JP2017177683A - Base material with water-repellent coating film and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a base material with a water-repellent coating film which keeps excellent water repellency for a long period of time and has abrasion resistance, and is excellent in adhesion strength between mutual particles in a coating film and the coating film and the base material, and to provide a method for producing the same.SOLUTION: A base material with a water-repellent coating film has a water-repellent coating film on a surface of a base material, where the coating film contains inorganic oxide particles and has a particle layer where an adhesive is interposed between mutual gaps of the inorganic oxide particles and gaps between the inorganic oxide particles and the base material, and a water-repellent overcoat layer covering the particle layer, and an upper part of the inorganic oxide particles forms an uneven shape exposed from the adhesive material and has an uneven structure covered with the overcoat layer so as to keep the uneven shape on the surface of the coating film. The base material with the water-repellent coating film is produced by applying a coating liquid for particle layer formation in which inorganic oxide particles and resin emulsion particles are mixed and dispersed onto a base material, making the resin emulsion particles interposed gaps between the mutual inorganic oxide particles, collapsing the resin emulsion particles to form the particle layer, and applying an overcoat layer onto the surface of the particle layer.SELECTED DRAWING: Figure 4

Description

  TECHNICAL FIELD The present invention relates to a coated substrate having excellent water repellency and a method for producing the same, and more specifically, a fiber or building material having excellent water repellency, adhesion, durability, waterproof performance, chemical resistance, and the like. The present invention relates to a substrate with a water-repellent coating that can be suitably used for glass, plastic substrates, automobiles and various electronic devices, water treatment, and other uses.

  In order to prevent the adhesion and penetration of water, it has been widely practiced to provide a water-repellent coating on the surface of various substrates and products. The water-repellent coating is also used as a waterproof coating for electrical circuits and semiconductor devices. Has been. Various types of such water-repellent coatings are conventionally known.

  In Patent Document 1 (Japanese Patent Laid-Open No. 2005-343016), in a water-repellent film-coated article in which a surface of a base material is coated with a water-repellent film, the water-repellent film is provided with a protrusion and a water-repellent film composed of fine particle aggregates. A water-repellent film-coated article is disclosed in which a portion where a protrusion is present and a portion where a protrusion is not present are mixed in the coating region of the film, and unevenness due to the protrusion is formed on the surface of the film where the protrusion is present. Has been.

  Patent Document 2 (WO2003 / 039856) discloses a water-repellent substrate including a substrate, a base film having minute irregularities formed on the surface of the substrate, and a water-repellent film formed on the minute irregularities of the substrate film. A water-repellent substrate is disclosed in which the surface shape of the water-repellent coating is composed of particulate protrusions and columnar protrusions whose height measured from the surface of the substrate is higher than that of the particulate protrusions. .

  Patent Document 3 (Japanese Patent Application Laid-Open No. 2004-137137) discloses an article having a coating mainly composed of silicon oxide having minute irregularities on the surface, and the minute irregularities are constituted by minute protrusions and columnar protrusions. A coated article is disclosed that is characterized by: As its manufacturing method, it is disclosed that a coating film having a micro uneven structure can be formed by applying a coating solution in which a chlorosilyl group-containing compound is dissolved in a solvent mainly composed of silicon oil.

In Patent Document 4 (Japanese Patent Laid-Open No. 8-40748), at least one of a micropit-like surface layer, a concavo-convex surface layer, and a convex surface layer in a state where a film is formed on the surface of the glass substrate and the substrate without surface treatment. An underlayer composed of an oxide thin film or a mixed oxide thin film having a surface layer shape of more than one species, tin oxide particles containing at least fluoroalkylsilane and antimony oxide as a dopant on the underlayer, and a silicone compound And a water / oil repellent solution in which an acid is added in an amount of 5 × 10 ⁴ mol to 2 × 10 ² mol with respect to 1 mol of fluoroalkylsilane, to a mixed solution of water and an organic solvent. A water repellent glass having a water layer is disclosed.

  In Patent Document 5 (Japanese Patent Application Laid-Open No. 2007-144916), a superstructure comprising a base, a base film having minute irregularities formed on the surface of the base, and a water-repellent coating formed on the surface of the base film. A water-repellent substrate, wherein the contact angle of distilled water with respect to the surface of the super-water-repellent substrate is 140 ° or more, and the contact angle of pure ethanol with respect to the surface of the super-water-repellent substrate is 30 ° or less. Is disclosed.

Patent Document 6 (Japanese Patent Laid-Open No. 2015-116731) includes a substrate and a water-repellent coating on the surface of the substrate, and the water-repellent coating covers the surface of the base metal oxide particles (A). A particle layer composed of metal oxide particles coated with metal oxide fine particles (B) and an overcoat layer on the metal oxide particle layer, the water-repellent coating surface has a concavo-convex structure, The average height (T _F ) is in the range of 50 to 500 nm, the distance between the average protrusions (pitch width: W _F ) is in the range of 20 to 1000 nm, the substrate is a fiber or cloth, A substrate with a water-repellent coating is disclosed in which the contact angle is in the range of 100 to 180 °.

Patent Document 7 (Japanese Patent Laid-Open No. 2015-110285) includes a substrate and a water-repellent transparent coating on the surface of the substrate, and the water-repellent transparent coating has an average particle diameter (D _A ) in the range of 10 to 150 nm. It consists of a metal oxide particle layer containing deformed metal oxide particles and an overcoat layer on the metal oxide particle layer, and the surface of the water-repellent transparent coating film has an uneven structure, and the average height of the protrusions ( T _F ) is in the range of 30 to 500 nm, the average inter-convex distance (pitch width) (W _F ) is in the range of 20 to 1000 nm, the substrate is a fiber or cloth, and the contact angle with water is A substrate with a water-repellent coating characterized by being in the range of 100 to 180 ° is disclosed.

JP 2005-343016 A WO2003 / 039856 JP 2004-137137 A JP-A-8-40748 JP 2007-144916 A JP, 2015-116731, A JP2015-110285A

  (A) The water-repellent article of Patent Document 1 is formed with a film in which silicon oxide fine particles are laminated non-uniformly, the surface has relatively large irregularities, and the adhesion and strength of the film to the substrate are poor. In some cases, sufficient reproducibility of water repellency could not be obtained. (B) The water-repellent substrate of Patent Document 2 may be insufficient in hydrolysis and polycondensation of the base film-forming component and the water-repellent treatment agent, or may not have sufficient film strength and hardness. Although the initial value of the aqueous solution is high, it may be greatly reduced due to wear or the like.

  (C) The water-repellent article of Patent Document 3 has a problem that the initial contact angle is super-water-repellent, but the contact angle after a wear resistance test using a dry cloth is greatly reduced. (D) The water-repellent glass of Patent Document 4 has a small decrease in contact angle with water after a wear resistance test using an automobile wiper, but the initial contact angle is also a contact angle after a wear resistance test and a weather resistance test. Subsequent contact angles are about 110 to 100, and super water repellency with a contact angle of 150 ° C. or higher is not obtained. (E) The water-repellent substrate of Patent Document 5 has a problem that the adhesion between the substrate and the film is weak and the durability is poor.

  (F) The water-repellent coatings of Patent Document 6 and Patent Document 7 are different from the conventional fractal structure in that the regularity is low, and the convex portions have finer irregularities, and adhesion to the base material and transparency. It has excellent advantages in hardness, scratch resistance, abrasion resistance, haze and the like. On the other hand, in these substrates with a water-repellent coating, an overcoat layer also serving as an adhesive is provided on the surface of the metal oxide particle layer. Since the height difference of the structure is reduced by the overcoat layer, the effect of the uneven structure tends to be reduced. Moreover, in order to improve the adhesiveness of the particle layer with respect to a base material, when an adhesive material is provided between a base material and a particle layer, a manufacturing process will increase and it will take an effort.

  The substrate with a water-repellent coating of the present invention solves the problems (a) to (e) seen in conventional water-repellent coatings, while the water-repellent coatings of Patent Document 6 and Patent Document 7 It is possible to sufficiently maintain the difference in level of the concavo-convex structure of the layer so that the effect of the concavo-convex structure can be sufficiently exerted, and it is not necessary to previously provide an adhesive on the surface of the substrate and to provide a particle layer on the adhesive, The coating strength of the coating to the substrate is increased while simplifying the manufacturing process. According to the present invention, excellent water repellency is maintained for a long period of time, sufficient bonding strength to the substrate and good wear resistance. A substrate with a water-repellent coating and a method for producing the same are provided.

The substrate with a water-repellent coating of the present invention has the following configuration.
[1] A water-repellent substrate having a water-repellent coating on the surface of the substrate, wherein the coating includes inorganic oxide particles, the gap between the inorganic oxide particles, and the inorganic oxide particles and the substrate. It has a particle layer in which an adhesive is interposed in the gap, and a water-repellent overcoat layer that covers the particle layer, and has an uneven shape in which the upper part of the inorganic oxide particles is exposed from the adhesive, and the uneven shape A substrate with a water-repellent coating, characterized by having a concavo-convex structure covered with the overcoat layer on the surface of the coating so as to keep it.
[2] The average particle diameter (D _P ) of the inorganic oxide particles is 20 to 600 nm, the film thickness (U _F ) of the adhesive is 6 to 400 nm, and the average particle diameter (D a ratio _{(U F} / _{D P)} is 1 / 3-2 / 3 of the thickness of the adhesive _{(U F)} for _P), 1/3 of the average particle diameter of the inorganic oxide particles _{(D P)} The substrate with a water-repellent coating according to [1], wherein ~ 2/3 is exposed from the adhesive.
[3] The substrate with a water-repellent coating according to [1] or [2] above, wherein the water-repellent coating has a thickness of 30 nm to 700 nm.
[4] the average height of the projections of the uneven structure of the water-repellent film surface _{(T F)} is in the range of 10 to 300 nm, the average distance between convex portions (Bitch width) _{(W F)} is in the range of 1~1000nm The substrate with a water-repellent coating according to any one of [1] to [3], wherein the substrate has a water-repellent coating.
[5] The inorganic oxide particles have a spherical shape, a plate shape, a confetti shape, a lump shape, or a sunflower shape, or a shape that is a sphere shape, a plate shape, a confetti shape, a lump shape, or a sunflower shape. The substrate with a water-repellent coating according to any one of [1] to [4] above, which is porous.
[6] The sunflower-like particles are composed of base particles made of an inorganic oxide and fine particles of an inorganic oxide covering the surface of the base particle, and the sunflower-like particle surface has fine irregularities due to the fine particles. The substrate with a water-repellent coating as described in [5] above.
[7] The sunflower-like particles have fine irregularities on the surface of the irregular structure of the water-repellent coating, and the average height (T _FF ) of the fine irregularities is in the range of 0.5 to 10 nm. The substrate with a water-repellent coating according to [6] above, wherein an average distance (bitch width) (W _FF ) between the convex portions of the fine irregularities is in the range of 1 to 30 nm.
[8] The water repellent coated substrate according to any one of [1] to [7] above, wherein a contact angle with water is 130 ° or more.
[9] The inorganic oxide particles are SiO ₂ , Al ₂ O ₃ , Sb ₂ O ₅ , ZrO ₂ , TiO ₂ , Fe ₂ O ₃ , CeO ₂ , AgO, CuO, Cu ₂ O, ZnO, and composite oxides thereof. Or it is at least 1 sort (s) chosen from a mixture, The base material with a water-repellent film as described in any one of said [1]-[8] characterized by the above-mentioned.
[10] The adhesive is an emulsion resin, and is an ester resin, polycarbonate resin, amide resin, imide resin, polyphenylene oxide resin, acrylic resin, vinyl chloride resin, vinyl acetate resin, silicone resin The water repellent film-coated base according to any one of [1] to [9] above, which is at least one selected from a resin, a urethane-based resin, a styrene-based resin, or a copolymer resin thereof Wood.

The present invention includes a coating liquid for forming a water-repellent film having the following constitution.
[11] A coating solution for forming a particle layer in which inorganic oxide particles and resin emulsion particles are mixed and monodispersed in a polar solvent, and a coating solution for forming a water repellent overcoat layer. Coating liquid for forming a water repellent film.
[12] The average particle size (D _e ) of the resin emulsion particles is equal to or smaller than the average particle size (D _P ) of the inorganic oxide particles (D _e ≦ D _P ), A coating solution for forming a water-repellent film.
[13] The volume ratio (G / [G + M]) of the volume (G) of the inorganic oxide particles and the volume (M) of the resin emulsion particles is in the range of 0.25 to 0.9. The coating liquid for forming a water-repellent film as described in [11] or [12] above.
[14] A coating solution for forming a particle layer comprises a dispersion in which inorganic oxide particles are dispersed in a polar solvent, and a suspension in which resin emulsion particles are suspended in a polar solvent. For forming a water-repellent coating film according to any one of [11] to [13], wherein the inorganic oxide particles and the resin emulsion particles are mixed in a polar solvent and become a monodispersed coating solution for forming a particle layer. Coating liquid.
[15] The coating liquid for forming an overcoat layer contains at least one of a fluorine-containing compound, an alkyl group-containing compound, or a silicone-based compound, as described in any one of [11] to [14] above Coating liquid for forming a water repellent film.

This invention includes the manufacturing method of the base material with a water-repellent film which consists of the following structures.
[16] A coating solution for forming a particle layer in which inorganic oxide particles and resin emulsion particles are monodispersed and suspended in a polar solvent is applied to a base material, and the resin emulsion particles are placed in the gap between the inorganic oxide particles. After the application, the resin emulsion particles are disintegrated so that the resin enters the gap between the inorganic oxide particles and the gap between the inorganic oxide particles and the base material, and the adhesive is interposed between the inorganic oxide particles and the inorganic oxide particles. An overcoat layer is formed so as to form a particle layer having a concavo-convex shape in which the upper part of the oxide particles is exposed from the adhesive, and to maintain the concavo-convex shape on the concavo-convex shape surface of the particle layer where the inorganic oxide particles are exposed A method for producing a substrate with a water-repellent coating, which comprises applying a forming coating solution to form a water-repellent coating having a concavo-convex structure covered with the overcoat layer on the surface of the substrate.
[17] A coating solution for forming a particle layer in which a dispersion of inorganic oxide particles and a suspension of resin emulsion particles are mixed and the inorganic oxide particles and resin emulsion particles are mixed together in a polar solvent and monodispersed. The method for producing a substrate with a water-repellent coating according to [16], wherein the substrate is prepared and the coating solution is applied to the substrate.
[18] The average particle diameter (D _e ) of the resin emulsion particles contained in the coating liquid for forming the particle layer is equal to or smaller than the average particle diameter (D _P ) of the inorganic oxide particles (D _e ≦ D _P ). The method for producing a substrate with a water-repellent coating according to [16] or [17].
[19] The volume ratio (G / [G + M]) of the volume (G) of the inorganic oxide particles contained in the coating solution for forming the particle layer and the volume (M) of the resin emulsion particles is 0.25 to 0.25. The method for producing a substrate with a water-repellent coating according to any one of [16] to [18], which is in a range of 0.9.
[20] As emulsion resins, ester resins, polycarbonate resins, amide resins, imide resins, polyphenylene oxide resins, acrylic resins, vinyl chloride resins, vinyl acetate resins, silicone resins, urethane resins, Alternatively, a resin emulsion particle suspension obtained by suspending a resin emulsion particle composed of a styrene resin or a copolymer resin thereof in a polar solvent, and an inorganic oxide particle dispersion obtained by dispersing inorganic oxide particles in a polar solvent. The method for producing a substrate with a water-repellent coating according to any one of [16] to [19], wherein a coating solution for forming a particle layer is prepared by mixing.
[21] The method according to any one of [16] to [20], wherein the resin emulsion particles are collapsed by any one of heat drying, electron beam irradiation, or ultraviolet (UV) irradiation. A method for producing a substrate with a water-repellent coating.

In the substrate with a water-repellent coating according to the present invention, the water-repellent coating includes inorganic oxide particles, and an adhesive is interposed between the inorganic oxide particles and between the inorganic oxide particles and the substrate. A top and bottom of the inorganic oxide particles are exposed from the adhesive material to form a large uneven shape with a height difference, and the height difference covered with the overcoat layer so as to maintain the uneven shape. A large uneven structure is formed on the surface of the water-repellent coating. As described above, since the uneven shape of the portion where the inorganic oxide particles are exposed from the adhesive is not buried by the matrix component (adhesive), the water repellent property of the overcoat layer when the water droplet comes into contact with the coating surface. It is difficult for water droplets to adhere to the surface of the film, and the water droplets float from the surface of the film. Further, since air enters the concave portions of the uneven structure having a large height difference on the surface of the coating and becomes an air reservoir, water droplets are more difficult to adhere to the coating surface. Specifically, for example, a concavo-convex structure having a convex average height (T _F ) of 10 to 300 nm and an average distance (pitch width) (W _F ) between convex portions of 1 to 1000 nm is formed on the coating surface. Therefore, the contact angle with water can have a water repellency of 130 ° or more, preferably a super water repellency of 150 ° or more.

  Furthermore, the substrate with a water-repellent coating of the present invention has a large uneven structure due to the presence of the inorganic oxide particles themselves and the surface of the inorganic oxide particles when fine unevenness is formed on the surface of the inorganic oxide particles. By adopting two fractal-like structures with fine irregularities, it is considered that it has higher water repellency. In particular, since sunflower-like particles have fine particles having a uniform particle size arranged on base particles having a uniform particle size, the above-mentioned fractal-like structure is easily obtained, and therefore, the particle size is higher than that of other inorganic oxide particles. We think that it is easy to express water repellency. Although further details are not well understood, it is considered that these two fractal-like structures can provide both super water repellency and oil repellency functions.

  In the substrate with a water-repellent coating according to the present invention, an adhesive is interposed in the gap between the inorganic oxide particles and in the gap between the inorganic oxide particles and the substrate. The bonding strength between the particles and the substrate is high, the water-repellent coating can be maintained for a long time, and the wear resistance is excellent.

  Since the water-repellent coating of the present invention is transparent, a material in which the coating is formed on a transparent substrate such as glass or plastic is suitably used as a transparent material for a window of a building, an automobile, an observation device, or a meter display portion. be able to.

  Moreover, the base material with a water-repellent coating of the present invention can be suitably used for a separation membrane for water treatment. In general, hydrophilic or hydrophobic separation membranes having pores corresponding to applications such as filtration membranes and osmosis membranes are used for water treatment. What formed the water-repellent film of this invention in the surface of nonwoven fabric base materials, such as polysulfone which has the pore for water treatment, a polyethylene terephthalate, and polyester, is suitable as a base material for water treatment. Furthermore, since the water-repellent layer formed on the substrate is thin, the texture and design properties are not impaired when used for fibers.

  Furthermore, the substrate with a water-repellent coating of the present invention is an antifouling material that causes dirt to flow down with running water by forming a water-repellent coating on a fiber such as nylon, polyester, or cotton, exterior building materials, roof tiles, etc. Can also be suitably used. In addition, nylon, polyester, exterior building materials, etc. may also need anti-algae and antibacterial properties. In such cases, inorganic oxide particles obtained by supporting inorganic oxide particles such as Ag, Cu, Zn, etc. (Or composite oxide particles) and either or both of inorganic oxide particles (or composite oxide particles) modified with an organic compound or an organosilicon compound exhibiting anti-algal and antibacterial properties The substrate with a water-repellent coating according to the present invention can have a plurality of functions of algae and antibacterial properties as well as water repellency.

  The coating solution for forming a particle layer according to the present invention is used in a state where inorganic oxide particles and resin emulsion particles are mixed and dispersed, whereby the particles are arranged in a monodispersed state without agglomeration during film formation. The formation of such a structure is intended, and the particle layer in which the inorganic oxide particles are exposed from the adhesive can be easily formed on the substrate. In addition, since the coating liquid contains resin emulsion particles that form an adhesive together with inorganic oxide particles, it is not necessary to separately apply an adhesive to the surface of the substrate, and the work process can be simplified. it can.

  The method for producing a substrate with a water-repellent coating of the present invention uses a coating solution for forming a particle layer in which inorganic oxide particles and resin emulsion particles are mixed and monodispersed. Since it is applied together with the product particles, there is little application work and a water-repellent coating can be easily formed.

  In the method for producing a substrate with a water-repellent coating according to the present invention, resin emulsion particles are interposed in the gaps between inorganic oxide particles and in the gaps between the inorganic oxide particles and the substrate, and the resin emulsion particles are applied and formed. Since it is disintegrated by heating and drying, a resin is introduced into the gap and an adhesive is interposed, so that the inorganic oxide particles and the inorganic oxide particles and the base material are strongly bonded to each other. Large water-repellent coating can be formed. Furthermore, since the inorganic oxide particles are arranged in a single layer, a base material that is highly transparent and does not impair the texture can be obtained.

In the method for producing a substrate with a water-repellent coating according to the present invention, the resin emulsion particles are interposed in the gaps between the inorganic oxide particles, and the inorganic oxide particles are not covered with the resin emulsion particles. An uneven structure with a large difference in height exposed from the adhesive can be formed. For example, with the use of the inorganic oxide average particle diameter of the particles (D _P) and equal to or less (D _e ≦ D _P) average coating liquid resin emulsion particles are dispersed particle diameter (D _e), the average particle size upon drying The tension of the solvent present in the meniscus between the large inorganic oxide particles and the substrate may cause the resin emulsion particles to be drawn into the meniscus and ensure that the inorganic oxide particles are not covered by the resin emulsion particles. For example, a film in which 1/3 to 2/3 of the average particle radius of the inorganic oxide particles is exposed can be formed.

The schematic cross section of the base material with a water-repellent film of this invention. Explanatory drawing which shows the contact angle with the water of the base material with a water-repellent film of this invention. The schematic cross section of a sunflower-like inorganic oxide particle. The schematic cross section of the base material with a water-repellent film using a sunflower-like particle | grain. Explanatory drawing which shows the manufacturing process of the base material with a water-repellent film of this invention.

[Base material with water-repellent coating]
The substrate with a water-repellent coating of the present invention is a water-repellent substrate having a water-repellent coating on the surface of the substrate, the coating containing inorganic oxide particles, and the gap between the inorganic oxide particles and the inorganic oxide Concave and convexity having a particle layer in which an adhesive is interposed between the oxide particles and the base material, and a water-repellent overcoat layer covering the particle layer, the upper part of the inorganic oxide particles being exposed from the adhesive A substrate with a water-repellent coating, characterized by having a concavo-convex structure formed on the surface of the coating so as to have a shape and maintain the concavo-convex shape.

  An example of the substrate with a water-repellent coating of the present invention is shown in FIG. As shown in the drawing, a substrate 10 with a water-repellent coating has a substrate 1 and a water-repellent coating 2 formed on the surface of the substrate 1. The coating 2 is formed by the particle layer 3 and the overcoat layer 7.

  The particle layer 3 is a layer in which a large number of inorganic oxide particles 5 are arranged on the surface of a base material, and is basically formed as a single layer. This is a layer including the adhesive 4 interposed in the gap between the physical particles 5 and the substrate 1. Preferably, the adhesive 4 is formed by disintegrating the resin emulsion particles interposed in the gaps between the inorganic oxide particles 5 and the gaps between the inorganic oxide particles 5 and the substrate 1. The upper part of the inorganic oxide particles 5 is exposed from the surface of the adhesive 4, and the upper part of the inorganic oxide particles 5 is exposed to form a large uneven shape on the surface of the particle layer 3. Has been. The particle layer 3 in this is basically formed as a single layer, and may be formed in two or three layers as necessary. When four or more layers are formed, when used for fibers, the texture may be lowered or the particles may fall off, and the intended strength and adhesion may not be obtained. In order to form these two to three layers, it can be formed by adjusting the concentration of the coating solution for forming the water repellent coating film to an optimum concentration.

The average particle diameter (D _P ) of the inorganic oxide particles 5 is preferably in the range of 20 to 600 nm. When the average particle diameter (D _P ) of the inorganic oxide particles 5 is less than 20 nm, the thickness of the inorganic oxide particles 5 is large when the film thickness (U _F ) of the adhesive 4 is close to the upper limit value of the following film thickness range. A part is taken in by the adhesive material 4, and the height exposed from the adhesive material 4 becomes small, so that an uneven shape with a large height difference cannot be obtained. On the other hand, if the average particle diameter (D _P ) of the inorganic oxide particles exceeds 600 nm, the average height of the concavo-convex convex portions may be outside the desired range, and the desired concavo-convex shape cannot be obtained. The average particle diameter (D _P ) of the inorganic oxide particles is the layer thickness of the particle layer 3.

The layer thickness (U _F ) of the adhesive 4 is preferably in the range of 6 to 400 nm. If the film thickness (U _F ) of the adhesive 4 is less than 6 nm, the adhesive of the inorganic oxide particles 5 when the average particle diameter (D _P ) of the inorganic oxide particles 5 is close to the upper limit of the particle size range. The depth embedded in 4 decreases, and sufficient adhesive strength cannot be obtained. When the film thickness (U _F ) of the adhesive 4 exceeds 400 nm, the inorganic oxide particles 5 are bonded when the average particle diameter (D _P ) of the inorganic oxide particles 5 is close to the lower limit of the particle size range. The height exposed from the material 4 becomes small, and a large uneven shape with a difference in height cannot be obtained.

The ratio (U _F / D _P ) of the layer thickness (U _F ) of the adhesive to the average particle diameter (D _P ) of the inorganic oxide particles 5 is preferably 1/3 to 2/3. It is preferable that 1/3 to 2/3 of the average particle diameter (D _P ) of the particles 5 is exposed from the adhesive 4. In this way, when 1/3 to 2/3 of the average particle diameter (D _P ) of the inorganic oxide particles 5 is exposed from the adhesive 4, an uneven shape having a large height difference is formed on the surface of the coating 2. As a result, the coating 2 has high water repellency.

The substrate with a water-repellent coating of the present invention has a thickness (U _F ) of an adhesive of 10 to 70 nm when the average particle diameter (D _P ) of the inorganic oxide particles is 60 to 100 nm, for example, The ratio (U _F / D _P ) of the layer thickness (U _F ) of the adhesive to the average particle diameter (D _P ) of the inorganic oxide particles is 1/3 to 2/3, and therefore the average of the inorganic oxide particles 1/3 to 2/3 of the particle diameter (D _P ) is exposed from the adhesive.

The overcoat layer 7 is a thin, water-repellent surface layer that covers the surface of the particle layer 3, and preferably contains at least one of a fluorine-containing compound, an alkyl group-containing compound, or a silicone compound. Examples of the fluorine-containing compound include a fluorine-containing silane derivative and a fluorine-containing phosphonic acid derivative. Examples of the alkyl group-containing compound include carboxydecylphosphonic acid, hydroxyundecylphosphonic acid, and derivatives thereof. Examples of silicone compounds include modified reactive silicones. The modified reactive silicone preferably contains an acrylic group, acryloxy group, epoxy group, silanol group, phenol group, carboxyl group or the like as a functional group. Among them, the _formula: in R _n -SiX _4-n (wherein, R is a hydrocarbon group having 1 to 10 carbon atoms, optionally being the same or different .X: 1 to 4 carbon atoms Hydrolyzed polycondensates of hydrolyzable organosilicon compounds such as methoxysilane and ethoxysilane represented by an alkoxy group, a hydroxyl group, halogen, hydrogen, n: an integer of 1 to 3) are preferably used.

The film thickness (O _F ) of the overcoat layer 7 is preferably 0.5 to 10 nm. When the film thickness (O _F ) of the overcoat layer 7 is less than 0.5 nm, the water repellency of the overcoat layer 7 is insufficient and the durability is poor. On the other hand, if the film thickness (O _F ) of the overcoat layer 7 is larger than 10 nm, the uneven shape formed by the inorganic oxide particles 5 is filled with the overcoat layer 7 and it is difficult to obtain an uneven structure with a large height difference. .

  The film thickness of the water-repellent coating 2 including the overcoat layer 7 is preferably in the range of 20 nm to 700 nm, and more preferably in the range of 40 to 600 nm. When the film thickness is less than 20 nm, the durability is lowered and it is difficult to form a sufficient uneven structure on the surface. On the other hand, even if the film thickness is larger than 700 nm, the water repellency effect does not change much. Moreover, as long as the concavo-convex structure is formed in the outermost layer, the effect of water repellency is not so changed.

The substrate with a water-repellent coating of the present invention has a thickness (U _F ) of an adhesive of 10 to 70 nm when the average particle diameter (D _P ) of the inorganic oxide particles is 60 to 100 nm, for example, The ratio (U _F / D _P ) of the layer thickness (U _F ) of the adhesive to the average particle diameter (D _P ) of the inorganic oxide particles is 1/3 to 2/3, and the film thickness of the water repellent coating 2 is 25-160 nm.

The uneven structure on the surface of the water-repellent coating 2 preferably has a convex average height (T _F ) in the range of 10 to 300 nm, and an average distance (bitch width) (W _F ) between the convex portions in the range of 1 to 1000 nm. preferable. If the average height (T _F ) of the convex portion is less than 10 nm, the height difference of the concave-convex structure becomes small and it becomes difficult to increase the water repellency of the coating film. On the other hand, the water repellency does not change much even if the average height of the convex portion (T _F ) is larger than 300 nm. Further, if the pitch width (W _F ) between the protrusions is less than 1 nm, the recesses become narrow, and if the pitch width (W _F ) between the protrusions exceeds 1000 nm, the recesses are too wide. The effect of the uneven structure becomes insufficient, and it becomes difficult to increase the water repellency of the coating.

〔Base material〕
The material of the substrate 1 is not limited. For example, glass, polycarbonate, acrylic resin, PET, TAC, polyester resin, nylon resin or other plastic sheet, plastic film, plastic panel, fiber, nonwoven fabric, mortar material, slate material, concrete, or the like can be used. . The adhesive 4 is an ester resin, polycarbonate resin, amide resin, imide resin, polyphenylene oxide resin, acrylic resin, vinyl chloride resin, vinyl acetate resin, silicone resin, urethane resin, or styrene resin. It can be formed by at least one selected from a resin, a styrene resin, and a copolymer resin thereof.

[Inorganic oxide particles]
The inorganic oxide particles 5 are, for example, SiO ₂ , Al ₂ O ₃ , Sb ₂ O ₅ , ZrO ₂ , TiO ₂ , Fe ₂ O ₃ , CeO ₂ , AgO, CuO, Cu ₂ O, ZnO, and composite oxides thereof. At least one selected from a product or a mixture can be used. These particles are preferable because spherical particles having a desired particle diameter can be easily obtained and are chemically stable.

The shape of the inorganic oxide particles 5 may be any shape as long as the uneven structure can be formed, and is not limited. For example, any shape of spherical particles, plate-like particles, confetti particles, block particles, and sunflower particles can be used. These spherical particles, plate-like particles, confetti particles, massive particles and sunflower particles may have a porous structure. Spherical particles can be easily brought into a state in which 1/3 to 2/3 of the average particle diameter (D _P ) is exposed from the adhesive material 4, and a concavo-convex structure having a large difference in height can be formed on the coating surface. These particles are preferably single particles, but may have a continuous structure of 2 to 3 particles. In addition, when there are four or more continuous structures, voids exist between the substrate and the particles, and the film as shown in FIG. 1 may not be obtained. In addition, sunflower-like particles are exposed to the upper part of the particle from the adhesive material, so that a large uneven shape is formed on the surface of the sunflower, and since the sunflower-like particle surface has fine unevenness, the fractal effect of these unevenness makes the water repellent An excellent film can be obtained. The average particle diameter of these particles is determined based on the length of the major axis. Thus, since it has several uneven structure, it can also have an oil-repellent effect simultaneously.

  In addition, in this application, when the shape of the said inorganic oxide particle is spherical, it calls a spherical particle or a spherical inorganic oxide particle. Hereinafter, similarly, a plate-like case is called a plate-like particle or plate-like inorganic oxide particle, a gold flat sugar-like case is called a flat plate-like sugar-like particle or gold-plated sugar-like inorganic oxide particle, and a massive field is called a massive particle or massive inorganic oxide particle. . Moreover, when the shape of the said inorganic oxide particle is a sunflower shape, it is called a sunflower-like particle | grain, a sunflower-like particle | grain, or a sunflower-like inorganic oxide particle.

  As described above, the shape of the inorganic oxide particles may be any of spherical particles, plate-like particles, confetti particles, block particles, or sunflower particles. Further, the inorganic oxide particles are particles of these shapes, and may be further porous. When the inorganic oxide particles are porous, the specific surface area is relatively large as compared with the inorganic oxide particles having the same shape and the same average particle diameter. In general, the specific surface area of the inorganic oxide particles contributes to an improvement in water repellency of the inorganic oxide particles or a coating containing the inorganic oxide particles.

Gold-peeled inorganic oxide particles Gold-peeled inorganic oxide particles are spherical particles having a large number of hook-shaped protrusions on the particle surface, and the curvature radius of the hook-shaped protrusions and the meniscus on the particle surface is negative, and the structure Is generally similar to confetti. The sunflower-like particles to be described later have irregularities formed by bonding fine particles to base particles, but the radius of curvature of the meniscus of the fine particles and base particles is positive. The average particle diameter (D _A ) of the confetti-like inorganic oxide particles is preferably in the range of 10 to 150 nm, more preferably 10 to 130 nm. The confetti-like inorganic oxide average particle diameter (D _A) is less than 10nm particles, it is difficult to obtain as particles having a wart-like projections, it is difficult to form desired fine irregularities. On the other hand, if the average particle diameter (D _A ) of the confetti inorganic oxide particles exceeds 150 nm, the strength, hardness, and adhesion to the substrate of the water-repellent coating may be insufficient.

  The average height (H) of the ridge-like projections of the confetti-like inorganic oxide particles is preferably in the range of 0.3 to 45 nm, and more preferably in the range of 0.5 to 40 nm. If the average height (H) of the hook-shaped protrusions is less than 0.3 nm, the water repellency of the water repellent film may be insufficient. When the average height (H) of the hook-shaped protrusions exceeds 45 nm, the hook-shaped protrusions are too large, and the number of hook-shaped protrusions on the particle surface is reduced, so that the number of fine irregularities is reduced, which is effective for the expression of water repellency. The surface area is reduced.

The ratio (H) / (D _A ) between the average height (H) of the ridge-like protrusions of the confetti-like inorganic oxide particles and the average particle diameter (D _A ) of the confetti-like inorganic oxide particles is 0.03 to 0. The range of 30 is preferable, and the range of 0.05 to 0.27 is more preferable. When the ratio (H) / (D _A ) is less than 0.03, the water repellency of the water repellent film may be insufficient. On the other hand, when the ratio (H) / (D _A ) exceeds 0.30, the ridge-like protrusions are too large, and the number of ridge-like protrusions on the particle surface decreases, so the number of fine irregularities decreases.

The surface roughness formed by the ridge-like projections of the confetti-like inorganic oxide particles can be expressed by the following formula (1). In addition, (SA ₁ ) is a specific surface area measured by the BET method, (SA ₂ ) is a specific surface area calculated by an equivalent sphere conversion formula represented by the following formula (2), and d is a confetti-like inorganic substance It is the density of oxide particles, and 6000 is a conversion factor. (D _A ) is an average particle diameter of 100 arbitrarily selected from the TEM image.
Surface roughness of confetti sugar-like inorganic oxide particles = (SA ₁ ) / (SA ₂ ) (1)
(SA ₂ ) = 6000 / (D _A ) × d (2)

Here, since the specific surface area indicates the surface area per unit mass, the value of the surface roughness (SA ₁ ) / (SA ₂ ) is such that the more spherical the particle surface is, the more (SA) ₁ ) / (SA ₂ ) increases, while the smaller the number of wrinkles on the particle surface and the smoother, the smaller the value of (SA ₁ ) / (SA ₂ ), which is close to 1. Become.

The surface roughness (SA ₁ ) / (SA ₂ ) of the gold flat sugar-like inorganic oxide particles used in the present invention is preferably in the range of 1.7 to 5.0. When the surface roughness is less than 1.7, the ratio of the ridge-like protrusions is small, or the ridge-like protrusions themselves are extremely smaller than the particle diameter of the gold-plated sugar-like inorganic oxide particles and become close to spherical particles. On the other hand, when the value of surface roughness exceeds 5.0, preparation is difficult. The range of the surface roughness is more preferably in the range of 1.8 to 4.5.

The average particle diameter (D _A ) and the average height (H) of the ridge-like protrusions of the confetti-like inorganic oxide particles can be measured by image analysis of a scanning electron micrograph (SEM). Specifically, for example, for an arbitrary 50 particles in a projection image taken with a scanning electron microscope, the maximum diameter may be measured and the average value may be set as the average particle diameter (D _A ). Further, the distance from the apex of an arbitrary hook-shaped protrusion to the contact point between the hook-shaped protrusion and the spherical particle portion is measured at three locations, and the average value may be set as the average height (H) of the hook-shaped protrusion.

Bulk particles (bulk inorganic oxide particles)
Agglomerated particles are particles in which the particles are randomly set. The particles constituting this may have irregular shapes, irregular shapes, etc., or may be composed of a plurality of shapes. When it is agglomerated, irregular irregularities are formed on the particle surface, so that a higher water repellency can be obtained when a water-repellent coating is obtained.

Sunflower-like particles (sunflower-like inorganic oxide particles)
As shown in the cross-sectional view of FIG. 3, the sunflower-like particle 20 has inorganic oxide substrate particles 21 and inorganic oxide fine particles 22 covering the surface of the substrate particles, and the entire particle has a sunflower-like cross section. Particles. Although the illustrated base particles 21 are schematically spherical, they may be irregular, plate-like, or polyhedral. The fine particles 22 are generally spherical particles. Since the surface of the base particle 21 has fine irregularities due to the fine particles 22, the sunflower-like particles 20 have excellent water repellency, strong adhesion, and effective fouling and deterioration due to the hydrophilic coating. It is suppressed, has antifouling properties, and can maintain high water repellency over a long period of time.

  The average height of the convex and concave portions of the fine irregularities is preferably in the range of 0.5 to 10 nm. If the average height of the convex portion is smaller than the above range, it is difficult to form sufficient irregularities. If the average height exceeds the above range, the particle size of the fine particles 22 is large, so the number of fine particles 22 covering the surface of the base particle 21 is small. As a result, it becomes difficult to form sufficient fine irregularities on the surface of the substrate particles.

  The average distance (bitch width) between the convex portions of the fine irregularities is preferably in the range of 1 to 30 nm. When the average distance (bitch width) is less than 1 nm, the recesses become narrow, and when the pitch width between the protrusions exceeds 30 nm, the recesses are too wide. In any case, it is difficult to obtain a sufficient effect due to fine unevenness. .

The average particle diameter (D _C1 ) of the base particles 21 of sunflower-like particles is preferably in the range of 40 to 600 nm, and more preferably in the range of 50 to 500 nm. When this average particle diameter (D _C1 ) is small, the height of the convex portions and the distance between the convex portions (pitch width) may be too small when applied on the substrate, and it is difficult to obtain high water repellency. On the other hand, even if the average particle diameter (D _C1 ) is too large, the height of the projections and the distance between the projections (pitch width) are too large, and it is difficult to obtain a high water-repellent coating.

The average particle diameter (D _C2) having an average particle diameter (D _C1) and fine particles 22 of the base particles 11 is the average particle diameter determined by the equivalent spherical conversion formula represented by the following formula (3). Incidentally, Equation (3) is D having an average particle diameter (nm), SA _M is measured specific surface area by the BET method ^{(m 2} / g), d the density of the particle (g / cm ^3), 6000 is the conversion factor It is. The average particle diameter D can be measured using a dynamic light scattering method (Nikkiso Co., Ltd. product: Microtrac UPA). The actual measured value of the specific surface area is measured by the BET method.
D = 6000 / SA _M xd (3)

The average particle diameter (D _C2 ) of the fine particles 22 is preferably in the range of 4 to 60 nm, and more preferably in the range of 5 to 40 nm. When the average particle diameter (D _C2 ) is small, it is difficult to obtain sunflower-like inorganic oxide particles that are stably monodispersed. Even if the average particle diameter (D _C2 ) is too large, fine irregularities are increased and the specific surface area of the sunflower-like inorganic oxide particles is also decreased, so that it is difficult to obtain sufficient water repellency.

The average ratio of particle diameter _{(D C2)} having an average particle diameter _{(D C1)} and fine particles 22 of the base particles _{21 (D C2) / (D} C1) is preferably in the range of 0.007 to 0.5, 0. The range of 008 to 0.4 is more preferable. When the ratio (D _C2 ) / (D _C1 ) is smaller than the above range, fine irregularities are reduced, and it is difficult to obtain sufficient water repellency. Fine irregularities with the ratio (D _C2 ) / (D _C1 ) exceeding the above range become large, and it is difficult to obtain sufficient water repellency.

  The coverage of the base particles 21 with the fine particles 22 is expressed by the following formula (4). The coverage is preferably in the range of 30 to 100%, and more preferably in the range of 50 to 100%. If the coverage is small, sufficient fine irregularities cannot be formed. The average particle diameter of the sunflower-like particles with the fine particles 22 coated on the surface of the substrate particles 21 is generally in the range of 48 to 720 nm, although it varies depending on the coverage.

Covering rate (%) = {[actual specific surface area of sunflower-like inorganic oxide particles (S _C1 ) −measured specific surface area of inorganic oxide particles for substrate (S _M )] / [100% covered) Calculated specific surface area of sunflower-like inorganic oxide particles (S _C ) —Measured specific surface area of inorganic oxide particles for substrate (S _M )]} × 100 (4)

Computational specific surface area of the sunflower-like inorganic oxide particles when the surface of the base particles was coated 100% fine particles (S _C) was determined by the following calculation method.
Surface area per fine particle = 4π ((D _C2 ) / 2) ²
Surface area per substrate particle = 4π ((D _C1 ) / 2) ²
Number of fine particles per sunflower-like inorganic oxide particle (n) = 4π (D _C1 / 2 + D _C2 / 2) ² (R / (π (D _C2 / 2) ² )) Represents the filling rate during close packing. ]
Weight of fine particles per particle = (4 / 3π) (D _C2 / 2) (d _C2 )
Weight of substrate particles per particle = (4 / 3π) (D _C1 / 2) (d _C1 )
[Where d _C1 represents the particle density (g / ml) of the base particles, and d _C2 represents the particle density (g / ml) of the fine particles. ]
Weight per sunflower-like inorganic oxide particle = [number of fine particles (n)] × [weight per fine particle] + [weight of one base particle]
From these, the surface area per sunflower-like inorganic oxide particle = [surface area per substrate particle] + [surface area per fine particle] × [fine per sunflower-like inorganic oxide particle] The number of particles (n)].
Therefore, the calculated specific surface area (S _C ) (m ² / g) of the sunflower-like inorganic oxide particles is
Specific surface area (S _C ) = [surface area per sunflower-like inorganic oxide particle] / [weight per sunflower-like inorganic oxide particle]
The particle density of silica was 2.2 g / ml, and this value was used when silica was used as the base particle or fine particle.

The components of the base particles 21 and the fine particles 22 may be the same or different. SiO ₂ , Al ₂ O ₃ , Sb ₂ O ₅ , ZrO ₂ , TiO ₂ , Fe ₂ O ₃ , CeO ₂ , AgO, It is preferably at least one selected from CuO, Cu ₂ O, ZnO and complex oxides or mixtures thereof. As the particles of these components, spherical particles having a particle diameter in the above range can be easily obtained, and since they are chemically stable, they can be preferably used. Of these, SiO ₂ particles are preferable because spherical particles having a uniform particle size can be obtained regardless of the size of the particle size and are chemically stable.

The sunflower-like particles are prepared by mixing an aqueous dispersion of base particles having a positive or negative surface potential and an aqueous dispersion of fine particles having the opposite surface electricity to adjust the pH to a weak acidity, Is passed through an ion exchange resin to remove anions, the pH is adjusted to a neutral range, and drying is performed. Alternatively, when the surface potential of the substrate particles and the surface potential of the fine particles have the same sign, the product is preferably 400 mV ² or less.

  FIG. 4 shows a cross-sectional view of a water repellent coated substrate using sunflower-like particles 20 as the inorganic oxide particles 5. A water-repellent coating 2 formed on the surface of the substrate 1 is formed by a particle layer 3 and an overcoat layer 7. The particle layer 3 includes a large number of sunflower-like particles 20 arranged on the surface of the substrate 1, and the sunflower-like particles 20 are formed by substrate particles 21 and fine particles 22 on the surface of the substrate particles. The particle layer 3 is formed by a large number of the sunflower-like particles 20, the gaps between the sunflower-like particles 20 and the adhesive 4 interposed in the gaps between the sunflower-like particles 20 and the substrate 1.

  The upper part of the sunflower-like particles 20 is exposed from the surface of the adhesive material 4, and the upper and lower parts of the sunflower-like particles 20 are exposed to form an uneven shape with a large height difference. Further, the sunflower-like particles 20 have fine irregularities formed on the surface thereof by the fine particles 22 on the surface of the base particles.

  The overcoat layer 7 is a water-repellent surface layer, and is preferably a layer containing at least one of a fluorine-containing compound, an alkyl group-containing compound or a silicone compound. These compounds in the overcoat layer 7 may be the same as those contained in the overcoat layer 7 of the substrate 1 with a water-repellent film shown in FIG.

  The surface of the particle layer 3 is covered with the overcoat layer 7. The film thickness of the overcoat layer 7 is a thin film thickness that maintains the uneven shape formed by the sunflower-like particles 20 and the fine unevenness on the surface of the sunflower-like particles. The film thickness may be the same as that of the overcoat layer 7 of the substrate 1.

  When the surface of the particle layer of inorganic oxide particles is coated with a partial hydrolyzate of metal alkoxide, a monomer of an organic resin, or a molecular matrix component (adhesive) of a polymer to adhere the particle and the substrate, Alternatively, when a particle layer is formed using a coating liquid containing a matrix component in which emulsion resin particles and inorganic oxide particles larger than the inorganic oxide particles are mixed, the water repellency is obtained when the matrix component fills fine irregularities. High film thickness cannot be obtained. Alternatively, since the emulsion particles do not penetrate evenly between the substrate and the sunflower-like particles, the sunflower-like particles cannot be fixed to the substrate. In addition, when such a matrix component is used, it is known that inorganic oxide particles are clustered to form a film, but the film adhesion is insufficient, or a film is formed on the fiber. As a result, the texture of the fiber may be impaired, or a film with low transparency may be obtained when it is desired to obtain a transparent film.

  On the other hand, the water-repellent coating of the present invention has a large uneven shape with a difference in height formed by the inorganic oxide particles 5 and the sunflower-like particles 20 in which fine unevenness on the particle surface is not filled with the overcoat layer 7. Since the film thickness of the overcoat layer 7 covering the surface of the layer 3 is a thin film thickness that keeps the uneven shape and fine unevenness, the effect of the uneven structure on the surface of the coating is sufficiently exhibited and has high water repellency. Moreover, it is excellent in the adhesiveness of the coating, and even if a coating is formed on the fiber, the texture of the fiber is not impaired, and a highly transparent coating can be obtained.

[Coating liquid for forming a water-repellent film]
The coating solution for forming a film for producing a substrate with a water-repellent coating according to the present invention includes a coating solution for forming a particle layer in which inorganic oxide particles and resin emulsion particles are mixed and monodispersed in a polar solvent, and a water-repellent agent. And an overcoat layer forming coating solution.

Particle Layer Forming Coating Liquid The particle layer forming coating liquid is a liquid in which inorganic oxide particles and resin emulsion particles are mixed and monodispersed in a polar solvent. In the coating solution, the average particle size (D _e ) of the resin emulsion particles is preferably equal to or smaller than the average particle size (D _P ) of the inorganic oxide particles (D _e ≦ D _P ). When the average particle diameter (D _e ) of the resin emulsion particles is equal to or smaller than the average particle diameter (D _P ) of the inorganic oxide particles (D _e ≦ D _P ), the inorganic oxide particles are not easily covered with the resin emulsion particles. can do. When the average particle size (D _e ) of the resin emulsion particles is larger than the average particle size (D _P ) of the inorganic oxide particles, when the resin emulsion particles are collapsed, the inorganic oxide particles are covered with the collapsed resin There is.

  In the particle layer forming coating solution, the volume ratio (G / [G + M]) between the volume (G) of the inorganic oxide particles and the volume (M) of the resin emulsion particles is 0.25 or more (inorganic oxide) The range of the volume G of the particles is 25% or more is preferable, and the range of 0.29 to 0.9 is more preferable. When the amount ratio (G / [G + M]) is smaller than the above range, the number of inorganic oxide particles in the coating is decreased, and there is a concern that the water repellency and durability of the coating are insufficient. On the other hand, if the amount ratio (G / [G + M]) is larger than the above range, the amount of resin is relatively small, and there is a concern that the adhesive strength is lowered.

  The coating solution for forming a particle layer is composed of a dispersion in which inorganic oxide particles are dispersed in a polar solvent, and a suspension in which resin emulsion particles are suspended in a polar solvent. By mixing the dispersion and the suspension, A material in which inorganic oxide particles and resin emulsion particles are mixed and dispersed in a polar solvent can be used. By making the coating solution for forming the particle layer into two liquids of the inorganic oxide particle dispersion and the resin emulsion particle suspension, the storage stability can be improved.

  Instead of preparing a resin emulsion particle suspension, the coating liquid for particle layer formation may be prepared by directly adding a resin to the inorganic oxide particle dispersion and stirring to form resin emulsion particles. In this case, since it is not necessary to mix two liquids at the time of use, workability is good.

A process of preparing an inorganic oxide particle dispersion and a resin emulsion particle suspension and mixing them to prepare a coating solution for forming a particle layer is shown below.
Preparation of inorganic oxide particle dispersion The inorganic oxide particles are added to a polar solvent and stirred with a mixer or the like to prepare an inorganic oxide particle dispersion. The solid content concentration of the inorganic oxide particle dispersion is preferably 0.1 to 20% by weight, more preferably 0.2 to 15% by weight. The average particle diameter (D _P ) of the inorganic oxide particles is preferably in the range of 20 to 600 nm.

For example, the following solvents (A) to (G) can be used as the polar solvent of the inorganic oxide particle dispersion. These may be used singly or in combination of two or more.
(A) Alcohols such as methanol, ethanol, propanol, 2-propanol (IPA), butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol and the like.
(B) Esters such as methyl acetate, ethyl acetate, isopropyl acetate, isopropyl acetate, isobutyl acetate, butyl acetate, isopentyl acetate, pentyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, cyclohexyl acetate, and ethylene glycol monoacetate.
(C) Glycols such as ethylene glycol and hexylene glycol.
(D) Diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol isopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, pull Water repellent solvent containing ethers such as pyrene glycol monopropyl ether.
(E) Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, butyl methyl ketone, cyclohexanone, methyl cyclohexanone, dipropyl ketone, methyl pentyl ketone, and diisobutyl ketone.
(F) Toluene, N-methylpyrrolidone, etc.
(G) Water

Preparation of Resin Emulsion Particle Suspension Resin emulsion particle suspension is a suspension in which resin emulsion particles are suspended in a polar solvent. Emulsion resins include ester resins, polycarbonate resins, amide resins, imide resins, polyphenylene oxide resins, acrylic resins, vinyl chloride resins, vinyl acetate resins, silicone resins, urethane resins, or styrene. A resin based on these or a copolymer resin thereof is preferred. Since the resin emulsion particles are collapsed in the film forming step to form an adhesive, these resins become components of the adhesive.

  If the resin is added to a polar solvent and stirred with a mixer or the like, resin emulsion particles are formed in the polar solvent, and a resin emulsion particle suspension can be obtained. A polar solvent similar to the inorganic oxide particle dispersion can be used. The particle diameter of the resin emulsion particles can be adjusted by adding a surfactant or a pH adjuster and stirring at high speed. The addition amount of the surfactant and the pH adjusting agent and the stirring speed may be adjusted so that the resin emulsion particles have a desired particle size depending on the kind of the resin and the polar solvent, the amount of the resin in the dispersion, and the like. A commercially available product can be used as the resin emulsion particle suspension.

Preparation of coating solution for particle layer formation Inorganic particle dispersion and resin emulsion particle suspension are mixed and stirred to form a particle layer in which inorganic oxide particles and resin emulsion particles are mixed in a polar solvent and monodispersed. A coating solution is prepared. It is advisable to add a silicic acid solution to the inorganic oxide particle dispersion and heat aging to mix the resin emulsion particle suspension. When the silicic acid solution is added, when sunflower-like particles are used as the inorganic oxide particles, the fine particles of the sunflower-like particles are well fixed to the base particles and do not fall off.

  In the coating solution, a crosslinking material or a crosslinking inhibitor may be added to control the temperature at which the emulsion particles are disintegrated and fixed. Furthermore, a leveling agent and a dispersing agent can be added to make the coating film cleaner. Moreover, you may put a photoinitiator and a thermosetting accelerator as needed.

  In the coating solution for forming a particle layer, the inorganic oxide particle concentration is preferably in the range of 0.1 to 10% by weight, and more preferably in the range of 0.5 to 8% by weight. If the concentration is lower than the above range, the thickness of the inorganic oxide particle layer may be thin and desired irregularities may not be formed, and coating unevenness without inorganic oxide particles is likely to occur. , Hardness and scratch resistance may not be obtained. On the other hand, when the concentration is higher than the above range, although depending on the coating method, there are cases where the coating property is lowered and desired irregularities cannot be formed. In addition, the inorganic oxide particle layer may become too thick, resulting in a decrease in transparency and an increase in haze.

  The concentration of the resin emulsion in the coating solution for forming the particle layer is preferably in the range of 0.1 to 10% by weight, and more preferably in the range of 0.5 to 8% by weight. When the resin emulsion concentration is lower than the above range, an adhesive having a sufficient film thickness cannot be formed, and the adhesive strength may be lowered. On the other hand, when the resin emulsion concentration is higher than the above range, the inorganic oxide particle concentration is relatively low, the thickness of the inorganic oxide particle layer is thin, and desired unevenness may not be formed.

As described above, the average particle size (D _e ) of the resin emulsion particles contained in the coating solution for forming the particle layer is equal to or smaller than the average particle size (D _P ) of the inorganic oxide particles (D _e ≦ D _P ). Is preferred. The volume ratio (G / [G + M]) of the volume (G) of the inorganic oxide particles and the volume (M) of the resin emulsion particles is 0.25 or more (the volume of the inorganic oxide particles G is 25). % By weight) is preferable, and a range of 0.29 to 0.9 is more preferable. In order to calculate these volumes, the specific gravity of the resin emulsion was 1.1 and the specific gravity of silica was 2.2.

Preparation of Overcoat Layer Forming Coating Liquid The overcoat layer forming coating liquid is a liquid that forms a water-repellent overcoat layer that covers the surface of the particle layer, and includes at least a fluorine-containing compound, an alkyl group-containing compound, or a silicone-based compound. Those containing one kind are preferred.
Examples of the fluorine-containing compound include perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctylethyltriisopropoxysilane, trifluoropropyltrimethoxysilane, and other fluorine-containing silane derivatives, perfluorohexylphosphonic acid, Fluorine-containing phosphonic acid derivatives such as perfluorooctyl phosphonic acid and perfluorodecyl phosphonic acid, or commercially available products such as Fluorosurf manufactured by Fluoro Technology and INT series manufactured by NODASCREEN are listed.

  Examples of the alkyl group-containing compound include 10-carboxydecylphosphonic acid, 11-hydroxyundecylphosphonic acid, 11- (naphthalen-2-yloxy) undecylphosphonic acid, and 11- [2 [2- (2-methoxyethoxy) ethoxy. ] Ethoxy] undecylphosphonic acid, octadecylphosphonic acid, 11-phthalimidoundecylphosphonic acid and other phosphonic acid derivatives.

Examples of silicone compounds include modified reactive silicones. The modified reactive silicone preferably contains an acrylic group , a (meth) acryloxy group, an epoxy group, a silanol group, a phenol group, a carboxyl group or the like as a functional group. Among them, the _formula: R _n -SiX _4-n (In the formula, R represents a hydrocarbon group having 1 to 10 carbon atoms, optionally being the same or different .X: 1 carbon atoms Hydrolyzate of hydrolyzable organosilicon compound represented by -4 alkoxy group, hydroxyl group, halogen, hydrogen, n: integer of 1 to 3) or hydrolytic polycondensation in which the hydrolyzate is polycondensed by heat treatment Things are preferred.

  Examples of such hydrolyzable organosilicon compounds include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, Isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxymethyltrimethoxysilane, γ-glycidoxymethyltriethoxysilane, γ-glycidoxyethyltri Methoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltri Ethoxysilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, γ- (meth) acrylooxymethyltrimethoxysilane, γ- (meth) acrylooxymethyltriethoxysilane, γ- (meth) acryl Rooxyethyltrimethoxysilane, γ- (meth) acrylooxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meta ) Acryloxypropyltriethoxysilane, γ- (meth) a Lilooxypropyltriethoxysilane, butyltrimethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilaoctyltriethoxysilane, decyltriethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, octyltriethoxy Silane, decyltriethoxysilane, 3-ureidoisopropylpropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctylethyltriisopropoxysilane, trifluoropropyltrimethoxysilane, N- β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethylsilanol, methyltrichlorosilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ -Aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethylsilanol, methyltrichlorosilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropyl Methyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane and the like, and These mixtures are mentioned.

  Among the silane compounds, hydrolyzable containing fluorine-substituted hydrocarbon groups such as perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctylethyltriisopropoxysilane, and trifluoropropyltrimethoxysilane. A hydrolyzed polycondensate of an organosilicon compound can provide a film with better water repellency.

  An overcoat layer-forming coating solution is prepared by dispersing an overcoat layer-forming component such as a fluorine-containing compound, an alkyl group-containing compound, or a silicone-based compound in a dispersion medium. As the dispersion medium for the coating liquid for forming the overcoat layer, the same dispersion medium as that for the inorganic oxide particle dispersion liquid can be used.

  The concentration of the overcoat layer-forming coating solution is preferably 0.05 to 20% by weight, more preferably 0.1 to 10% by weight as the solid content. If the concentration of the coating solution is low, coating unevenness without a partial overcoat layer may occur, and sufficient water repellency may not be obtained. Even if the concentration of the overcoat layer forming coating solution is too high, the desired uneven structure may not be obtained, and the water repellency may not be improved, but rather may be lowered. However, the concentration of the overcoat layer forming coating solution is preferably adjusted as appropriate by the wettability with the substrate. If the substrate has good wettability, a small amount of adjustment is preferable. If the substrate is difficult to wet, it is preferable to pre-treat or adjust the solid content as much as possible.

[Method for producing substrate with water-repellent coating]
The substrate with a water-repellent coating of the present invention uses the coating-forming coating solution, and the coating solution is applied to the substrate to form a particle layer in which the resin emulsion particles are interposed between the inorganic oxide particles. After the coating, the resin emulsion particles are disintegrated by heating and drying so that a resin (adhesive) enters the gap between the inorganic oxide particles and the gap between the inorganic oxide particles and the base material. It is manufactured by forming a particle layer having a concavo-convex shape in which the upper part of the particle is exposed from the adhesive, and forming a water-repellent overcoat layer on the surface of the particle layer.

  An outline of a method for producing a substrate with a water-repellent coating is shown in FIG. The manufacturing process shown in the figure includes (I) inorganic oxide particle dispersion preparation step, (II) resin emulsion particle suspension preparation step, and (III) coating for forming a particle layer by mixing the dispersion and the suspension. A step of preparing a liquid, (IV) a coating step, (V) a particle layer forming step, and (VI) an overcoat layer forming step are shown. In addition, instead of the steps (I) to (III), a particle layer forming coating solution prepared in advance may be used. After the overcoat layer forming step, (VII) a substrate heat treatment step is performed.

(I) A step of adjusting the dispersion 30 in which the inorganic oxide particles 5 are dispersed in the polar solvent 31 (inorganic oxide particle dispersion preparing step).
(II) A step of preparing a resin emulsion particle suspension 34 in which the resin emulsion particles 32 are suspended in a polar solvent 33 (resin emulsion particle suspension adjustment step).
(III) A step of preparing the coating solution 35 for coating formation by mixing the dispersion 30 and the suspension 34 (coating solution preparation step).
(IV) A step of applying the coating solution 35 to the substrate 1 and forming a layer of the coating solution in which the resin emulsion particles 32 are interposed in the gaps between the inorganic oxide particles 5 (application step).
(V) The coating liquid is heated and dried to disintegrate the resin emulsion particles 34 so that the resin (adhesive) enters the gap between the inorganic oxide particles 5 and the gap between the inorganic oxide particles 5 and the substrate 1. A step of forming the particle layer 3 in which the upper part of the inorganic oxide particles is exposed from the adhesive (particle layer forming step).
(VI) A step of applying an overcoat layer forming coating solution on the surface of the particle layer 3 and drying to form the overcoat layer 7 (overcoat layer forming step).
(VII) The base material is heat-treated after the overcoat layer is formed (heat-treatment process of the base material).

The production steps (IV) to (VII) will be described in detail.
(IV) Coating step: A coating solution is coated on a substrate to form a particle layer in which resin emulsion particles are interposed between the inorganic oxide particles. The coating method is not particularly limited, and for example, a bar coater method, a dip method, a spray method, a spinner method, a roll coating method, a gravure coating method, a slit coating method, a pressure coating method, or the like can be used. Since the coating solution contains the resin emulsion particles together with the inorganic oxide particles, the inorganic oxide particles and the resin emulsion particles can be coated on the substrate by a single coating operation. In addition, since the inorganic oxide particles and the resin emulsion particles are uniformly dispersed in the coating solution, this coating operation forms a coating solution layer in which the resin emulsion particles are interposed between the inorganic oxide particles. can do.

(V) Particle layer forming step: The applied liquid is dried by heating, and the resin emulsion particles are collapsed to allow the resin (adhesive) to enter the gap between the inorganic oxide particles and the gap between the inorganic oxide particles and the substrate. Thus, the particle layer 3 is formed. The heating temperature may be a temperature at which the resin emulsion particles collapse. Although it varies depending on the type of resin, generally, when heated to 60 to 200 ° C., the resin emulsion particles collapse and the resin flows out. Thereafter, if necessary, curing may be promoted by UV irradiation or annealing. Since the particle diameter of the resin emulsion particles is equal to or smaller than the particle diameter of the inorganic oxide particles, the upper part of the inorganic oxide particles is not covered with the resin (adhesive) due to the collapse of the resin emulsion particles, and the inorganic oxide particles are the adhesive material. A particle layer exposed from is formed.

(VI) An overcoat layer forming coating solution is applied to the surface of the particle layer. The coating method is not limited as long as it is a method capable of uniformly coating the particle layer surface. For example, a dipping method, a bar coater method, a spray method, a spinner method, a roll coating method, a gravure coating method, a slit coating method, a curtain coating method, etc. may be used.

  It is preferable to dry after applying the overcoat layer forming coating solution, and a conventionally known method can be adopted as the drying method. The drying temperature may be any temperature that can substantially remove the dispersion medium of the overcoat layer forming coating solution. In general, 50 to 120 ° C is preferable, and 60 to 100 ° C is more preferable.

(VII) The substrate is heated after the drying treatment. Although heat processing temperature changes also with the kind of base material, 130-700 degreeC is preferable and the range of 150-500 degreeC is further more preferable. By drying and heating the substrate, the bond between the substrate and the particle layer and between the particle layer and the overcoat layer is increased, and the adhesion between the particle layer and the overcoat layer and the substrate, the strength of the film, the hardness, It is possible to form a water-repellent film having excellent scratch resistance and the like. When the heat treatment temperature is low, the adhesion, film strength, hardness, scratch resistance and the like may be insufficient. If the heat treatment temperature is too high, the substrate may be altered depending on the type of the substrate.

  The substrate with a water-repellent coating produced by the above process has a large concavo-convex shape formed by exposure of the inorganic oxide particles from the adhesive, and further, fine undulations on the surface of the inorganic oxide particles. It has high water repellency due to the synergistic uneven structure effect. Specifically, it can have water repellency with a contact angle with water of 130 ° or more, preferably 150 ° or more.

  Hereinafter, the present invention will be specifically described by way of examples. In addition, this invention is not limited by these Examples.

[Example 1]
[Standard particle size sunflower-like particles, resin standard, acrylic-styrene]
Preparation of inorganic oxide particle (sunflower-like particle) dispersion [A1] ( Preparation of substrate particles)
750 g of silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid SI-80P, average particle size 80 nm, surface potential -60 mV, SiO ₂ concentration 20 wt%, pH 10.2), 150 g of cation exchange resin (manufactured by ROHMHARS: Duolite) Were mixed and stirred for 0.5 hour. Next, after separating the cation exchange resin, 135 g of an anion exchange resin (Mitsubishi Chemical Co., Ltd .: SUNUP-C) was mixed, and after stirring for 0.5 hour, the anion exchange resin was separated to obtain a SiO ₂ concentration. 750 g of 20% by weight purified silica sol was prepared.
(Preparation of substrate particle dispersion)
To 750 g of purified silica sol, 5.1 g of polyaluminum chloride (manufactured by Taki Chemical Co., Ltd .: Takibaine # 1000, Al ₂ O ₃ concentration 23.55 wt%) was added and stirred at room temperature for 0.5 hour. Subsequently, 2903 g of pure water was added and diluted to prepare 3658 g of a base particle dispersion liquid composed of silica having a SiO ₂ concentration of 4.1% by weight. The pH of the substrate particle dispersion was 3.7.
(Addition of fine particles)
Silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid SN-350, average particle diameter 7 nm, surface potential -23 mV, SiO ₂ concentration as fine particles for coating in 3658 g of the substrate particle dispersion (SiO ₂ concentration 4.1 wt%) 294 g of 16.6 wt%, pH 3.7) were mixed. This mixed dispersion had a SiO ₂ concentration of 5.0% by weight and a pH of 3.5.
(Preparation of sunflower-like particle dispersion)
The mixed dispersion was mixed with 135 g of an anion exchange resin (Mitsubishi Chemical Corporation: SUNUP-C) and stirred for 0.5 hour, and then the anion exchange resin was separated, and the SiO ₂ concentration was 10 wt% by a rotary evaporator. A sunflower-like particle dispersion [A1] composed of silica was prepared. The dispersion H was 7.0.
(Measurement of average particle diameter D _P)
The average particle diameter (D _P ) of the sunflower-like particles was taken as an average value obtained by taking a transmission electron micrograph (TEM) and measuring 10 major axes.
(Measurement of coverage)
The sunflower-like particle dispersion was heated to 120 ° C. and dried, and the specific surface area of the sunflower-like particles was measured by the BET method to determine the coverage. The coverage was determined according to the above equation (4).

Preparation of Particle Layer Forming Coating Solution [C1] 1.8 g of 5% silicic acid solution was added to 90 g of the sunflower particle dispersion [A1] and aged at 80 ° C. for 3 hours. Thereafter, 2 g of resin emulsion particle suspension [B1] (CG 8370 manufactured by DIC: particle size 100 nm: concentration 50 wt%, acrylic-styrene) was added, and then ethanol was added to adjust the solid content concentration to 5 wt%. Then, the mixture was stirred with a magnetic stirrer at room temperature for 1 hour to obtain a coating solution [C1] for forming a particle layer. The coating solution had a pH of 7.5. Concentration of sunflower-like particles, the kind of the resin, the particle diameter _{(D e), D e /} D P ratio of the resin emulsion particles, the amount of resin, the amount ratio of the sunflower-like particles and resin emulsion particles [Sunflower particles / (Sunflower particles + Resin emulsion particles], solid content concentration, pH are shown in Table 1.

Preparation of coating liquid for overcoat layer formation [D1] Modified alcohol (Nippon Alcohol Sales Company product: Solmix A-11, mixed alcohol of methanol, ethanol and isopropyl alcohol) 2252 . 5 g of water 159 . 0 g and 61 wt% nitric acid 3 . 3 g was added and stirred at 25 ° C. for 5 minutes. Then, tridecafluorooctyltrimethoxysilane (product of MOMENTIVE: TSL8257, solid content concentration 98%) 46 . After adding 4 g and stirring at 25 ° C. for 5 minutes, the mixture was treated at 60 ° C. for 3 hours. Thereafter, 356.9 g of propylene glycol monomethyl ether (PGM) and diacetone alcohol (DAA) 213 . 91 g was added and treated at 25 ° C. for 30 minutes to obtain a solid content of 1 . A 50 wt% fluorine-containing silica-based coating solution was prepared.
Next, 100 g of fluorine-containing silica-based coating solution having a solid content concentration of 1.50% by weight is added with 10 g of PGM and mixed alcohol (Japan Alcohol Sales Company product: Solmix A-11, mixed alcohol of methanol, ethanol and isopropyl alcohol). , Solid content concentration 1 . A 0% overcoat layer forming coating solution [D1] was prepared.

Manufacture of substrate [E1] with water-repellent coating Nylon fiber was dipped in coating solution [C1] for particle layer formation for 1 minute, and then pulled up at 4 mm / sec. Thereafter, it was dried at 80 ° C. for 30 minutes. Then, after dipping for 1 minute in an overcoat layer forming coating solution [D1] having a solid content concentration of 1.0%, it was pulled up at 4 mm / sec. Thereafter, it was dried at 80 ° C. for 30 minutes. Further, the substrate was then heat-treated at 150 ° C. for 30 minutes to prepare a substrate [E1] with a water-repellent coating. For the substrate with water-repellent coating [E1], the film thickness of the particle layer (D _P ), the film thickness of the adhesive (U _F ), the average convexity height (T _F ) of the concave-convex structure of the coating, the average convexity The distance (W _F ), fine unevenness (T _FF ), fine uneven pitch width (W _FF ), water repellency (contact angle), texture, dirt removal, and adhesion were measured. The results are shown in Table 2.

The average height of projections (T _F ) and pitch width (W _F ) of the coatings were obtained by taking a transmission electron micrograph (TEM) of the cross section of the water-repellent coating. The distance was measured and taken as the average value. The inorganic oxide particle layer thickness (D _P ) and the adhesive material thickness (U _F ) are similarly measured by taking a transmission electron micrograph (TEM) of the cross section of the water-repellent coating and measuring the thickness of these 10 locations. The average value was used, and the film thickness ratio (U _F / D _P ) was calculated using this average value.

The fine irregularities (T _FF ) on the surface of the coating were measured in a 500 nm range using AFM, and the surface roughness (Ra) on a single particle was measured at three points, and the average value was defined as fine irregularities. The pitch width (W _FF ) of the fine irregularities was obtained by photographing a scanning electron microscopic amount (SEM), measuring the height of 10 convex portions and the distance between pitches, and taking the average value.

  The water repellency of the coating was measured using a fully automatic contact angle meter (DM700 manufactured by Kyowa Interface Science Co., Ltd.) and the contact angle with 5 μL water and the contact angle with 5 μL oleic acid.

  Washing resistance of the film is determined by placing the substrate with water-repellent transparent film [E1] in a fully automatic washing machine, putting detergent (10g of Kao Attack), repeating 30 minutes of washing and 5 minutes of dehydration 10 times. The contact angle of water after drying was measured, and the change in contact angle before washing was shown in Table 3.

The stain removal property of the film is the same as that of the water-repellent transparent coated substrate [E1] with a 3cm line drawn on the surface using a Mitsubishi oil marker (small piece red). Evaluation was made by visual confirmation. The evaluation criteria are shown below.
Ink completely falls: ◎ If ink looks closely, it remains: ○
Ink is slightly left: △ Ink is clearly left: ×

The texture of the coating was evaluated based on the hand touch before and after the coating. The evaluation criteria are shown below.
The feel does not change before and after application: ◎
Slightly irritating after application: ○
Somewhat awkward after application: △
Clearly tingling after application: ×

[Example 2]
[Standard particle size sunflower particles, small amount of resin, acrylic-styrene]
Preparation of particle layer forming coating solution [C2 ] To 90 g of the sunflower-like particle dispersion [A1], 5% silicic acid solution was added . 8 g was added and aged at 80 ° C. for 3 hours. Thereafter, 0.2 g of resin emulsion particle suspension [B1] (CG 8370 manufactured by DIC Corporation: particle size 100 nm: concentration 50 wt%, acrylic-styrene) was added, and then ethanol was added to obtain a solid content concentration of 5 wt. And stirred with a magnetic stirrer at room temperature for 1 hour to obtain a particle layer forming coating solution [C2]. The coating solution had a pH of 7.5. Table 1 shows the concentration of sunflower-like particles, the type of resin, the particle diameter of resin emulsion particles, the ratio of sunflower-like particles to resin emulsion particles [sunflower-like particles / (sunflower-like particles + resin emulsion particles), solid content concentration, pH. It was shown to.
Production of water repellent coated substrate [E2] A water repellent coated substrate [E2] was produced in the same manner as in Example 1 except that the particle layer forming coating solution [C2] was used. The physical properties of the film were measured. The results are shown in Table 2.

Example 3
[Standard particle size sunflower-like particles, large amount of resin, acrylic-styrene]
Preparation of coating solution [C3] for coating film formation To 90 g of the sunflower-like particle dispersion [A1], 1% of 5% silicic acid solution was added . 8 g was added and aged at 80 ° C. for 3 hours. Thereafter, 5 g of resin emulsion particle suspension [B1] (CG 8370 manufactured by DIC: particle size 100 nm: concentration 50 wt%, acrylic-styrene) was added, and then ethanol was added to adjust the solid content concentration to 5 wt%. Then, the mixture was stirred with a magnetic stirrer at room temperature for 1 hour to obtain a particle layer forming coating solution [C3]. The pH of the coating solution is 7 . It was 5. Table 1 shows the concentration of sunflower-like particles, the type of resin, the particle diameter of resin emulsion particles, the ratio of sunflower-like particles to resin emulsion particles [sunflower-like particles / (sunflower-like particles + resin emulsion particles), solid content concentration, pH. It was shown to.
Production of water repellent coated substrate [E3] A water repellent coated substrate [E3] was produced in the same manner as in Example 1 except that the particle layer forming coating solution [C3] was used. The physical properties of the film were measured. The results are shown in Table 2.

Example 4
[Standard particle size sunflower-like particles, resin standard, emulsion particle size small, acrylic-styrene]
Preparation of emulsion resin particle suspension [B2] 1% hydrochloric acid and pure water were added to 100 g of resin emulsion particle suspension [B1] (CG 8370 manufactured by DIC: particle size 100 nm: concentration 50% by weight, acrylic-styrene). 250 g of a 20% diluted solution with a pH of 4.5 was prepared. Then, it stirred for 15 minutes at 1500 rpm using the homomixer, and prepared emulsion resin particle suspension [B2]. When this resin emulsion suspension [B2] was observed using TEM, it was a resin emulsion having an average particle diameter of 30 nm.
Preparation of particle layer forming coating solution [C4 ] To 90 g of the sunflower-like particle dispersion [A1], 5% silicic acid solution was added . 8 g was added and aged at 80 ° C. for 3 hours. Thereafter, 5 g of the resin emulsion particle suspension [B2] is added, and then ethanol is added to adjust the solid content concentration to 5% by weight. The mixture is stirred for 1 hour at room temperature with a magnetic stirrer to form a particle layer. A coating solution [C4] was obtained. The pH of the coating solution was 6.0. Table 1 shows the concentration of sunflower-like particles, the type of resin, the particle diameter of resin emulsion particles, the ratio of sunflower-like particles to resin emulsion particles [sunflower-like particles / (sunflower-like particles + resin emulsion particles), solid content concentration, pH. It was shown to.
Production of water-repellent coated substrate [E4] A water-repellent coated substrate [E4] was produced in the same manner as in Example 1 except that the particle layer forming coating solution [C4] was used. The physical properties of the film were measured. The results are shown in Table 2.

Example 5
[Standard particle size sunflower particles, resin standard, acrylic-urethane]
Preparation of Particle Layer Forming Coating Solution [C5] 1.8 g of 5% silicic acid solution was added to 90 g of the sunflower particle dispersion [A1] and aged at 80 ° C. for 3 hours. Thereafter, 2.22 g of resin emulsion particle suspension [B3] (CG-5010EF manufactured by DIC: particle size 100 nm: concentration 45 wt%, acrylic-urethane) was added, and then ethanol was added to obtain a solid content concentration of 5 The mixture was prepared in a weight percent and stirred with a magnetic stirrer at room temperature for 1 hour to obtain a particle layer forming coating solution [C5]. The pH of the coating solution is 7 . It was 5. Table 1 shows the concentration of sunflower-like particles, the type of resin, the particle diameter of resin emulsion particles, the ratio of sunflower-like particles to resin emulsion particles [sunflower-like particles / (sunflower-like particles + resin emulsion particles), solid content concentration, pH. It was shown to.
Production of water repellent coated substrate [E5] A water repellent coated substrate [E5] was produced in the same manner as in Example 1 except that the particle layer forming coating solution [C5] was used. The physical properties of the film were measured. The results are shown in Table 2.

Example 6
[Standard particle size sunflower particles, resin standard, acrylic-silicone]
Preparation of particle layer forming coating solution [C6 ] To 90 g of the sunflower-like particle dispersion [A1], 5% silicic acid solution was added . 8 g was added and aged at 80 ° C. for 3 hours. Thereafter, 2 g of a resin emulsion particle suspension [B4] (SA-6360 manufactured by DIC: particle size 150 nm: concentration 50 wt%, acrylic-silicone) was added, and then ethanol was added to obtain a solid content concentration of 5 wt%. And stirred with a magnetic stirrer at room temperature for 1 hour to obtain a coating solution [C6] for forming a particle layer. The pH of the coating solution was 8.5. Table 1 shows the concentration of sunflower-like particles, the type of resin, the particle diameter of resin emulsion particles, the ratio of sunflower-like particles to resin emulsion particles [sunflower-like particles / (sunflower-like particles + resin emulsion particles), solid content concentration, pH. It was shown to.
Production of water repellent coated substrate [E6] A water repellent coated substrate [E6] was produced in the same manner as in Example 1 except that the particle layer forming coating solution [C6] was used. The physical properties of the film were measured. The results are shown in Table 2.

Example 7
[Small particle sunflower-like particles, resin standard, acrylic-styrene]
Preparation of inorganic oxide particle (sunflower-like particle) dispersion [A2] ( Preparation of substrate particles)
150 g of cation exchange resin (ROHMHARS: Duolite) is added to 750 g of silica sol (manufactured by JGC Catalysts & Chemicals: Cataloid SI-45P, average particle size 45 nm, surface potential -60 mV, SiO ₂ concentration 20 wt%, pH 10.2). Mix and stir at 30 ° C. for 0.5 h. Next, after separating the cation exchange resin, 135 g of an anion exchange resin (Mitsubishi Chemical Co., Ltd .: SUNUP-C) is mixed and stirred for 0.5 hour, and then the anion exchange resin is separated to obtain SiO _2. 750 g of purified silica sol having a concentration of 20% by weight was prepared. Next, 9.2 g of polyaluminum chloride (manufactured by Taki Chemical Co., Ltd .: Takibaine # 1000, Al ₂ O ₃ concentration 23.55 wt%) was added to 750 g of purified silica sol, and the mixture was stirred at room temperature for 0.5 hour. Next, 3661 g of a metal oxide particle dispersion [a-2] for a substrate made of silica having a SiO ₂ concentration of 4.1 wt% diluted by adding 2903 g of pure water was prepared. Subsequently, to the 3662 g of the metal oxide particle dispersion [a-2] for the substrate, silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid SN-350, average particle diameter 7 nm, surface potential -23 mV, SiO ₂ concentration 16.6 wt% , PH 3.7) 595 g was mixed. At this time, the pH of the mixed dispersion was 3.5. Next, 135 g of an anion exchange resin (Mitsubishi Chemical Co., Ltd .: SUNUP-C) was mixed with the mixed dispersion and stirred for 0.5 hour. Then, the anion exchange resin was separated and the SiO ₂ concentration was measured by a rotary evaporator. An inorganic oxide particle (sunflower particle) dispersion [A2] composed of 10% by weight of silica was prepared. The pH of the dispersion was 6.5.
Preparation of Particle Layer Forming Coating Solution [C7] A particle layer forming coating solution [C7] was obtained in the same manner as in Example 1 except that 90 g of the sunflower particle dispersion [A2] was used. The pH of the coating solution is 7 . It was 5. Table 1 shows the concentration of sunflower-like particles, the type of resin, the particle diameter of resin emulsion particles, the ratio of sunflower-like particles to resin emulsion particles [sunflower-like particles / (sunflower-like particles + resin emulsion particles), solid content concentration, pH. It was shown to.
Production of water repellent coated substrate [E7] A water repellent coated substrate [E7] was produced in the same manner as in Example 1 except that the particle layer forming coating solution [C7] was used. The physical properties of the film were measured. The results are shown in Table 2.

Example 8
[Kinpei particles, resin standard, acrylic-styrene]
Preparation of coating liquid [C8] for particle layer formation Dispersion of gold flat sugar silica (manufactured by JGC Catalysts & Chemicals: Cataloid CO-80A, average particle diameter 80 nm, specific surface area 43 m ² / g, surface potential −60 mV, SiO ₂ concentration 40 weight % to obtain a pH 10. 2) except for using 22.5g in the same manner as in example 1 particle layer forming coating solution [C8]. The pH of the coating solution was 9.5. Table 1 shows the concentration of confetti particles, the type of resin, the particle diameter of resin emulsion particles, the quantitative ratio of confetti particles to resin emulsion particles [competitive saccharide particles / (competitive saccharide particles + resin emulsion particles), solid content concentration, and pH.
Production of water repellent coated substrate [E8] A water repellent coated substrate [E8] was produced in the same manner as in Example 1 except that the particle layer forming coating solution [C8] was used. The physical properties of the film were measured. The results are shown in Table 2.

Example 9
[Substrate change of Example 1]
Manufacture of substrate [E9] with water repellent coating A coating solution [C1] for forming a particle layer is applied to a glass substrate (Hamashinsha product: FL glass, thickness: 3 mm, refractive index: 1.51) by a bar coater method. A substrate [E9] with a water-repellent coating was produced in the same manner as in Example 1 except that it was applied and dried at 80 ° C. for 10 minutes, and the physical properties of the film were measured in the same manner as in Example 1 except for the washing resistance.

The adhesion of the film was made by making 11 parallel scratches on the surface of the substrate [E9] with a water-repellent transparent film [E9] at intervals of 1 mm in length and width by making 100 squares, and attaching cellophane tape to this. When peeled, the number of cells of the film remaining without being peeled was evaluated by classifying into the following three stages. The evaluation criteria are shown below.
Number of remaining cells: ◎ Number of remaining cells: 95 to 99: ○
Number of remaining cells 90 to 94: Δ Number of remaining cells 89 or less: ×
The measurement results are shown in Tables 1 and 2.

Example 10
[Sunflower particle AgO composite, resin standard, acrylic-styrene]
Preparation of inorganic oxide particle (sunflower-like particle) dispersion [A3] ( Preparation of substrate particles)
750 g of silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid SI-80P, average particle size 80 nm, surface potential -60 mV, SiO ₂ concentration 20 wt%, pH 10.2), 150 g of cation exchange resin (manufactured by ROHMHARS: Duolite) Were mixed and stirred for 0.5 hour. Next, after separating the cation exchange resin, 135 g of an anion exchange resin (Mitsubishi Chemical Co., Ltd .: SUNUP-C) was mixed, and after stirring for 0.5 hour, the anion exchange resin was separated to obtain a SiO ₂ concentration. 750 g of 20% by weight purified silica sol was prepared.
(Preparation of substrate particle dispersion)
To 750 g of the purified silica sol, 5.1 g of polyaluminum chloride (manufactured by Taki Chemical Co., Ltd .: Takibaine # 1000, Al ₂ O ₃ concentration 23.55 wt%) was added and stirred at room temperature for 0.5 hour. Subsequently, 2903 g of pure water was added and diluted to prepare 3658 g of a base particle dispersion liquid composed of silica having a SiO ₂ concentration of 4.1% by weight. The pH of the substrate particle dispersion was 3.7.
(Addition of fine particles)
3658 g of the substrate particle dispersion (SiO ₂ concentration: 4.1 wt%), AgO—SiO—Al ₂ O ₃ nanoparticles (manufactured by JGC Catalysts & Chemicals Co., Ltd .: ATOMY BALL UA average particle diameter of 10 nm, surface) as fine particles for coating 3253 g of an electric potential of −20 mV, a concentration of 1.5% by weight, and a pH of 7.0 were mixed. Thereafter, the solution was concentrated to 5.0 weight by a rotary evaporator.
(Preparation of sunflower-like particle dispersion)
135 g of anion exchange resin (manufactured by Mitsubishi Chemical Co., Ltd .: SUNUP-C) was mixed with the mixed dispersion, and the mixture was stirred for 0.5 hours, and then the anion exchange resin was separated, and the SiO ₂ concentration was 10% by weight using a rotary evaporator. A sunflower-like particle dispersion [A3] comprising silica was prepared. The dispersion H was 7.0.
(Measurement of average particle diameter D _P)
The average particle diameter of the sunflower-like particles was taken as an average value obtained by taking a transmission electron micrograph (TEM) and measuring 10 major diameters.
(Measurement of coverage)
The dispersion of the sunflower-like particles was heated to 120 ° C. and dried, and the specific surface area of the sunflower-like particles was measured by the BET method to determine the coverage. The coverage was determined according to the above equation (4).
Preparation of Particle Layer Forming Coating Solution [C10] 1.8 g of 5% silicic acid solution was added to 90 g of the sunflower particle dispersion [A3] and aged at 80 ° C. for 3 hours. Thereafter, 2 g of resin emulsion particle suspension [B1] (CG 8370 manufactured by DIC: particle size 100 nm: concentration 50 wt%, acrylic-styrene) was added, and then ethanol was added to adjust the solid content concentration to 5 wt%. Then, the mixture was stirred with a magnetic stirrer at room temperature for 1 hour to obtain a coating solution [C11] for forming a particle layer. The coating solution had a pH of 7.5. Table 1 shows the concentration of sunflower-like particles, the type of resin, the particle diameter of resin emulsion particles, the ratio of sunflower-like particles to resin emulsion particles [sunflower-like particles / (sunflower-like particles + resin emulsion particles), solid content concentration, pH. It was shown to.
Production of water repellent coated substrate [E10] A water repellent coated substrate [E10] was produced in the same manner as in Example 10 except that the particle layer forming coating solution [C10] was used. The physical properties of the film were measured in the same manner as in Example 1. The results are shown in Table 2.

[Comparative Example 1]
[Standard particle size sunflower-like particles, resin oligomer (non- emulsion )]
Preparation of Adhesive Forming Coating Solution [R1] Modified alcohol (manufactured by Nippon Alcohol Sales Co., Ltd .: Solmix A-11, mixed alcohol of methanol, ethanol and isopropyl alcohol) 72.5 g of water 10.0 g and concentration 61% by weight Nitric acid 0.1g was added and it stirred at 25 degreeC for 10 minutes. Next, 17.4 g of tetraethoxysilane (manufactured by Tama Chemical Industry Co., Ltd .: normal ethyl silicate-A, SiO ₂ concentration of 28.8 wt%) was added and stirred at 30 ° C. for 30 minutes to hydrolyze tetraethoxysilane (solid An adhesive forming coating solution [R1] made of silica having a concentration of 5.0% by weight and a molecular weight of 1000) was prepared.
Preparation of Particle Layer Forming Coating Solution [R2] To 90 g of the sunflower particle dispersion [A1], 1.8 g of 5% silicic acid solution was added and aged at 80 ° C. for 3 hours. Thereafter, 20 g of the particle layer forming coating solution [R1] was added, and then ethanol was added to adjust the solid content concentration to 5% by weight, followed by stirring with a magnetic stirrer at room temperature for 1 hour for coating forming. A liquid [R2] was obtained. The coating solution had a pH of 3.8. Table 3 shows the concentration of sunflower-like particles, the type of resin, the ratio of the amount of sunflower-like particles to the resin (sunflower-like particles / (sunflower-like particles + resin emulsion particles)), solid content concentration, and pH.
Production of water-repellent coated substrate [R3] A water-repellent coated substrate [R3] was produced in the same manner as in Example 1 except that the particle layer forming coating solution [R2] was used. The physical properties of the film were measured. The results are shown in Table 4.

[Comparative Example 2]
[Standard particle size sunflower-like particles, no resin added]
Preparation of Particle Layer Forming Coating Liquid [L2] 1.8 g of 5% silicic acid solution was added to 90 g of the sunflower particle dispersion [A1] and aged at 80 ° C. for 3 hours. Thereafter, ethanol was added to adjust the solid concentration to 5% by weight, and the mixture was stirred with a magnetic stirrer at room temperature for 1 hour to obtain a particle layer forming coating solution [L2]. The coating solution had a pH of 7.5. Table 3 shows the concentration of sunflower-like particles, the type of resin, the ratio of the amount of sunflower-like particles to the resin (sunflower-like particles / (sunflower-like particles + resin emulsion particles)), solid content concentration, and pH.
Production of water-repellent coated substrate [L3] A water-repellent coated substrate [L3] was produced in the same manner as in Example 1 except that the particle layer forming coating solution [L2] was used. The physical properties of the film were measured. The results are shown in Table 4.

[Comparative Example 3]
[Standard particle size sunflower-like particles, excess resin]
Preparation of Particle Layer Forming Coating Solution [M2] 1.8 g of 5% silicic acid solution was added to 90 g of the sunflower particle dispersion [A1] and aged at 80 ° C. for 3 hours. Thereafter, 72 g of resin emulsion particle suspension [B1] (CG 8370 manufactured by DIC Corporation: particle size 100 nm: concentration 50 wt%, acrylic-styrene) was added, and then ethanol was added to obtain a solid content concentration of 5 wt%. The resulting mixture was stirred with a magnetic stirrer at room temperature for 1 hour to obtain a particle layer forming coating solution (R3). The pH of the coating solution was 7.5. Table 3 shows the concentration of sunflower-like particles, the type of resin, the particle diameter of resin emulsion particles, the ratio of sunflower-like particles to resin emulsion particles [sunflower-like particles / (sunflower-like particles + resin emulsion particles), solid content concentration, pH. It was shown to.
Production of water repellent coated substrate [M3] A water repellent coated substrate [M3] was produced in the same manner as in Example 1 except that the particle layer forming coating solution [M2] was used. The physical properties of the film were measured. The results are shown in Table 4.

[Comparative Examples 4 to 6]
[Physical properties of the substrate]
The physical properties of the base materials (nylon, glass, slate) used in Examples 1 to 10 were measured and shown in Table 4.

1-Substrate, 2-Coating, 3-Particle Layer, 4-Adhesive, 5-Inorganic Oxide Particle, 6-Water Drop, 7-Overcoat Layer, 10-Substrate with Water-repellent Coating, 20-Sunflower-like Particle 21-substrate particles, 22-fine particles, 30-dispersion, 31-polar solvent, 32-resin emulsion particles, 33-polar solvent, 34-suspension.

Claims (21)

  A water-repellent substrate having a water-repellent coating on the surface of the substrate, wherein the coating contains inorganic oxide particles and adheres to the gap between the inorganic oxide particles and the gap between the inorganic oxide particles and the substrate. A particle layer interposing a material and a water-repellent overcoat layer covering the particle layer, the upper portion of the inorganic oxide particles having an uneven shape exposed from the adhesive, and maintaining the uneven shape A substrate with a water-repellent coating, characterized by having a concavo-convex structure covered with the overcoat layer on the surface of the coating. The average particle diameter (D _P ) of the inorganic oxide particles is 20 to 600 nm, the film thickness (U _F ) of the adhesive is 6 to 400 nm, and the average particle diameter (D _P ) of the inorganic oxide particles is The ratio of the film thickness (U _F ) of the adhesive (U _F / D _P ) is 1/3 to 2/3, and the average particle diameter (D _P ) of the inorganic oxide particles is 1/3 to 2 / 3. The substrate with a water-repellent coating according to claim 1, wherein 3 is exposed from the adhesive.   The substrate with a water-repellent coating according to claim 1 or 2, wherein the water-repellent coating has a thickness of 30 nm to 700 nm. The average height of the projections of the bumpy structure of the water repellent coating film surface _{(T F)} is in the range of 10 to 300 nm, the average distance between convex portions (Bitch width) _{(W F)} is in the range of 1~1000nm The substrate with a water-repellent coating according to any one of claims 1 to 3.   The inorganic oxide particles have a spherical shape, a plate shape, a confetti shape, a lump shape or a sunflower shape, or a spherical shape, a plate shape, a confetti shape, a lump shape or a sunflower shape, and are porous. The substrate with a water-repellent coating according to any one of claims 1 to 4, wherein the substrate has a water-repellent coating.   The sunflower-like particles are composed of base particles made of an inorganic oxide and fine particles of an inorganic oxide covering the surface of the base particle, and the sunflower-like particle surface has fine irregularities due to the fine particles. The substrate with a water-repellent coating according to claim 5. The sunflower-shaped particles have fine irregularities on the surface of the irregular structure of the water-repellent coating, and the average height of the fine irregularities (T _FF ) is in the range of 0.5 to 10 nm. The base material with a water-repellent coating according to claim 6, wherein an average distance (bitch width) (W _FF ) between the convex portions is in the range of 1 to 30 nm.   The contact angle with water is 130 degrees or more, The substrate with a water-repellent coating according to any one of claims 1 to 7. Inorganic oxide particles are composed of SiO ₂ , Al ₂ O ₃ , Sb ₂ O ₅ , ZrO ₂ , TiO ₂ , Fe ₂ O ₃ , CeO ₂ , AgO, CuO, Cu ₂ O, ZnO and their complex oxides or mixtures. The substrate with a water-repellent coating according to any one of claims 1 to 8, which is at least one selected.   Adhesive is emulsion resin, ester resin, polycarbonate resin, amide resin, imide resin, polyphenylene oxide resin, acrylic resin, vinyl chloride resin, vinyl acetate resin, silicone resin, urethane The base material with a water-repellent coating according to any one of claims 1 to 9, wherein the base material is at least one selected from a base resin, a styrene resin, or a copolymer resin thereof.   A water-repellent coating comprising: a coating solution for forming a particle layer in which inorganic oxide particles and resin emulsion particles are mixed and monodispersed in a polar solvent; and a coating solution for forming a water-repellent overcoat layer Coating liquid for forming. 12. The water repellent coating film according to claim 11, wherein the average particle size (D _e ) of the resin emulsion particles is equal to or smaller than the average particle size (D _P ) of the inorganic oxide particles (D _e ≦ D _P ). Coating liquid for forming.   The volume ratio (G / [G + M]) of the volume (G) of the inorganic oxide particles and the volume (M) of the resin emulsion particles is in the range of 0.25 to 0.9. The coating liquid for forming a water repellent film according to claim 11 or claim 12.   The coating solution for forming a particle layer is composed of a dispersion in which inorganic oxide particles are dispersed in a polar solvent, and a suspension in which resin emulsion particles are suspended in a polar solvent. By mixing the dispersion and the suspension, The coating liquid for forming a water-repellent coating according to any one of claims 11 to 13, wherein the coating liquid for forming a particle layer is formed by mixing inorganic oxide particles and resin emulsion particles in a polar solvent and monodispersing them.   The coating liquid for overcoat layer formation contains at least 1 sort (s) of a fluorine-containing compound, an alkyl-group containing compound, or a silicone type compound, The water repellent film formation in any one of Claims 11-14 characterized by the above-mentioned. Coating liquid.   A coating solution for forming a particle layer in which inorganic oxide particles and resin emulsion particles are monodispersed and suspended in a polar solvent is applied to a base material, and the resin emulsion particles are interposed between the inorganic oxide particles. After the coating, the resin emulsion particles are disintegrated so that the resin enters the gap between the inorganic oxide particles and the gap between the inorganic oxide particles and the base material to interpose an adhesive and the inorganic oxide particles An overcoat layer forming coating is formed so as to maintain a concavo-convex shape on the surface of the concavo-convex shape where the inorganic oxide particles of the particle layer are exposed. A method for producing a substrate with a water-repellent coating, comprising applying a liquid to form a water-repellent coating having a concavo-convex structure covered with the overcoat layer on the surface of the substrate.   A dispersion of inorganic oxide particles and a suspension of resin emulsion particles are mixed to prepare a coating solution for forming a particle layer in which inorganic oxide particles and resin emulsion particles are mixed in a polar solvent and monodispersed. The manufacturing method of the base material with a water-repellent film of Claim 16 which apply | coats this coating liquid to a base material. The average particle size (D _e ) of the resin emulsion particles contained in the coating liquid for forming the particle layer is equal to or smaller than the average particle size (D _P ) of the inorganic oxide particles (D _e ≦ D _P ). Item 18. A method for producing a substrate with a water-repellent coating according to Item 16 or Item 17.   The volume ratio (G / [G + M]) between the volume (G) of the inorganic oxide particles contained in the coating liquid for forming the particle layer and the volume (M) of the resin emulsion particles is 0.25 to 0.9. The method for producing a substrate with a water-repellent coating according to any one of claims 16 to 18, wherein the substrate has a water-repellent coating.   As emulsion resin, ester resin, polycarbonate resin, amide resin, imide resin, polyphenylene oxide resin, acrylic resin, vinyl chloride resin, vinyl acetate resin, silicone resin, urethane resin, or styrene resin A resin emulsion particle suspension obtained by suspending resin emulsion particles composed of a resin or a copolymer resin thereof in a polar solvent and an inorganic oxide particle dispersion obtained by dispersing inorganic oxide particles in a polar solvent are mixed. The method for producing a substrate with a water-repellent coating according to any one of claims 16 to 19, wherein a coating liquid for forming a particle layer is prepared. 21. The water-repellent film-coated base according to claim 16, wherein the resin emulsion particles are collapsed by any one of heat drying, electron beam irradiation, or ultraviolet (UV) irradiation. A method of manufacturing the material.

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