second chemical adsorption liquids containing the alkoxysilane compound include a ketimine compound, an organic acid, One or more compounds selected from the group consisting of an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound may be further included.

In the method for producing a water- and oil-repellent and antifouling reflective plate according to the eighth invention, the cocatalyst further comprises a ketimine compound, an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound. One or more selected compounds may be included.

The water repellent / oil repellent / antifouling reflective plate according to claims 1 to 11 and the method for producing a water / oil repellent / antifouling reflective plate according to claims 18 to 34 require a water / oil repellent / antifouling function. Water repellent excellent in water-drop separation (also referred to as water slidability), antifouling properties, wear resistance, weather resistance, etc. in tunnels, road signs, display boards, signboards, vehicles, and building reflectors An oil-repellent antifouling glass plate can be provided.

A water repellent and oil repellent antifouling reflector according to claims 1 to 11, a tunnel according to claim 12, a road sign according to claim 13, a display sign according to claim 14, a signboard according to claim 15, and a claim 16. In the manufacturing method of the vehicle according to claim 17, the building according to claim 17, and the water / oil repellent / antifouling reflecting plate according to claims 18 to 34, the water / oil / oil repellent / antifouling property in which the surface of the substrate is fused. Therefore, the water and oil repellent and antifouling reflector has a complex surface shape with irregularities. Therefore, it has high water and oil repellency and antifouling properties due to the so-called “lotus leaf effect”.

In particular, the water / oil / oil repellent / antifouling reflector according to claim 2 has a surface having a complex uneven structure because the transparent fine particles are fused to the surface of the base material at a part of the surface. Since the exposed portion is covered with a water / oil repellent / antifouling film, it has high water / oil repellent / antifouling properties.

The water / oil repellent / antifouling reflective plate according to claim 3 can improve durability because the water / oil repellent / antifouling coating is covalently bonded to the surface of the transparent fine particles and the glass substrate.

Since the water- and oil-repellent and antifouling reflective plate according to claim 4 is used by mixing transparent fine particles having different particle diameters, the surface shape of the water and oil-repellent and antifouling reflective plate has fractal properties. Water and oil repellency can be improved.

The water / oil repellent / antifouling reflective plate according to claim 5 can improve the water / oil repellent / antifouling property since the water / oil repellent / antifouling coating film contains —CF ₃ groups.

The water- and oil-repellent and antifouling reflecting plate according to claim 6, wherein the transparent fine particles are translucent and the softening temperature thereof is silica, alumina or zirconia higher than the softening temperature of the substrate surface. Can be fused to the surface of the substrate without impairing the shape of the substrate.

In the water and oil repellent and antifouling reflecting plate according to claim 7, since the particle diameter of the transparent fine particles is less than 400 nm, which is smaller than the wavelength of visible light, there is little scattering of visible light and high translucency can be maintained.

In the water / oil repellent / antifouling reflective plate according to claim 8, since the contact angle with respect to water is 130 degrees or more, the falling angle of the water droplet becomes small, and the water droplet does not substantially adhere.

The water- and oil-repellent and antifouling reflective plate according to claim 9 has a metal oxide transparent film that is fused to the transparent fine particles at a lower temperature than the substrate. It is possible to lower the heat treatment temperature at the time, and it is possible to suppress the thermal deformation of the transparent fine particles during fusion.

In the water and oil repellent and antifouling reflecting plate according to claim 10, since the base material is either a light reflecting stainless steel plate or an aluminum plate, and the coating is transparent, reflected light from the base material is also effective. Available.

The water / oil / oil repellent / antifouling reflective plate according to claim 11 is such that the substrate is any one of paper, cloth, resin, glass plate, metal plate, and ceramic plate, and the coating is a dye, pigment, metal fine particle, And any one or more of mica fine particles, the reflective surface can be colored.

Since the tunnel according to claim 12 is equipped with the water- and oil-repellent and antifouling reflecting plate according to claims 1 to 11, for example, even if the headlamp of a car passing through the tunnel is not lit, illumination Since the light is reflected by the side wall, the visibility of the side wall can be greatly improved, and the illumination power in the tunnel can be reduced, which is economical.
Moreover, the cleaning of the tunnel wall is facilitated by the reflector.

Since the road sign according to claim 13 is equipped with the water- and oil-repellent antifouling reflective plate according to claims 1 to 11, visibility at night can be improved, and safety can be improved as compared with the past.

Since the display board of Claim 14 is equipped with the water- and oil-repellent antifouling reflective board of Claims 1 to 11, visibility at night can be improved and safety can be improved as compared with the conventional display board.

Since the sign of Claim 15 is equipped with the water- and oil-repellent and antifouling reflecting plate of Claims 1 to 11, visibility at night can be improved, and safety can be improved as compared with the prior art.

Since the vehicle according to claim 16 is equipped with the water- and oil-repellent antifouling reflective plate according to claims 1 to 11, it is possible to improve the visibility of the vehicle, particularly at night, and it is safer than before. Can be improved.

Since the building according to claim 17 is equipped with the water- and oil-repellent and antifouling reflecting plate according to claims 1 to 11, the illumination power of the building can be reduced and it is economical.

In the method for producing a water- and oil-repellent and antifouling reflecting plate according to claims 18 to 34, the fine particle dispersion is applied to the surface of the base material and dried to adhere the transparent fine particles to the surface of the base material. Is heated to produce a fine particle fusion base material, and a water and oil repellent and antifouling film is formed thereon, so that it is covered with transparent fine particles substantially uniformly over the entire surface. A water and oil repellent antifouling reflector excellent in transparency and durability can be obtained.
Moreover, since the heat treatment temperature is lower than the softening temperature of the transparent fine particles, thermal deformation of the transparent fine particles at the time of fusion can be suppressed.

The method for producing a water- and oil-repellent and antifouling reflector according to claim 19 does not dissolve in the fine particle dispersion on the surface of the base material before Step D, and melts the transparent fine particles and the fine particles at a temperature lower than that of the base material. Since it has the process B which forms the transparent film of the metal oxide to wear, it becomes possible to perform the heat processing in the process E at lower temperature.

In the method for producing a water- and oil-repellent and antifouling reflecting plate according to claim 20, since the substrate is either a light-reflective stainless steel plate or an aluminum plate, and the coating is transparent, reflection from the substrate Can also be used effectively.

In the method for producing a water / oil / oil repellent antifouling reflector according to claim 21, since the coating film contains any one or more of a dye, a pigment, a metal fine particle, and a mica fine particle, Can be adjusted.

In the method for producing a water- and oil-repellent and antifouling reflective plate according to claim 22, since the coating is silica-based glass formed by a sol-gel method, for example, when paper, cloth, or resin is used as the substrate Can produce a water and oil repellent antifouling reflector at a lower temperature. Further, when a glass plate, a metal plate, or a ceramic plate is used as the substrate, a more durable water / oil repellent / antifouling reflecting plate can be produced.

In the method for producing a water- and oil-repellent and antifouling reflective plate according to claim 23, since the heat treatment temperature in step E is lower than both the base material and the softening temperature of the transparent fine particles, the surface roughness of the base material is maximized. Therefore, it is possible to produce a reflector having excellent water and oil repellency and antifouling performance.

The method for producing a water- and oil-repellent and antifouling reflective plate according to claim 24 comprises the first chemistry comprising a first silane compound containing a linear group and a non-aqueous organic solvent before Step C. Transparent fine particles in which transparent fine particles a are dispersed in an adsorbent and the surfaces are covered with a monomolecular film of the first silane compound by the reaction between the silyl group of the first silane compound and the reactive groups on the surface of the transparent fine particles a In the step C, transparent fine particles whose surface is covered with a monomolecular film of the first silane compound are used in the step C, so that the transparent fine particles in the fine particle dispersion are used. Can be dispersed uniformly.
In addition, since the heat treatment in step E is performed in an atmosphere containing oxygen, the monomolecular film of the first silane compound can be completely decomposed and removed at a low heating temperature.

In the method for producing a water- and oil-repellent and antifouling reflective plate according to claim 25, an organic solvent is used for the fine particle dispersion, and the linear group of the first silane compound is a fluorocarbon group. The surface energy of the fine particles is reduced, and the aggregation of transparent fine particles can be reliably suppressed.

In the method for producing a water- and oil-repellent and antifouling reflecting plate according to claim 26, one or a mixture of water and alcohol is used as the fine particle dispersion, and the linear group of the first silane compound is used. Since is a hydrocarbon group, the cost required for the preparation of the fine particle dispersion can be reduced, and the safety of the fine particle acid solution is further increased.

28. In the method for producing a water / oil / oil / repellency / antifouling reflector according to claim 27, the formation of the water / oil / oil / repellency / antifouling film in the step G is carried out by applying a second silane compound containing a fluorocarbon group to a fine particle fusion group. Since the contact is made with the silyl group of the second silane compound and the reactive group on the surface of the fine particle fusion base material in contact with the material, the durability of the water / oil repellent / antifouling coating can be improved. .

In the method for producing a water- and oil-repellent and antifouling reflecting plate according to claim 28, the unreacted second silane compound is washed away after the reaction between the silyl group and the reactive group in Step G. By forming only the water / oil repellent / antifouling coating covalently bonded to the surface of the substrate, the water / oil repellent / antifouling property and durability of the water / oil repellent / antifouling reflector can be improved.

30. The method for producing a water / oil / oil repellent antifouling reflector according to claim 29, wherein one or both of the first and second silane compounds generate harmful hydrogen chloride upon reaction with a reactive group. Since the non-alkoxysilane compound is used, the production of the water / oil repellent / antifouling reflective plate can be performed more safely, and the corrosion of the production facility and the generation of acidic waste liquid can be suppressed.

In the method for producing a water- and oil-repellent and antifouling reflective plate according to claim 30, one or both of the first and second silane compounds are halosilane compounds having high reactivity with a reactive group. The production of the water / oil repellent / antifouling reflective plate can be carried out more efficiently, and the addition of a catalyst becomes unnecessary.

32. In the method for producing a water / oil / oil repellent antifouling reflector according to claim 31, any one or both of the first and second silane compounds generate harmful hydrogen chloride upon reaction with a reactive group. In addition, since it is a highly reactive isocyanate silane compound, corrosion of production facilities and generation of acidic waste liquid can be suppressed, and addition of a catalyst becomes unnecessary.

The method for producing a water- and oil-repellent and antifouling reflective plate according to claim 32, wherein the first and second chemical adsorption liquids containing an alkoxysilane compound are further used as a condensation catalyst as a carboxylic acid metal salt or a carboxylic acid. Since it contains one or more compounds selected from the group consisting of ester metal salts, carboxylate metal salt polymers, carboxylate metal salt chelates, titanate esters, and titanate ester chelates, alkoxysilane compounds and reactive groups The reaction time can be shortened, and the production of the water- and oil-repellent and antifouling reflector can be carried out more efficiently.

35. The method for producing a water- and oil-repellent and antifouling reflective plate according to claim 33, wherein the first and second chemical adsorption liquids containing an alkoxysilane compound are ketimine compounds, organic acids, aldimine compounds, enamines. Further comprising one or more compounds selected from the group consisting of a compound, an oxazolidine compound and an aminoalkylalkoxysilane compound, the reaction time between the alkoxysilane compound and the active hydrogen group is shortened, and the water and oil repellent and antifouling agent is reduced. The reflective reflector can be manufactured with higher efficiency. In particular, when both of these compounds and the above condensation catalyst are included, the reaction time can be further shortened.

Hereinafter, a water / oil repellent / antifouling reflective plate according to an embodiment of the present invention will be described with reference to the drawings.
As shown in FIG. 1, a water- and oil-repellent and antifouling reflective plate (hereinafter also simply referred to as a reflective plate) 10 according to an embodiment of the present invention includes a plate-like aluminum substrate 11 and an aluminum substrate 11. Water-repellent / oil-repellent antifouling silica fine particles (an example of transparent fine particles) 13 fused to the surface of the aluminum substrate 11 via a silica-based transparent film (an example of the film) 12 and silica fine particles 13 out of the surface of the aluminum base 11. And a chemisorbed monomolecular film (an example of a water / oil repellent / antifouling film) 14 containing a fluorocarbon group covering a portion that is not fused.

As shown in FIGS. 2 (a) and 2 (b), the manufacturing method of the water / oil repellent / antifouling reflective plate 10 includes a first silane compound containing a linear group and a non-aqueous organic solvent. Silica fine particles 15 as an example of transparent fine particles (original transparent fine particles a) are dispersed in the first chemical adsorption liquid, and the silyl groups of the first silane compound and the hydroxyl groups (reactive groups of the reactive groups) of the silica fine particles 15 are dispersed. Example) Step A for producing silica fine particles 18 whose surface is covered with a monomolecular film 17 of a first silane compound by reaction with 16, and a silica-based material on the surface of an aluminum substrate 11 as shown in FIG. As shown in FIG. 4 (a), a process B for forming the transparent coating 12, a process C for preparing a fine particle dispersion in which the silica fine particles 18 whose surface is covered with the monomolecular film 17 of the first silane compound is dispersed. On the surface of the aluminum substrate 11 (in detail, silica The fine particle dispersion is applied to the surface of the transparent coating 12 and dried to thereby attach the silica fine particles 18 on the silica-based transparent coating 12 on the surface of the aluminum substrate 11, and the silica fine particles 18 are attached to the surface. The aluminum base material 11 is heat-treated, the silica fine particles 18 are fused to the surface of the aluminum base material 11 through the silica-based transparent coating 12, and the uneven aluminum base material covered with the fused silica fine particles 13 (fine particle fusion) An example of a base material) Step E for producing 19; Step F for washing and removing silica fine particles 18 that have not been fused to the surface of the aluminum base material 11; And a step G of forming the chemical adsorption monomolecular film 14.
Hereinafter, steps A to G will be described in more detail.

In step A, silica fine particles 18 whose surfaces are covered with the monomolecular film 17 of the first silane compound are produced.
In order not to impair the transparency of the manufactured water / oil repellent / antifouling reflector 10, the diameter of the silica fine particles 15 used for the production of the silica fine particles 18 whose surface is covered with the monomolecular film 17 of the first silane compound. Is preferably smaller than the visible light wavelength (380 to 700 nm). Specifically, the diameter of the fine particles is preferably 10 to 400 nm, more preferably 10 to 300 nm, and even more preferably 10 to 100 nm. The silica fine particles 15 to be used may have a single particle size, but when silica fine particles having two or more different particle sizes are mixed and used, the surface has a fractal structure. 20 (see FIG. 5) is obtained, which is preferable because the water and oil repellency and antifouling properties are improved.

In the present embodiment, silica fine particles are used as the transparent fine particles. However, the surface has active hydrogen groups (an example of reactive groups) that react with alkoxysilyl groups and halosilyl groups, such as hydroxyl groups and amino groups. Any fine particles that are light and have a softening point higher than that of the aluminum substrate can be used. Examples of transparent fine particles that can be used other than silica include alumina or zirconia fine particles.

The first chemical adsorption liquid used for the production of the silica fine particles 18 whose surface is covered with the monomolecular film 17 of the first silane compound includes the first silane compound, the silyl group, and the hydroxyl groups 16 on the surface of the silica fine particles 15. It is prepared by mixing a condensation catalyst for accelerating the condensation reaction with a non-aqueous organic solvent.

As the first silane compound, an alkoxysilane compound represented by any one of the following chemical formulas 1 and 2 is used.

In the above chemical formulas 1 and 2, m represents an integer of 5 to 20, n represents an integer of 0 to 9, and R represents an alkyl group having 1 to 4 carbon atoms.
Y represents (CH ₂ ) _k (k represents an integer of 1 to 3) and a single bond, and Z represents O (ether oxygen), COO, Si (CH ₃ ) ₂ , and a single bond. Represents one of the bonds.

Specific examples of the alkoxysilane compound that can be used as the first silane compound include alkoxysilane derivatives containing a fluorocarbon group shown in the following (1) to (12), and the following (21) to (32). And alkoxysilane derivatives containing the hydrocarbon group shown in FIG.

(1) CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(2) CF ₃ (CH ₂ ) ₃ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(3) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OCH ₃ ) ₃
(4) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OCH ₃ ) ₃
(5) CF ₃ COO (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(6) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
(7) CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃
(8) CF ₃ (CH ₂ ) ₃ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃
(9) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₃
(10) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₃
(11) CF ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃
(12) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃

(21) CH ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OCH ₃ ) _{3
(22) CH 3 (CH 2} ) 3 Si (CH 3) 2 (CH 2) 15 Si (OCH 3) 3
_{(23) CH 3 (CH 2} ) 5 (CH 2) 2 Si (CH 3) 2 (CH 2) 9 Si (OCH 3) 3
(24) CH ₃ (CH ₂ ) ₉ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OCH ₃ ) ₃
(25) CH ₃ COO (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(26) CH ₃ (CH ₂ ) ₇ Si (OCH ₃ ) _{3
(27) CH 3 CH 2 O} (CH 2) 15 Si (OC 2 H 5) 3
_{(28) CH 3 (CH 2} ) 3 Si (CH 3) 2 (CH 2) 15 Si (OC 2 H 5) 3
_{(29) CH 3 (CH 2} ) 7 Si (CH 3) 2 (CH 2) 9 Si (OC 2 H 5) 3
_{(30) CH 3 (CH 2} ) 9 Si (CH 3) 2 (CH 2) 9 Si (OC 2 H 5) 3
(31) CH ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) _{3
(32) CH 3 (CH 2} ) 7 Si (OC 2 H 5) 3

As the condensation catalyst, metal salts such as carboxylic acid metal salts, carboxylic acid ester metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanate esters, and titanate ester chelates can be used.
The addition amount of the condensation catalyst is preferably 0.2 to 5% by mass of the alkoxysilane compound, and more preferably 0.5 to 1% by mass.

Specific examples of carboxylic acid metal salts include stannous acetate, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, stannous dioctanoate, naphthenic acid Lead, cobalt naphthenate, and iron 2-ethylhexenoate.

Specific examples of the carboxylic acid ester metal salt include dioctyltin bisoctylthioglycolate ester salt and dioctyltin maleate ester salt.
Specific examples of the carboxylic acid metal salt polymer include dibutyltin maleate polymer and dimethyltin mercaptopropionate polymer.
Specific examples of the carboxylic acid metal salt chelate include dibutyltin bisacetylacetate and dioctyltin bisacetyllaurate.

Specific examples of the titanate ester include tetrabutyl titanate and tetranonyl titanate.
Specific examples of titanate chelates include bis (acetylacetonyl) dipropyl titanate.

When the silica fine particles 15 are dispersed in the first chemical adsorption liquid containing the alkoxysilane compound and reacted in air at room temperature, the alkoxysilyl group and the hydroxyl groups 16 on the surface of the silica fine particles 15 cause a condensation reaction, and A monomolecular film 17 of the first silane compound having a structure as shown in either chemical formula 3 or chemical formula 4 is generated. The three single bonds extending from the oxygen atom are bonded to the surface of the silica fine particle 15 or the silicon (Si) atom of the adjacent silane compound, and at least one of them is bonded to the silicon atom on the surface of the silica fine particle 15. is doing.

Since the alkoxysilyl group decomposes in the presence of moisture, the reaction is preferably performed in air with a relative humidity of 45% or less. The condensation reaction is hindered by oils and fats and moisture adhering to the surface of the silica fine particles 15, and it is preferable to remove these impurities in advance by thoroughly washing and drying the silica fine particles 15.
When any of the above metal salts is used as the condensation catalyst, the time required for completion of the condensation reaction is about 2 hours.

Instead of the above metal salt, one or more compounds selected from the group consisting of ketimine compounds, organic acids, metal oxides such as TiO ₂ , aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds are used. When used as a condensation catalyst, the reaction time can be shortened to about 1/2 to 2/3.

Alternatively, when these compounds are used as a co-catalyst and mixed with the above-described metal salt (mass ratio 1: 9 to 9: 1 can be used, preferably around 1: 1), the reaction time is further shortened. it can.

For example, as a condensation catalyst, silica fine particles 18 whose surface is covered with a monomolecular film 17 of the first silane compound under the same conditions except that H3 of Japan Epoxy Resin Co., which is a ketimine compound, is used instead of dibutyltin oxide. When the production of is carried out, the reaction time can be shortened to about 1 hour without impairing the quality.

In addition, as a condensation catalyst, a mixture of H3 and dibutyltin bisacetylacetonate (Japan epoxy resin) (mixing ratio is 1: 1) was used, and the other conditions were the same. When the silica fine particles 18 whose surface is covered are manufactured, the reaction time can be shortened to about 20 minutes.

The ketimine compound that can be used here is not particularly limited, and examples thereof include 2,5,8-triaza-1,8-nonadiene, 3,11-dimethyl-4,7,10-triaza- 3,10-tridecadiene, 2,10-dimethyl-3,6,9-triaza-2,9-undecadiene, 2,4,12,14-tetramethyl-5,8,11-triaza-4,11-penta Decadiene, 2,4,15,17-tetramethyl-5,8,11,14-tetraaza-4,14-octadecadiene, 2,4,20,22-tetramethyl-5,12,19-triaza -4,19-trieicosadiene and the like.

Moreover, although it does not specifically limit as an organic acid which can be used, For example, a formic acid, an acetic acid, propionic acid, a butyric acid, malonic acid etc. are mentioned.

For the preparation of the first chemical adsorption solution, an organic chlorine solvent, a hydrocarbon solvent, a fluorocarbon solvent, a silicone solvent, and a mixed solvent thereof can be used. In order to prevent hydrolysis of the alkoxysilane compound, it is preferable to remove water from the desiccant or the solvent used by distillation. Moreover, it is preferable that the boiling point of a solvent is 50-250 degreeC.

Specific usable solvents include non-aqueous petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, normal paraffin, decalin, industrial gasoline, nonane, decane, kerosene, dimethyl silicone, phenyl silicone, and alkyl-modified silicone. , Polyether silicone, dimethylformamide and the like.
Furthermore, alcohol solvents such as methanol, ethanol, propanol, or a mixture thereof can also be used.

Fluorocarbon solvents that can be used include fluorocarbon solvents, Fluorinert (manufactured by 3M, USA), Afludo (manufactured by Asahi Glass Co., Ltd.), and the like. In addition, these may be used individually by 1 type and may mix 2 or more types as long as it mixes well. Furthermore, an organic chlorine solvent such as dichloromethane or chloroform may be added.

A preferable concentration of the alkoxysilane compound in the first chemical adsorption solution is 0.5 to 3% by mass.

After the reaction, washing with a solvent to remove excess alkoxysilane compound and condensation catalyst remaining on the surface, silica particles 18 covered with the monomolecular film 17 of the first silane compound are obtained. FIG. 2B shows a schematic diagram of a cross-sectional structure of the silica fine particles 18 covered with the monomolecular film 17 of the first silane compound thus manufactured. In FIG. 2B, an example having the structure represented by the following chemical formula 5 is shown as an example of the monomolecular film 17 of the first silane compound.

As the cleaning solvent, any solvent that can dissolve the alkoxysilane compound can be used, but dichloromethane, chloroform, N-methylpyrrolidone, etc. that are inexpensive, have high solubility, and can be easily removed by air drying are preferable. .

After the reaction, when the fine silica particles 18 covered with the monomolecular film 17 of the first silane compound formed are left in the air without being washed with a solvent, a part of the alkoxysilane compound remaining on the surface is part of the moisture in the air. The resulting silanol group undergoes a condensation reaction with the alkoxysilyl group. As a result, an ultrathin polymer film made of polysiloxane is formed on the surface of the silica fine particles 18 covered with the monomolecular film 17 of the first silane compound. This polymer film is not fixed to the surface of the silica fine particles 18 covered with the monomolecular film 17 of the first silane compound by a covalent bond, but does not particularly hinder the manufacturing process after the process A.

Although the case where an alkoxysilane compound is used as the first silane compound has been described in this embodiment, a halosilane compound or an isocyanate silane compound having a fluorocarbon group may be used. When these silane compounds are used, a condensation catalyst and a co-catalyst are not required, alcohol solvents cannot be used, and they are more susceptible to hydrolysis than alkoxysilane compounds. Except that the reaction is carried out at a humidity of 30% or less, the first chemical adsorption solution can be prepared and the silica fine particles covered with the monomolecular film of the first silane compound can be produced in the same manner as the alkoxysilane compound. .
Examples of the halosilane compound and isocyanate silane compound that can be used as the first silane compound include compounds shown in the following (41) to (52).

(41) CF ₃ CH ₂ O (CH ₂ ) ₁₅ SiCl ₃
(42) CF ₃ (CH ₂ ) ₃ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ SiCl ₃
(43) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ SiCl ₃
(44) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ SiCl ₃
(45) CF ₃ COO (CH ₂ ) ₁₅ SiCl ₃
(46) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (NCO) ₃
(47) CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (NCO) ₃
(48) CF ₃ (CH ₂ ) ₃ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (NCO) ₃
(49) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (NCO) ₃
(50) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (NCO) ₃
(51) CF ₃ COO (CH ₂ ) ₁₅ Si (NCO) ₃
(52) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (NCO) ₃
(Step A).

In Step B, a silica-based transparent coating 12 that does not dissolve in the fine particle dispersion (used in Step C) and is fused with the silica fine particles 18 at a temperature lower than that of the aluminum base 11 is formed on the surface of the aluminum base 11. (See FIG. 3).
There is no restriction | limiting in particular about the material of the aluminum base material 11 to be used, a shape, and a magnitude | size, Arbitrary materials used in a tunnel, a road sign, a display board, a signboard, a vehicle, and a building can be used. Moreover, as long as an active hydrogen group exists on the surface, a surface film may be formed. The active hydrogen group may be a hydroxyl group, but may be another functional group having an active hydrogen such as an amino group.

As the silica-based transparent film 12 formed on the surface of the aluminum substrate 11, a silica dry gel film formed by a sol-gel method is preferable.
Since there are more free hydroxyl groups on the surface and inside of the unsintered dry gel film than on the surface of the aluminum base material 11 having no transparent coating, the silica fine particles 18 and Can be fused.

The formation of a silica dry gel film is achieved by using a sol solution (an example of a metal alkoxide solution) obtained by mixing a tetraalkoxysilane such as tetramethoxysilane (Si (OCH ₃ ) ₄ ), a condensation catalyst, and a solvent with an aluminum substrate. 11 can be applied by evaporating the solvent.
As a result, a condensation reaction occurs between the hydroxyl group generated by hydrolysis of the alkoxyl group by moisture in the air and the alkoxyl group, and a transparent dry gel film of silica (silica-based transparent film 12) is formed on the surface of the aluminum substrate 11. Example) is formed.
Since the condensation catalyst, cocatalyst, solvent type, tetraalkoxysilane concentration, and addition amount of the catalyst that can be used are the same as those in the first chemical adsorption solution, description thereof is omitted.

The application of the sol solution can be performed by an arbitrary method such as a dip coating method, a spin coating method, a spray method, or a screen printing method.
Moreover, although the film thickness of a dry gel film is based also on the particle size of the silica fine particle 15 used for manufacture of the water-repellent / oil-repellent antifouling reflector 10, it is preferably 10 to 50 nm.
FIG. 3 shows a schematic diagram of a cross-sectional structure of the aluminum base material 11 having a silica dry gel film produced in this manner.
When the water-repellent / oil-repellent antifouling reflective plate 10 is produced using the aluminum substrate 11 having a silica dry gel film as a transparent film, the heat treatment in the step E can be performed at a low temperature of 300 ° C. or less. The uneven aluminum base material 19 in which the silica fine particles 13 are fused can be produced without deteriorating the strengthening degree of the aluminum base material.

In the present embodiment, a dry gel film of silica is formed as the transparent film. However, the silica gel 15 can be fused arbitrarily at a temperature lower than that of the aluminum substrate 11. A transparent film can be formed and used. Examples of the transparent film that can be used include dry gel films such as alumina and titanium oxide.
Moreover, when phosphoric acid or boric acid is added to the sol solution at several percents, a dry gel film of phosphorus silicate glass (PSG) or boron silicate glass (BSG) is formed, and the heat treatment temperature in step E is 250 ° C. It can be reduced to the extent (step B above).

In step C, a fine particle dispersion in which silica fine particles 18 whose surfaces are covered with the monomolecular film 17 of the first silane compound is dispersed is prepared.
By adding the silica fine particles 18 whose surface is covered with the monomolecular film 17 of the first silane compound to the solvent and stirring vigorously by any stirring means such as a stirring spring and a magnetic stirrer, or by performing ultrasonic irradiation, The silica fine particles 15 whose surface is covered with the monomolecular film 17 of the first silane compound are uniformly dispersed in the solvent.
As the solvent that can be used for the preparation of the fine particle dispersion, any solvent that can uniformly disperse the silica fine particles 18 and that can be easily removed by evaporation after being coated on the aluminum substrate 11 is used. Can do.

When a silane compound having a fluorocarbon group represented by the chemical formula 1 (for example, the above (1) to (12)) is used as the first silane compound, any water and alcohol-based solvents can be excluded. A non-aqueous organic solvent is preferable, and when using a silane compound having a hydrocarbon group represented by Chemical Formula 2 (for example, the above (21) to (32)), any organic material including water and an alcohol-based solvent is used. Although a solvent can be used, water and alcohol solvents are preferable from the viewpoint of low toxicity and ease of waste disposal.

The mass ratio in the fine particle dispersion of the silica fine particles 18 whose surface is covered with the monomolecular film 17 of the first silane compound is preferably 0.5 to 5% by mass. When the mass ratio is less than 0.5% by mass, a large amount of the fine particle dispersion is required, and when it exceeds 5% by mass, it is difficult to uniformly disperse the silica fine particles 18, which is not preferable.

The monomolecular film 17 of the first silane compound covering the surface of the silica fine particles 18 has an effect of reducing the surface energy of the silica fine particles 18, and has an effect of suppressing aggregation in the fine particle liquid and improving dispersibility.
In the present embodiment, the silica fine particles 18 whose surfaces are covered with the monomolecular film 17 of the first silane compound produced in the process A are used. However, the silica fine particles 15 are directly removed by omitting the process A. Even when a fine particle dispersion is prepared by dispersing in a solvent, although the defect density on the surface of the concavo-convex aluminum substrate 19 produced in the step E is slightly increased, the water- and oil-repellent and antifouling reflective plate 10 is produced. There will be no major hindrance (step C).

In step D, the fine particle dispersion is applied to the surface of the aluminum base 11 (the surface of the silica-based transparent coating 12) and dried, whereby the silica fine particles 18 are formed on the surface of the aluminum base 11 via the silica-based transparent coating 12. Adhere.
The fine particle dispersion can be applied by an arbitrary method such as a dip coating method, a spin coating method, a spray method, or a screen printing method. Further, for the evaporation of the solvent, known methods such as air drying, reduced pressure drying, heat drying and the like can be used alone or in appropriate combination depending on the boiling point, vapor pressure and the like of the solvent used.
FIG. 4 is a schematic diagram of the cross-sectional structure of the aluminum base material 11 having the silica-based transparent coating 12 to which the silica fine particles 18 whose surfaces are covered with the monomolecular film 17 of the first silane compound attached are obtained in this manner. Shown in (a) (step D above).

In step E, the aluminum substrate 11 having the silica-based transparent coating 12 on which the silica fine particles 18 whose surfaces are covered with the monomolecular film 17 of the first silane compound is mounted is heat-treated in an atmosphere containing oxygen, and silica The silica fine particles 18 were fused by decomposing the monomolecular film 17 of the first silane compound covering the surfaces of the fine particles 18 and fusing the silica-based transparent coating 12 and the silica fine particles 18 on the surface of the aluminum substrate 11. An uneven aluminum base 19 (see FIG. 4B) is manufactured (that is, having fused silica fine particles 13 on the surface).
The heat treatment is performed in an atmosphere containing oxygen at a temperature higher than the temperature at which the aluminum base material 11 and the silica fine particles 18 are fused and lower than the melting temperature of the aluminum base material 11 and the silica fine particles 18. The higher the heat treatment temperature, the stronger the silica fine particles 18 can be fused to the surface of the aluminum base 11. However, when the temperature becomes too high, the silica fine particles 18 are placed inside the aluminum base 11 (or the silica-based transparent coating 12). Since it will be buried, it is not preferable.

When the aluminum substrate 11 has the silica-based transparent coating 12, the heat treatment can be performed at a low temperature of about 250 to 300 ° C. for fusing the aluminum substrate 11 and the silica fine particles 18 together. However, in order to completely decompose the monomolecular film 17 of the first silane compound covering the surface of the silica fine particles 18, it is necessary to perform a heat treatment at 350 to 400 ° C.
When the first silane compound has a fluorocarbon group, it is necessary to perform heat treatment at about 400 ° C. in order to completely decompose the monomolecular film, but in the case of having a hydrocarbon group, 350 ° C. The monolayer can be completely decomposed to a certain degree. Therefore, when the 1st silane compound containing a hydrocarbon group is used in the process A, even if the aluminum base material 11 is used, since the intensity | strength does not fall, it is preferable.
A schematic view of the cross-sectional structure of the uneven aluminum base material 19 obtained in this way is shown in FIG.

In the present embodiment, the aluminum substrate 11 on which the silica-based transparent coating 12 is formed is used. However, the step B may be omitted and the aluminum substrate 11 that does not have the silica-based transparent coating 12 may be used as it is. Good. When blue plate glass is used as the glass substrate instead of the aluminum substrate 11, a preferable heat treatment temperature is about 650 degrees. The treatment time is 30 minutes when heat treatment is performed in air at 650 ° C. (step E above).

In step F, the silica fine particles 18 that have not been fused to the surface of the aluminum substrate 11 are removed by washing. Although any solvent can be used for washing, water that is harmless and can easily be disposed of is most preferable (step F).

In step G, a chemically adsorbed monomolecular film 14 containing a fluorocarbon group is formed on the surface of an uneven aluminum substrate 19 having fused silica fine particles 13 to manufacture a water / oil / oil / oil / repellency reflecting plate 10.

The second chemisorption liquid used for forming the chemisorption monomolecular film 14 containing a fluorocarbon group is composed of an alkoxysilane compound containing a fluorocarbon group (an example of the second silane compound) and the uneven aluminum substrate 19. It is prepared by mixing a condensation catalyst for promoting a condensation reaction between a hydroxyl group on the surface (an example of a reactive group) and an alkoxysilyl group and a non-aqueous organic solvent.

Examples of the alkoxysilane compound containing a fluorocarbon group include the alkoxysilane compounds represented by the general formula (Formula 1).

Concentrations of the condensation catalyst, cocatalyst and combinations thereof that can be used for the second chemical adsorption solution, solvent type, alkoxysilane compound, condensation catalyst, and cocatalyst concentration, reaction conditions and reaction time are Since it is the same as a chemical adsorption liquid, description is abbreviate | omitted.

In the chemisorption monomolecular film 14 having a fluorocarbon group, the exposed portion of the fused silica fine particles 13 and the silica fine particles 13 on the surface of the aluminum base 11 (the surface of the silica-based transparent coating 12) are not fused. It is covalently attached to the part.

Although the case where an alkoxysilane compound is used as the second silane compound has been described in this embodiment, a halosilane compound or an isocyanate silane compound having a fluorocarbon group may be used. When a halosilane compound is used, a condensation catalyst and a cocatalyst are not required, an alcohol solvent cannot be used, and it is more susceptible to hydrolysis than an alkoxysilane compound. %), The second chemical adsorption solution can be prepared and reacted with the concavo-convex aluminum base material 19 in the same manner as the alkoxysilane compound.
FIG. 1 shows a schematic diagram of a cross-sectional structure of the water / oil repellent / antifouling reflective plate 10 obtained in this manner. In addition, in FIG. 1, what has the structure represented by said Chemical formula 5 is shown as an example of the chemical adsorption monomolecular film 14 containing a fluorocarbon group (the above process G).

Since the film thickness of the chemical adsorption monomolecular film 14 having a fluorocarbon group is at most about 1 nm, the unevenness of about 50 nm formed on the surface of the aluminum base material covered with the fused silica fine particles 13 is Almost no damage. In addition, due to this unevenness effect (so-called “lotus leaf effect”), the apparent surface energy of the water / oil repellent / antifouling reflector 10 can be reduced, and the water droplet contact angle is 130 degrees or more (this embodiment). Is about 150 degrees), and super water repellency can be realized.

Also, silica fine particles 13 having a hardness higher than that of aluminum are fused to the surface of the aluminum base 11 of the water / oil repellent / antifouling reflective plate 10 via the silica-based transparent coating 12, so that the wear resistance is improved. Has also improved significantly.
Moreover, in the water / oil / oil / repellency antifouling reflector 10, the thickness of the coating including the silica fine particles 13 fused to the surface of the aluminum substrate 11 and the chemical adsorption monomolecular film 14 having a fluorocarbon group is as a whole. Since it is about 100 nm, the transparency of the aluminum base 11 is not impaired.

After the reaction, if the produced water / oil / oil / antifouling reflective plate 10 is left in the air without being washed with a solvent, a part of the alkoxysilane compound remaining on the surface is hydrolyzed by moisture in the air and produced. The resulting silanol group causes a condensation reaction with the alkoxysilyl group. As a result, an ultrathin polymer film made of polysiloxane is formed on the surface of the water / oil repellent / antifouling reflective plate 10. Unlike the monomolecular film, this polymer film is not entirely fixed to the surface of the water / oil repellent / antifouling reflective plate 10 by a covalent bond, but has a fluorocarbon group so that it has water repellent properties. It has oil repellency and antifouling properties. Therefore, it can be used as the water / oil / oil repellent / antifouling reflecting plate 10 in this state as long as the durability is somewhat inferior.

Moreover, as an alkoxysilane compound containing the fluorocarbon group which can be used in the process G, the compound shown to said (1)-(12) is mentioned.

Examples of the halosilane compound and isocyanate silane compound containing a fluorocarbon group that can be used in Step G include the compounds shown in the above (41) to (52).

From the relationship between the contact angle to the water droplet on the water-repellent surface and the falling angle obtained from the experiment using water droplets of different volumes (0.02 to 0.08 ml), when the water droplet contact angle is 150 degrees or more, It is known that the falling angle is 15 degrees or less regardless of the volume.
Therefore, when the water / oil / oil / repellency antifouling reflector 10 is used in tunnels, road signs, display boards, signboards, interiors and exteriors of vehicle bodies, and exterior and interior walls of buildings, illumination power can be reduced and nighttime. It can be seen that the visibility can be improved.

The water / oil / oil repellent / antifouling reflector 10 is excellent in durability such as abrasion resistance and weather resistance, water droplet separation (sliding), and antifouling, and is required to have a water / oil repellent / antifouling function. Can be used for tunnels, road signs, display boards, signs, vehicles, and buildings.
In particular, when the substrate is a glass plate, it can be used as a glass plate for windows of vehicles and buildings.
Vehicles that can use this water / oil repellent / antifouling reflective plate include automobiles, railway vehicles, ships, etc., and can be used as glass plates for windows in any windows, regardless of driver seats, cabins, etc. Can do.
Moreover, as a building which can use a water repellent and oil repellent antifouling reflecting plate, arbitrary buildings, such as a detached house, an apartment house, an office building, are mentioned.

Examples carried out for confirming the effects of the present invention will be described below, but the present invention is not limited to these examples.

Example 1
(1) Production of silica fine particles covered with a monomolecular film having a fluorocarbon group Silica fine particles having an average particle diameter of 100 nm were prepared, washed thoroughly and dried.
(Heptadecafluoro-1,1,2,2-tetrahydrodecyl) trimethoxysilane (Chemical 6, Shin-Etsu Chemical Co., Ltd.) 0.99 parts by weight, and dibutyltin diacetylacetonate (condensation catalyst) 0.01 parts by weight Were weighed and dissolved in 100 parts by weight of a hexamethyldisiloxane solvent to prepare a first chemical adsorption solution.

The first chemisorbed liquid thus obtained was mixed and stirred with dried silica fine particles and reacted in air (relative humidity 45%) for about 1 hour.
Thereafter, the mixture was washed with chloroform to remove excess alkoxysilane compound and dibutyltin diacetylacetonate.

(2) Formation of a silica-based transparent coating on the surface of an aluminum base An aluminum plate (same as a stainless steel plate) having a mirror surface was prepared, washed well, and dried.
0.99 parts by weight of tetramethoxysilane (Si (OCH ₃ ) ₄ ) and 0.01 parts by weight of dibutyltin diacetylacetonate (condensation catalyst) were weighed and dissolved in 100 parts by weight of hexamethyldisiloxane solvent, A sol solution was prepared. When the sol solution thus obtained is applied to the surface of an aluminum plate and the solvent is evaporated, tetramethoxysilane is hydrolyzed and dealcoholized to cause a silica-based transparent film containing a large amount of hydroxyl groups having a film thickness of about 500 nm. (Silica dry gel film) was formed.

(3) Application of the fine particle solution to the surface of the aluminum substrate (1), 1 part by weight of silica fine particles whose surface was covered with a monomolecular film containing a fluorocarbon group was added to 99 parts by weight of xylene, A fine particle dispersion was prepared by vigorous stirring.
Silica fine particles whose surface is covered with a monomolecular film containing a fluorocarbon group after applying the fine particle dispersion to the surface of the aluminum plate having the transparent coating of the silica dry gel film formed in (2) The aluminum base material which adhered to the surface was obtained.

(4) Production of concavo-convex aluminum base material fused with silica fine particles An aluminum base material having silica fine particles whose surface is covered with a monomolecular film containing a fluorocarbon group adhered to the surface is baked at 450 ° C. in air for 30 minutes. As a result, the monomolecular film containing the fluorocarbon group covering the surface of the silica fine particles was decomposed and removed, and the silica fine particles were fused to the surface of the aluminum substrate. Thereafter, when washed with water, the silica fine particles that were not fused to the surface of the aluminum base material were removed, and an uneven aluminum base material with the single layer silica fine particles fused was obtained.

Here, when the surface roughness is smaller than the wavelength of visible light, most of the incident light is regularly reflected, and the irregular reflection performance is deteriorated.
When fine particles of about 100 to 1 μm having different sizes were mixed and used, a reflector plate having further excellent water / oil repellent / antifouling performance and reflection performance was obtained. In order to increase the reflection efficiency, the size of the fine particles is preferably larger than the visible light wavelength (380 to 700 nm), and preferably smaller to prevent contamination, so that the particle size is preferably 100 to 1 μm. Preferably it was 10-1 micrometer. There was no problem whether the shape was spherical or irregular.

Further, here, when the baking temperature is 250 to 350 ° C., it ends with calcination of the silica glass film, but when it exceeds 400 ° C., the monomolecular film can be completely decomposed and removed as described above, and the fine particles Fused.

As the firing temperature in the atmosphere containing oxygen is higher than 250 ° C. or lower than the softening temperature of the base material, the finer particles can be firmly bonded to the surface of the base material. Silica fine particles were melted and buried in the coating film or substrate.

On the other hand, at this time, the chemisorption monomolecular film containing fluorocarbon groups on the surface of the fine particles has the effect of reducing the surface energy of the silica fine particles, and has the effect of suppressing aggregation in the fine particle liquid and improving dispersibility. It was. Even when the chemisorption monomolecular film containing the fluorocarbon group on the fine particle surface was not formed, there was no major problem, but the defect density of the fused silica fine particle 1 'film was slightly high.

Further, when the solvent of the fine particle liquid is not an organic solvent such as xylene but an alcoholic or aqueous solvent, a water / oil repellent / antifouling monomolecular film is formed on the surface of the fine particle, for example, The same function can be achieved even when a water-repellent, oil-repellent and antifouling film as shown in FIG.

Furthermore, the heating temperature is not less than the softening temperature of the base material, for example, the base reflector is a commercially available blue plate glass, and the particles are silica fine particles, even if a coating film for fusing silica-based fine particles to be a binder layer is not formed in advance. In this case, the silica fine particles could be fused and fixed to the substrate surface by heating at 655 ° C. for 30 minutes in the air.
At this time, the chemically adsorbed monomolecular film on the surface of the silica fine particles was completely decomposed and removed, but the silica fine particles themselves did not fuse with each other because the melting point was much higher than 700 ° C.
Further, when several percent of phosphoric acid or boric acid was added at the time of preparing the silica coating solution, phosphoric acid silicate glass (PSG) or (boron silicate glass BSG) was formed, so that the firing temperature could be reduced to 250 ° C. at the minimum. If the sintering temperature could be reduced to about 250 to 350 ° C., a reflector having the same surface roughness could be produced without impairing the strength even if air-cooled tempered glass was used as the substrate.

Finally, after applying a fluorocarbon chemical adsorption solution similar to the case of the fine particles to the surface of the uneven substrate and reacting for about 2 hours, an excess unreacted adsorption solution is added with a chlorine-based solvent such as chloroform. When removed by washing, a chemically adsorbed monomolecular film containing fluorocarbon groups chemically bonded to the surface can be formed over the entire surface of the uneven substrate, and the fused water- and oil-repellent antifouling transparent fine particles and fluorocarbon groups A water / oil repellent / antifouling reflective plate having a water droplet contact angle of about 140 ° covered with a water / oil / oil repellent / antifouling coating film containing water can be produced. (FIG. 3C).

Here, the silica fine particles on the surface of the aluminum base material are fused and fixed to the reflecting plate surface through a silica glass film, and the fused surface where the silica fine particles are exposed and the silica fine particles are fused. The exposed surface of the coating is entirely covered with a water / oil / oil repellent coating containing fluorocarbon groups. Further, the size of the silica fine particles on the surface is about 5 μm, and the chemisorption monomolecular film containing a fluorocarbon group has a thickness of about 1 nm. Therefore, the unevenness of the uneven substrate is not damaged at all. Due to the leaf effect, super water repellency with a water droplet contact angle of approximately 140 degrees could be realized.

(Example 2)
On the other hand, when using a mixture of fine particles having different sizes, for example, fine particles of about 5 μm and fine particles of 50 nm in a ratio of about 1:10 to produce a water / oil repellent / antifouling reflective plate in the same manner as in the examples, the surface becomes A fractal water-repellent / oil-repellent antifouling film was obtained, and a reflector having a higher water / oil-repellent / antifouling effect with a water droplet contact angle of about 155 ° could be produced.
In this way, if fine particles having a particle size of 100 to 1 μm are mixed with fine particles of about 500 to 10 nm (for example, at a mixing ratio of 1:10 to 50), the surface roughness of an ideal fractal structure is obtained. And improved water and oil repellent and antifouling performance. As long as the size of the fine particles to be added is 1000 to 10 nm, any shape is effective, and a reflecting plate excellent in water and oil repellency and antifouling properties is obtained.

In addition, as a solvent for the film-forming solution, an organic chlorine-based solvent, a hydrocarbon-based solvent, a fluorocarbon-based solvent or a silicone-based solvent that does not contain water, regardless of whether the chemical adsorbent is an alkoxysilane-based or chlorosilane-based solvent, Alternatively, it was possible to use a mixture thereof. In addition, when it is going to raise particle concentration by evaporating a solvent, without wash | cleaning, the boiling point of a solvent is good at about 50-250 degreeC.

Therefore, the above results revealed that ketimine compounds, organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds are more active than silanol condensation catalysts.

Furthermore, it was confirmed that the activity was further increased when one of a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkylalkoxysilane compound was mixed with a silanol condensation catalyst.

In the above two embodiments, silica fine particles have been described as an example. However, the present invention is not limited as long as the surface contains active hydrogen, that is, fine particles containing hydroxyl hydrogen, amino group or imino group hydrogen, and the like. Such fine particles can also be selected.

Specifically, if the substrate is paper, cloth, or resin, various low melting point resins or silica-based coatings using a sol-gel method are used for the fine particle fusion coating, and the fine particle fusion coating is used for fine particles. Resin fine particles, glass fine particles, alumina fine particles, zirconia fine particles, metal fine particles, and mica fine particles having a melting point higher than that of the coating resin could be used.

For example, even for nylon fine particles whose surface is hydrophilic resin fine particles, the same repellent property can be obtained by using a vinyl acetate resin having a lower melting point as a coating for fusing fine particles, and using alcohol that does not dissolve the base material or fine particles in the solvent system. A water / oil repellent antifouling reflector could be manufactured.

If the substrate is glass, metal, or ceramic, various low melting point resins or silica-based coatings or capsular films using a sol-gel method are used for the fine particle fusion coating. Resin fine particles, glass fine particles, alumina fine particles, zirconia fine particles, metal fine particles, and mica fine particles having a higher melting point than the coating resin to be worn could be used.
When metal fine particles or mica fine particles were used, the diffuse reflection performance could be further improved even though the particles themselves were not transparent. In addition, when the base material is glass, the reflection efficiency can be further improved by attaching a mirror surface aluminum or a mirror surface stainless steel plate to the back surface.

Furthermore, when the above reflector is used as a poster, signboard, or display plate, various low-melting point resins or sol-gel methods are used for the fine particle fusion coating if the substrate is paper, cloth, or resin. By using a silica-based coating and further mixing dyes, pigments, metal fine particles, or mica fine particles, an arbitrary pattern could be colored.
If the substrate is glass, metal, or ceramics, a silica-based film or capsular film using a sol-gel method is used as the fine particle fusion film, and pigment, metal fine particles, or mica fine particles are mixed. It was possible to color an arbitrary pattern.

(Example 3)
The water droplet contact angle prepared under the same conditions as the reflector prepared in Example 2 is about 150 degrees (the higher the water droplet contact angle, the higher the antifouling property, but practically the same if the water droplet contact angle is 130 degrees or more. The water- and oil-repellent and antifouling reflecting plate was mounted on the side wall in the tunnel, and a running experiment was attempted.

First, when running with the illumination in the tunnel turned on, the side wall visibility could be greatly improved because the illumination light reflected off the side wall as with the center line even when the headlamp was not turned on.
Next, I tried driving with the lighting in the tunnel half lit, but even if the headlamp was not lit, the illumination light reflected off the side wall in the same way as the center line, so the side wall visibility was sufficiently secured and safe. There was no problem in driving.

Furthermore, if the headlamps are turned on even when the lighting in the tunnel is turned off, the illumination light from the headlamps will be reflected by the side walls toward the driver's seat, ensuring side wall visibility as well as the road center line, and safe driving. There was no hindrance.

On the other hand, after examining the degree of dirt after 1, 3 and 6 months, the white wall without the reflector of the present invention had a large amount of soot and the whiteness deteriorated significantly after 6 months. The reflector of the present invention was able to maintain whiteness. Furthermore, as a result of one year later, a white wall surface not equipped with the reflector of the present invention deteriorated in whiteness due to a large amount of soot, but the reflector of the present invention has a certain degree of whiteness. I was able to maintain it.
Therefore, when evaluating the ease of cleaning, the conventional white reflector could not remove the soot to the extent that it was sprayed with water, but with the reflector of the present invention, it could be easily washed and removed. The performance was recovered. This is because the apparent surface energy of the reflector of the present invention is very small (actually, it was 3 mN / m or less when actually measured using a Jisman plot).

In addition, the cause of dirt is because the floating oil in the air adheres to some extent, and the film and soot mix and adhere to the reflector surface. Therefore, it has been found that the conventional reflector has a high surface energy, and therefore has a greater dirt adhesion strength than water pressure, and cannot be removed by repelling water. On the other hand, in the reflector of the present invention, the surface energy was very small like the lotus leaf, and the dirt could be easily peeled off by water pressure, washed and removed, and the reflecting performance could be recovered.

Example 4
Using a reflector manufactured by the same method as in Example 1, a road sign, a display board, and a signboard were prototyped and installed in the vicinity of the road, and the degree of dirt and durability were compared and evaluated.
Conventional road signs, display boards, and signboards could hardly be distinguished from a distance when the lights were turned off, but the road sign, display board, and signboard of the present invention could greatly improve the discrimination performance over the road center line.

Further, in this case, dust and floating oil and fat adhere to the surface and become dirty depending on the period of use, but when it rains, it is almost completely washed away, and there is no practical inconvenience at all.
Furthermore, it has been found that antifouling durability can be guaranteed for more than 5 years.
Further, when a prototype of an automobile in which the reflector of the present invention was mounted on the tail lamp part was prototyped and the head lamp was irradiated from the rear, the same identification as the lit tail lamp could be made.

(Example 5)
In the same manner as in Example 2, a building interior cloth having high reflection performance was prototyped and mounted in a room, and its energy saving performance was compared with conventional cloth pasting.
In this case, even if the illumination power was reduced to about 70%, the room brightness similar to that in the case of the conventional cloth pasting could be maintained.

In this case as well, dust and floating oil and fat adhere to the surface and become dirty depending on the period of use, but it becomes almost clean just by suction with a vacuum cleaner, and there is no practical inconvenience at all. Furthermore, it has been found that antifouling durability can be guaranteed for more than 10 years.
On the other hand, when the exterior panel was prototyped and mounted on the building wall, the energy-saving effect was hardly seen compared to the conventional exterior plate, but the antifouling effect was significantly improved and water was supplied with a hose. Dirt was removed by spraying.

As described above, the present invention has been described with reference to the embodiment. However, the present invention is not limited to the configuration described in the above-described embodiment, and the matters described in the claims are not limited. Other embodiments and modifications conceivable within the scope are also included. For example, the water repellent / oil repellent / antifouling reflective plate of the present invention and a manufacturing method thereof, and a tunnel, a road sign, a display plate, and a signboard using the same according to the present invention by combining some or all of the above-described embodiments and modifications In the case of constructing vehicles, vehicles, and buildings, the scope of rights of the present invention is also included.

It is explanatory drawing which represented typically the cross-sectional structure of the water-repellent | oil-repellent | antifouling | stain_proof anti-reflective board which concerns on one embodiment of this invention. In the manufacturing method of the same water and oil repellent and antifouling reflective plate, a conceptual diagram expanded to the molecular level to explain the process of forming a fluorocarbon monomolecular film on the surface of silica fine particles, (a) is a reaction The cross-sectional structure of the previous silica fine particle, (b) represents the cross-sectional structure of the silica fine particle on which a monomolecular film containing a fluorocarbon group is formed. It is a schematic diagram showing the cross-sectional structure of the aluminum base material in which the silica type transparent coating film was formed in the manufacturing method of the same water-repellent / oil-repellent antifouling reflector. (A) is explanatory drawing of the state which the silica fine particle coat | covered with the fluorocarbon type | system | group monomolecular film has adhered to the aluminum base material surface in which the silica type transparent film was formed in the process D, (b) is in the process E It is explanatory drawing which shows typically the state which the silica fine particle fuse | melted. It is explanatory drawing which represented typically the cross-sectional state of the water-repellent | oil-repellent | antifouling | stain-proof anti-reflective board which has a fractal structure on the surface.

Explanation of symbols

10: Water- and oil-repellent antifouling reflecting plate, 11: Aluminum base material, 12: Silica-based transparent film (film), 13: Silica fine particles (transparent fine particles), 14: Chemisorption monomolecular film containing fluorocarbon group (Water / oil repellent antifouling coating), 15: silica fine particles, 16: hydroxyl group (reactive group), 17: monomolecular film, 18: silica fine particles, 19: uneven aluminum substrate (fine particle fusion substrate), 20: Water and oil repellent antifouling reflector

Claims (34)

A plate-shaped substrate, water- and oil-repellent and antifouling transparent fine particles fused to the surface of the substrate, and a water-repellent and repellent covering the portion of the surface of the substrate where the transparent fine particles are not fused. A water and oil repellent antifouling reflector having an oil antifouling coating. 2. The water / oil repellent / antifouling reflective plate according to claim 1, wherein a part of the surface of the transparent fine particles is fused to the surface of the substrate, and the other exposed part is the water / oil repellent. A water and oil repellent antifouling reflector characterized by being covered with an antifouling coating. The water / oil repellent / antifouling reflective plate according to claim 2, wherein the water / oil repellent / antifouling coating is covalently bonded to the surface of the transparent fine particles and the substrate. Oil antifouling reflector. The water / oil repellent / antifouling reflective plate according to any one of claims 1 to 3, wherein the transparent fine particles having different particle diameters are mixed and used. Oil antifouling reflector. 5. The water / oil repellent / antifouling reflective plate according to claim 1, wherein the water / oil repellent / antifouling coating contains —CF ₃ groups. Dirty reflector. The water- and oil-repellent and antifouling reflective plate according to any one of claims 1 to 5, wherein the transparent fine particles are translucent and the softening temperature thereof is higher than the softening temperature of the substrate surface. A water- and oil-repellent antifouling reflecting plate, characterized in that it is any one of alumina, zirconia and zirconia. The water / oil repellent / antifouling reflective plate according to claim 1, wherein the transparent fine particles have a particle size of less than 400 nm. The water / oil repellent / antifouling reflective plate according to claim 1, wherein the water contact angle is 130 degrees or more. 9. The water / oil repellent / antifouling reflective plate according to claim 1, wherein the transparent fine particles are interposed through a coating film made of any one of a resin film, a silica-based glass film, and a capsular film. The water-repellent oil-repellent antifouling film is fused to the surface of the base material and covers a portion where the transparent fine particles are not fused via the transparent film. Oil repellent antifouling reflector. The water / oil repellent / antifouling reflective plate according to claim 9, wherein the base material is one of a light reflective stainless steel plate and an aluminum plate, and the coating is transparent. Oil antifouling reflector. 10. The water / oil repellent / antifouling reflective plate according to claim 9, wherein the substrate is any one of paper, cloth, resin, glass plate, metal plate and ceramic plate, and the coating is a dye, pigment, metal. A water / oil repellent / antifouling reflector comprising any one or more of fine particles and mica fine particles. A tunnel comprising the water-repellent / oil-repellent / antifouling reflecting plate according to claim 1 mounted on a wall surface. A road sign using the water / oil repellent / antifouling reflective plate according to claim 1. A display panel comprising the water / oil / oil repellent / antifouling reflector according to claim 1. A signboard using the water / oil repellent / antifouling reflecting plate according to claim 1. A vehicle comprising the water- and oil-repellent and antifouling reflecting plate according to any one of claims 1 to 11 inside and outside a vehicle body. A building using the water and oil repellent and antifouling reflecting plate according to any one of claims 1 to 11 for an outer wall and an inner wall. A step C of preparing a fine particle dispersion in which transparent fine particles are dispersed; a step D in which the fine particle dispersion is applied to the surface of the substrate and then dried to attach the transparent fine particles to the surface of the substrate; and the transparent The substrate on which the fine particles adhere to the surface is heated at a temperature lower than the softening temperature of the transparent fine particles, and the transparent fine particles are fused to the surface of the substrate. And a step F of washing and removing the transparent fine particles not adhered, and a step G of forming a water- and oil-repellent and antifouling coating on the surface of the fine particle-fused substrate on which the transparent fine particles are fused. A method for producing a water- and oil-repellent antifouling reflector. The method for producing a water- and oil-repellent and antifouling reflective plate according to claim 18, wherein before the step D, the surface of the base material does not dissolve in the fine particle dispersion and is at a temperature lower than that of the base material. A method for producing a water- and oil-repellent and antifouling reflective plate, further comprising a step B of forming a film fused with the transparent fine particles. 20. The method for producing a water / oil / oil / repellent antifouling reflecting plate according to claim 19, wherein the substrate is one of a light reflecting stainless steel plate and an aluminum plate, and the coating is transparent. A method for producing a water- and oil-repellent antifouling reflector. The method for producing a water / oil repellent / antifouling reflective plate according to claim 19, wherein the substrate is any one of paper, cloth, resin, glass plate, metal plate, and ceramic plate, and the coating is a dye, A method for producing a water- and oil-repellent and antifouling reflective plate comprising any one or more of a pigment, metal fine particles, and mica fine particles. 20. The method for producing a water / oil repellent / antifouling reflective plate according to claim 19, wherein the coating is a silica glass formed by a sol-gel method. . 23. The method for producing a water / oil repellent / antifouling reflective plate according to any one of claims 18 to 22, wherein the heat treatment temperature in the step E is higher than any of the softening temperatures of the substrate and the transparent fine particles. A method for producing a water- and oil-repellent antifouling reflective plate characterized by being low. 24. In the method for producing a water / oil repellent / antifouling reflective plate according to any one of claims 18 to 23, before the step C, the first silane compound containing a linear group and a non-aqueous system are used. Transparent fine particles a are dispersed in a first chemical adsorption solution containing an organic solvent, and the first silane compound is reacted with a silyl group of the first silane compound and a reactive group on the surface of the transparent fine particles a. A process A for producing the transparent fine particles whose surface is covered with a monomolecular film, and the heat treatment in the process E is performed in an oxygen-containing atmosphere. A manufacturing method of the reflector. 25. The method for producing a water- and oil-repellent and antifouling reflective plate according to claim 24, wherein an organic solvent is used for the fine particle dispersion, and the linear group is a fluorocarbon group. A method for producing a water / oil repellent antifouling reflector. 25. The method for producing a water / oil / oil repellent / antifouling reflecting plate according to claim 24, wherein the fine particle dispersion is one or both of water and alcohol, and the linear group is a hydrocarbon. A method for producing a water- and oil-repellent and antifouling reflector, characterized in that it is a base. 27. The method for producing a water / oil repellent / antifouling reflective plate according to any one of claims 24 to 26, wherein the formation of the water / oil repellent / antifouling coating film in the step G includes a fluorocarbon group. A second chemical adsorption liquid containing a second silane compound and a non-aqueous organic solvent is brought into contact with the fine particle fused glass substrate, so that the silyl group of the second silane compound and the fine particle fused glass substrate are brought into contact with each other. A method for producing a water- and oil-repellent and antifouling reflective plate, wherein the method is carried out by reaction with a reactive group on the surface. 28. The method for producing a water / oil / oil repellent antifouling reflector according to claim 27, wherein after the reaction between the silyl group and the reactive group in the step G, the unreacted second silane compound is washed away. A method for producing a water- and oil-repellent and antifouling reflective plate. 29. The method for producing a water / oil repellent / antifouling reflective plate according to any one of claims 27 and 28, wherein the first and second silane compounds contained in the first and second chemical adsorption liquids, respectively. Any one or both of these are alkoxysilane compounds, A method for producing a water- and oil-repellent and antifouling reflective plate. 29. The method for producing a water / oil repellent / antifouling reflective plate according to any one of claims 27 and 28, wherein the first and second silane compounds contained in the first and second chemical adsorption liquids, respectively. Either or both of these are a halosilane compound. A method for producing a water- and oil-repellent and antifouling reflective plate. 29. The method for producing a water / oil repellent / antifouling reflective plate according to any one of claims 27 and 28, wherein the first and second silane compounds contained in the first and second chemical adsorption liquids, respectively. Any one or both of them is an isocyanate silane compound. 30. The method for producing a water / oil repellent / antifouling reflective plate according to claim 29, wherein the first and second chemical adsorption liquids containing the alkoxysilane compound further include a metal carboxylate as a condensation catalyst, Water repellent and water repellent characterized by comprising one or more compounds selected from the group consisting of carboxylate metal salts, carboxylate metal salt polymers, carboxylate metal salt chelates, titanate esters, and titanate ester chelates. Manufacturing method of oil-stain-proof reflector. 30. The method for producing a water- and oil-repellent and antifouling reflective plate according to claim 29, wherein the first and second chemical adsorption liquids containing the alkoxysilane compound are ketimine compounds, organic acids, aldimines as condensation catalysts. A method for producing a water / oil repellent / antifouling reflective plate, further comprising one or more compounds selected from the group consisting of a compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound. 33. The method for producing a water / oil repellent / antifouling reflective plate according to claim 32, wherein the cocatalyst is further selected from the group consisting of ketimine compounds, organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds. A method for producing a water- and oil-repellent and antifouling reflector, comprising one or more compounds.

Images