JP2015116731A - Substrate with repellent coating film and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a substrate with a repellent coating film especially excellent in repellency, and also excellent in transparency, haze, hardness, scratch resistance, abrasion resistance, adhesiveness and the like.SOLUTION: There is provided a substrate with a repellent coating film consisting of a substrate and a repellent coating film on a surface of the substrate where the repellent coating film consists of a particle layer containing a metal oxide particle in which a surface of a metal oxide particle for substrate (A) is coated by a metal oxide particle for coating (B) and an overcoat layer on the metal oxide particle layer, the surface of the repellent coating film has an uneven structure with an average height (T) of the projection portion in a range of 50 to 500 nm and an average distance between projection portions (pitch width) (W) in the range of 20 to 1000 nm, and the substrate is fiber or fabric and a contact angle with water is in the range of 100 to 180°.

Description

  The present invention relates to a substrate with a water-repellent coating and a method for producing the same. In particular, the present invention relates to a substrate with a water-repellent coating that is excellent in water repellency and excellent in transparency, haze, hardness, strength, scratch resistance, abrasion resistance, adhesion, and the like, and a method for producing the same.

  In general, when the solid surface has a fractal structure, when the solid surface is hydrophilic, the hydrophilicity is improved and super hydrophilicity is exhibited. Conversely, when the solid surface is hydrophobic, the water repellency is improved. It is known that it exhibits super water repellency.

  Patent Document 1 (Japanese Patent Application Laid-Open No. 2005-343016) discloses a super-water-repellent film-coated article in which a super-water-repellent film is coated on the surface of a base material, and a protrusion and a water-repellent film in which the super-water-repellent film is a fine particle aggregate. A super-water-repellent coating in which in the coating area of the coating, there are a portion where the protrusion is present and a portion where the protrusion is not present, and the surface of the coating where the protrusion is present is uneven A coated article is disclosed.

  Specifically, colloidal silica bonded in three dimensions, alkylalkoxysilane, and alkylalkoxysilane containing fluorine are mixed to prepare a cohydrolyzed / condensed polymer of water repellent material and silicon oxide fine particles. Is used as a dispersion for water repellent treatment, applied by a flow coat method, and naturally dried to prepare a super water repellent treated glass substrate.

  Patent Document 2 (WO2003 / 039856) discloses a superstructure including a base, a base film having micro unevenness formed on the surface of the base, and a water-repellent film formed on the micro unevenness of the base film. A super-water-repellent substrate comprising a water-repellent substrate, wherein the surface shape of the water-repellent coating is composed of particulate protrusions and columnar protrusions having a height measured from the surface of the substrate higher than the particulate protrusions. It is disclosed.

  Specifically, a decamethylcyclopentasiloxane solution of tetrachlorosilane is prepared as a coating liquid for forming an uneven base film that is a base film containing silica as a main component, and a decamethylalkoxysilane containing fluorine is separately prepared. Prepare a methylcyclopentasiloxane solution as a water repellent treatment agent. First, apply a coating solution for forming an uneven base film on the surface of a windshield glass for automobiles and leave it standing, then apply a water repellent treatment agent and leave it still. After that, it is washed with ethyl alcohol to completely wash away the water repellent agent on the surface, and is naturally dried (without firing) to prepare a windshield glass which has been subjected to water repellent treatment.

  Patent Document 3 (Japanese Patent Application Laid-Open No. 2004-137137) discloses an article coated with a film mainly composed of silicon oxide having fine irregularities on the surface, and the fine irregularities are formed by minute protrusions and columnar protrusions. A film-coated article characterized by being configured is disclosed. As its production method, it is disclosed that a film having such a 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 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 Then, a water / oil repellent liquid in which an acid is added to 5 × 10 ⁻⁴ mol to 2 × 10 ⁻² mol with respect to 1 mol of fluoroalkylsilane was applied to a mixed solution composed of water and an organic solvent. A water repellent glass comprising a water repellent layer that is a thin film is disclosed.

  Specifically, an underlayer is formed using an isopropyl alcohol dispersion of a mixture of silica sol (molecular weight of about 3,000) and silica sol (molecular weight of about 100,000) at a specific molar ratio as a coating solution for forming the underlayer. Separately, as a water / oil repellent solution, an ethanol solution of silica sol (molecular weight of about 3,000) and tin oxide particles (particle size 20 nm) using antimony oxide as a dopant, propyl alcohol and heptadecatridecylfluoroalkylsilane, A mixture with an aqueous nitric acid solution is applied and dried at 250 ° C. to prepare a water-repellent glass.

JP 2005-343016 A WO2003 / 039856 JP 2004-137137 A JP-A-8-40748

  However, in the method of Patent Document 1, a film in which silicon oxide fine particles are laminated non-uniformly is formed, the unevenness formed on the surface is relatively large, and the adhesion and strength of the film to the substrate are insufficient. In some cases, the reproducibility of water repellency could not be obtained sufficiently.

  In addition, in the method of Patent Document 2, hydrolysis and polycondensation of the base film forming component and the water repellent treatment agent may be insufficient, or the strength and hardness of the coating may not be sufficiently obtained. Although the value was high, it sometimes dropped significantly due to wear or the like.

  Further, in Patent Document 3, although the initial contact angle exhibits super water repellency, there is a problem that the contact angle after the abrasion resistance test using a dry cloth is greatly reduced. As in Patent Document 4, although the decrease in contact angle with water after a wear resistance test using an automobile wiper is small, the initial contact angle, the contact angle after the wear resistance test, and the contact angle after the weather resistance test are both Super water repellency of about 110 to 100 and a contact angle of 150 ° C. or higher is not obtained.

  As described above, depending on the application and usage, further improvement of water repellency, improvement of adhesion of the water-repellent film to the substrate, wear resistance, scratch resistance, etc., in addition to maintaining these performances over a long period of time Is required.

  As a result of intensive studies in view of the above problems, the present inventors constituted a particle layer from metal oxide particles in which the surface of the metal oxide particles (A) for the substrate was coated with the metal oxide fine particles (B) for coating. When a water-repellent film having a predetermined concavo-convex structure is formed, water repellency is high, adhesion to the base material, wear resistance, scratch resistance, etc. are improved, and in addition, these performances are maintained over a long period of time. Found that it would be possible.

  Then, the present inventors applied such metal oxide particle dispersion on a glass substrate and dried, and then applied a hydrolyzate dispersion of normal ethyl silicate and dried. After heat treatment, apply a hydrolyzed dispersion of water and nitric acid to tridecafluorooctyltrimethoxysilane alcohol solution, dry, heat treatment, adhesion to the substrate, transparency, hardness The inventors have found that a super-water-repellent substrate with a thin film excellent in scratch resistance, abrasion resistance, haze and the like can be obtained, and have completed the present invention.

[1] A substrate and a water-repellent coating on the surface of the substrate,
The water-repellent coating comprises a particle layer comprising metal oxide particles obtained by coating the surface of the metal oxide particles for substrate (A) with the metal oxide particles for coating (B), and an overcoat layer on the metal oxide particle layer The surface of the water-repellent coating has a concavo-convex structure, and the average height (T _F ) of the convex portions is in the range of 50 to 500 nm,
With a water-repellent coating with an average inter-convex distance (pitch width) (W _F ) in the range of 20 to 1000 nm, the substrate is a fiber or cloth, and a contact angle with water is in the range of 100 to 180 ° Base material.

[2] The substrate with a water-repellent coating according to [1], wherein the metal oxide particles for substrate (A) are spherical particles, and the average particle diameter (D _A ) is in the range of 40 to 600 nm.
[3] The substrate with a water-repellent coating according to [1], wherein the coating metal oxide fine particles (B) have an average particle diameter (D _B ) in the range of 4 to 60 nm.

[4] The water repellency of [1], wherein the coverage of the metal oxide particles for substrate (A) by the metal oxide particles for coating (B) represented by the following formula (1) is in the range of 30 to 100%. Base material with coating.
Coverage (%) = [[Measured Specific Surface Area of Metal Oxide Particles (S _A ) −Measured Specific Surface Area of Metal Oxide Particles for Substrate (S _M )] / [Calculation When 100% Covered Specific surface area (S _C ) -measured specific surface area of metal oxide particles for substrate (S _M )]] × 100 (1)
(Where (S _C ) = surface area per metal oxide particle × number of particles per unit weight (1 g),
Surface area per metal oxide particle = 4π · [(D _A ) / 2 + (D _B ) / 2] ² , Number of metal oxide particles for substrate (A) per unit weight (1 g) = 1 / [ 4/3 · π [(D _A ) / 2] ³ · d, d represents the particle density (g / ml) of the metal oxide particles (A) for the substrate. )

[5] The water repellency of [1], wherein the ratio (D _B ) / (D _A ) of the average particle size (D _B ) to the average particle size (D _A ) is in the range of 0.007 to 0.5. Base material with coating.
[6] The metal oxide particles for substrate (A) and the metal oxide particles for coating (B) are SiO ₂ , Al ₂ O ₃ , Sb ₂ O ₅ , ZrO ₂ , TiO ₂ , Fe ₂ O ₃ , CeO. ₂ and a composite oxide or mixture thereof (provided that the metal oxide particles for substrate (A) and the metal oxide particles for coating (B) may be the same). The substrate with a water-repellent coating according to claim 1.
[7] The substrate with a water-repellent coating according to [1], wherein the metal oxide particles for substrate (A) and the metal oxide particles for coating (B) are both SiO ₂ .
[8] The substrate with a water repellent coating according to [1], wherein the overcoat layer comprises at least one of a fluorine-containing compound, an alkyl group-containing compound, and a silicone compound.
[9] The substrate with a water-repellent coating according to [8], wherein the overcoat layer is a hydrolyzed polycondensate of a hydrolyzable organosilicon compound represented by the following formula (1).
_{R n -SiX 4-n (1} )
(In the formula, R is a hydrocarbon group having 1 to 10 carbon atoms and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a halogen, hydrogen, n: an integer of 1 to 3)

[10] The water repellency according to [9], wherein the formation amount of the overcoat layer is in the range of 1 to 100 parts by weight as SiO ₂ with respect to 100 parts by weight of the metal oxide particles of the metal oxide particle layer as a solid content. Base material with coating.
[11] The adhesive layer (a1) between the substrate and the metal oxide particle layer or the adhesive layer (a2) between the metal oxide particle layer and an overcoat layer described later. Base material with water repellent coating.
[12] The surface of the convex portion of the concave-convex structure further has fine irregularities, the average height (T _FF ) of the fine convex portion is in the range of 0.1 to 5 nm, and the average distance between the fine convex portions (W _FF ) is smaller than the average distance between protrusions (W _F ) of the protrusions and is in the range of 0.1 to 5 nm [1].
[13] The method includes the following steps (b) to (d), the surface has a concavo-convex structure, the average height (T _F ) of the convex portions is in the range of 30 to 500 nm, and the average convex portion distance ( Pitch width) (W _F ) is in the range of 50 to 1000 nm, and the method for producing a water repellent coated substrate having a contact angle with water in the range of 100 to 180 °;
(B) A dispersion of metal oxide particles in which the surface of the metal oxide particles for substrate (A) is coated with the metal oxide particles for coating (B) is applied onto the substrate to form a metal oxide particle layer. Step (c) Step of forming an overcoat layer by applying an overcoat layer forming coating solution on the metal oxide particle layer (d) Step of heat treatment.

[14] The method for producing a substrate with a water-repellent coating according to [13], wherein the following step (a1) is performed before the step (b);
(A1) The process of apply | coating the coating liquid for contact bonding layer formation on the base-material surface, and forming a contact bonding layer (a1).
[15] The method for producing a substrate with a water-repellent coating according to [13], wherein the following step (a2) is performed after the step (b);
(A2) A step of forming an adhesive layer (a2) by applying an adhesive layer-forming coating solution on the metal oxide particle layer.
[16] The method for producing a substrate with a water-repellent coating according to [13], wherein the concentration of the metal oxide particle dispersion is in the range of 0.1 to 10% by weight as a solid content.
[17] With respect to 100 parts by weight of the metal oxide particles in the metal oxide particle layer formed in the step (b), the overcoat layer forming coating solution is 1 to 100 parts by weight based on the solid content. [13] The method for producing a substrate with a water-repellent coating according to [13].

  In the present invention, a water-repellent transparent film having irregularities of a specific size on the surface using metal oxide particles having a specific shape and further having fine irregularities on the convex portions is formed. Such a water-repellent coating is different from the conventionally proposed fractal structure in that the regularity is low and the convex portions have finer irregularities.

  As a result, according to the present invention, it is possible to provide a super-water-repellent coated substrate having excellent adhesion to the substrate, transparency, hardness, scratch resistance, abrasion resistance, haze, and the like. This substrate with a water-repellent coating can be suitably used for automobiles, various electronic devices, and the like that require waterproof performance, chemical resistance, and the like.

The substrate with a water-repellent coating according to the present invention will be described.
[Substrate with water-repellent coating]
The substrate with a water-repellent coating according to the present invention comprises a substrate and a water-repellent coating on the surface of the substrate, and has a predetermined uneven structure and water repellency.

The base material used for the substrate present invention is not particularly limited, for example, be a glass, metal substrates such as SUS, polycarbonate, acrylic resin, polyester, PET, plastic sheet, such as TAC, plastic film, a plastic panel or the like Can do.

  Moreover, a fiber or cloth can also be used depending on a use. For example, cellulose acetate, cellulose triacetate, cellulose nitrate, cellulose, polyacrylonitrile, polyamide, aromatic polyamide, polysulfone, polyethersulfone, polyethylene terephthalate, polyimide, polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl chloride Resin fibers such as polyvinyl alcohol and cloth (including non-woven fabric) can be suitably used.

Water repellent coating The water repellent coating comprises a metal oxide particle layer and an overcoat layer on the metal oxide particle layer.
(i) Metal Oxide Particle Layer In the present invention, predetermined metal oxide particles constitute irregularities on the surface of the water-repellent coating.

Metal Oxide Particles In the present invention, metal oxide particles are particles in which the surface of the base metal oxide particles (A) is coated with the coating metal oxide fine particles (B) (this shape may be referred to as a sunflower shape) Is used.

When such metal oxide particles are used, a water repellent film having fine irregularities, which will be described later, is obtained on the convex portions of the surface of the water repellent coating.
If necessary, the metal oxide particles may be surface-treated, and the surface treatment agent will be described later.

Metal oxide particles for substrate (A)
The metal oxide particles (A) for the substrate are spherical particles, and the average particle diameter (D _A ) is preferably in the range of 40 to 600 nm, more preferably 50 to 500 nm.

  When the metal oxide particles for the substrate (A) are spherical particles, the metal oxide particles can be uniformly coated on the substrate, and a convex portion having a desired height and a desired height are formed on the surface of the water-repellent coating described later. A water-repellent film having a distance (pitch width) between the protrusions can be formed.

When the average particle diameter (D _A ) of the metal oxide particles (A) for the substrate is small, a repellent layer having a desired height and a desired distance (pitch width) when applied onto the substrate. An aqueous film cannot be obtained, that is, the height of the protrusions and the distance between the protrusions (pitch width) may be too small, and the water repellency of the resulting water-repellent film may be insufficient.

Even if the average particle diameter (D _A ) of the metal oxide particles (A) for the substrate is too large, the height of the protrusions and the distance between the protrusions (pitch width) become too large, and a water-repellent coating described later is obtained. In some cases, the water repellency of the resulting water-repellent transparent film may be insufficient.

In the present invention, the average particle diameter (D _A ) of the metal oxide particles for substrate (A) and the average particle diameter of the metal oxide fine particles for coating (B) described later are equivalent sphere conversion formulas expressed by the following formulas. The required average particle diameter is used.
D = 6000 / SA _M * d
(Where D is the average particle size (nm), SA _M is the specific surface area (m ² / g) measured by the BET method, d is the particle density (g / cm ³ ), and 6000 is the conversion factor)
The average particle diameter of the metal oxide particles is measured using a dynamic light scattering method (manufactured by Nikkiso Co., Ltd .: Microtrac UPA). Note that the actual measured value of the specific surface area is measured by the BET method.

Metal oxide fine particles for coating (B)
The average particle diameter (D _B ) of the coating metal oxide fine particles (B) is preferably 4 to 60 nm, more preferably 5 to 40 nm.

When the average particle diameter (D _B ) of the coating metal oxide fine particles (B) is small, it is difficult to obtain metal oxide fine particles that are stably monodispersed.
Even if the average particle diameter (D _B ) of the metal oxide fine particles (B) for coating is too large, the fine irregularities described later are larger than the predetermined range, and the specific surface area of the metal oxide particles is low, so that sufficient water repellency is achieved. May not be obtained.

The ratio (D _B ) / (D _A ) between the average particle size (D _B ) of the coating metal oxide fine particles (B) and the average metal particle size (D _A ) of the base metal oxide particles ( _A ) is 0. It is preferably in the range of 0.007 to 0.5, more preferably 0.008 to 0.4.

When the ratio (D _B ) / (D _A ) is smaller than the lower limit of the range, the fine irregularities described later may be smaller than the predetermined range, and sufficient water repellency may not be obtained.
If the ratio (D _B ) / (D _A ) exceeds the upper limit of the range, fine irregularities described later may be larger than a predetermined range, and sufficient water repellency may not be obtained.

The coverage represented by the following formula (1) of the metal oxide particles for base (A) by the metal oxide particles for coating (B) in the metal oxide particles is 30 to 100%, further 50 to 100%. It is preferable to be in the range.
Covering rate (%) = [[actual specific surface area of metal oxide particles (S _A ) −measured specific surface area of metal oxide particles for substrate (S _M )] / [metal oxidation when 100% coated) Calculated specific surface area (S _C ) of the product particles—measured specific surface area (S _M )] of the metal oxide particles for the substrate]] × 100 (1)

Where (S _C ) = surface area per metal oxide particle × number of particles per unit weight (1 g),
Surface area per metal oxide particle = 4π · [(D _A ) / 2 + (D _B ) / 2] ² ,
Number of metal oxide particles for substrate (A) per unit weight (1 g) = 1 / [4/3 · π [(D _A ) / 2] ³ · d, d are metal oxide particles for substrate (A) Represents the particle density (g / ml). In the case of silica, the particle density is 2.2 g / ml.

  If the coverage is small, fine irregularities described later cannot be formed sufficiently, and water repellency may be insufficient. What has a large coverage beyond the 100% range does not exist in the production method of the present invention.

The metal oxide particles for base (A) and the metal oxide fine particles for coating (B) may be the same or different, and SiO ₂ , Al ₂ O ₃ , Sb ₂ O ₅ , ZrO ₂ , It is preferably at least one selected from TiO ₂ , Fe ₂ O ₃ , CeO ₂ , and complex oxides or mixtures thereof.

Particles having such a component can be suitably used because spherical particles having a particle diameter in the above range are easily obtained and are chemically stable.
In particular, in the present invention, it is preferable that both the metal oxide particles for substrate (A) and the metal oxide particles for coating (B) are composed of SiO ₂ .

Particles made of SiO ₂ can be suitably used because spherical particles having a uniform particle diameter can be obtained regardless of the particle diameter.
The average particle diameter of the metal oxide particles coated with the coating metal oxide fine particles (B) on the surface of the base metal oxide particles (A) described above varies depending on the coverage, but is generally in the range of 48 to 720 nm. It is in.
The method for producing such metal oxide particles is not particularly limited as long as particles satisfying the above-described configuration are obtained, but the following method is recommended for the metal oxide particles used in the present invention.

The manufacturing method of metal oxide particles Specifically includes the following steps (m) and (n).
( _M ) a metal oxide particle for a substrate ( _A ) having a positive or negative surface potential (V _A ) and an average particle diameter (D _A ) in the range of 40 to 600 nm, and a different positive or negative A step of preparing a mixed dispersion with coating metal oxide particles (B) having a surface potential and having an average particle diameter (D _B ) in the range of 4 to 60 nm.
(N) A step of adjusting the pH of the mixed dispersion to 6 to 10.

Process (m)
_A metal oxide particle (A) for a substrate having a positive or negative surface potential (V _A ) and an average particle diameter (D _A ) in the range of 40 to 600 nm, and a different positive or negative surface potential A mixed dispersion with the coating metal oxide particles (B) having an average particle diameter (D _B ) in the range of 4 to 60 nm is prepared.

The base metal oxide particles (A) are combined with those having a surface potential opposite to that of the coating metal oxide particles (B). When the metal oxide particles for substrate (A) have a positive surface potential, the surface potential (V _A ) is preferably in the range of 10 to 60 mV, more preferably 15 to 50 mv.

When the surface potential (V _A ) of the base metal oxide particles (A) is less than 10 mV, the potential difference is small although it depends on the surface potential (V _B ) of the coating metal oxide particles (B) described later. In some cases, the coating metal oxide particles (B) cannot be coated uniformly.

It is difficult to obtain a substrate metal oxide particle (A) having a surface potential (V _A ) exceeding 60 mV. Even if it is obtained, there are cases where a large amount of reagents such as electrolytes used for charge adjustment exist and cause aggregation as necessary.

When the metal oxide particles for substrate (A) have a negative surface potential, the surface potential (V _A ) is preferably in the range of −60 to 0 mv, more preferably −55 to −10 mv.
A surface potential (V _A ) having a negative potential higher than −60 mv is difficult to obtain.

When the surface potential (V _A ) becomes positive (exceeds 0 mv), the surface potential (V _B ) varies depending on the surface potential (V _B ) of the metal oxide particles for coating (B) described later, but the same positive surface potential is obtained. Coating with the metal oxide particles (B) for coating does not occur.

In the above, Al ₂ O ₃ and ZrO ₂ mainly have a positive surface potential, and SiO ₂ , Sb ₂ O ₅ , TiO ₂ depending on the pH of the aqueous dispersion of metal oxide particles (A) for the substrate. Fe ₂ O ₃ and CeO ₂ mainly have a negative potential.

At this time, particles having a positive or negative surface potential can be appropriately converted to the opposite surface potential and used.
Examples of the method for converting particles having a negative surface potential into particles having a positive surface potential include (1) a method of treating with a polyaluminum chloride (PAC) aqueous solution, (2) a method of treating with a quaternary amine aqueous solution, (3) A method of treating with an aminosilane solution or the like can be mentioned.

  Specifically, in the case of (1), it can be obtained by adding a polynuclear metal cation such as polyaluminum chloride to a metal oxide particle dispersion obtained by removing impurities such as cations and anions with an ion exchange resin or the like. .

  In the case of (2), by adding an amine such as a quaternary amine (Senca Co., Ltd .: KHE-100) to the metal oxide particle dispersion from which impurities such as cations and anions have been removed with an ion exchange resin or the like. Can be obtained.

In the case of (3), it can be obtained by adding an amine-based silane coupling agent to the metal oxide particle dispersion obtained by removing impurities such as cations and anions with an ion exchange resin or the like.
At this time, the surface charge amount can be adjusted by adjusting the addition amount of a polynuclear metal cation, an amine, an amine-based silane coupling agent, and the like, and the pH of the metal oxide particle dispersion. Examples of the pH adjuster include organic acids such as ammonia, sodium hydroxide, potassium hydroxide, hydrochloric acid, nitric acid, sulfuric acid, and acetic acid.

  Next, as a method of converting particles having a positive surface potential into particles having a negative surface potential, for example, (4) a method of coating with a silica material having a negative surface potential, (5) anionic The method etc. which process with surfactant etc. are mentioned.

  Specifically, in the case of (4), ethanol is added to a metal oxide particle dispersion from which impurities such as cations and anions have been removed with an ion exchange resin or the like, and then added with normal alkyl silicate, followed by heating and stirring for aging. be able to.

  In the case of (5), an anionic surfactant, preferably an anionic surfactant having a carboxyl group, is added to the metal oxide particle dispersion from which impurities such as cations and anions have been removed with an ion exchange resin or the like. Can be obtained.

  At this time, the amount of surface charge can be adjusted by adjusting the addition amount of a normal alkyl silicate, an anionic surfactant, and the like, and the pH of the metal oxide particle dispersion. Examples of the pH adjuster include organic acids such as ammonia, sodium hydroxide, potassium hydroxide, hydrochloric acid, nitric acid, sulfuric acid, and acetic acid.

  The surface potential is measured using a Zevernizer Nano ZS90 manufactured by Malvern, using a 0.1 wt% dispersion of the metal oxide particles for substrate (A) or the metal oxide particles for coating described later (B).

The coating metal oxide particles (B) have a surface potential opposite to that of the substrate metal oxide particles (A).
The range of the surface potential and the method for converting the surface potential are the same as in the case of the metal oxide particles for substrate (A).

An aqueous dispersion of the metal oxide particles for substrate (A) and an aqueous dispersion of the metal oxide particles for coating (B) are mixed.
The concentration of the mixed dispersion is preferably in the range of 1 to 30% by weight, more preferably 2 to 20% by weight as the solid content.

Even if the concentration of the mixed dispersion is low, there is no problem. However, if it is too thin, the productivity is low and the cost is high.
When the concentration of the mixed dispersion liquid is high, the coated metal oxide particles (B) may aggregate and cannot be uniformly coated on the surface of the base metal oxide particles (A).

At this time, the pH of the mixed dispersion is preferably in the range of 2 to 6, more preferably 3 to 5.
When the pH of the mixed dispersion does not become less than 2, obtain metal oxide fine particles in which the metal oxide particles for substrate (A) are coated with the single layer metal oxide particles for coating (B). Is difficult.

If the pH of the mixed dispersion exceeds 6, the difference in surface potential between the metal oxide particles for substrate (A) and the metal oxide particles for coating (B) may be reduced or the same surface potential may be generated. It is difficult to obtain metal oxide fine particles obtained by coating the metal oxide particles (A) for coating with the single layer metal oxide particles for coating (B).
In addition, it is preferable that the temperature of the dispersion liquid in a process (m) is the range of 5-200 degreeC in general.

Step (n)
The mixed dispersion is treated with an anion exchange resin to remove anions.
At this time, the treatment with the anion exchange resin is preferably carried out until the pH of the mixed dispersion is in the range of 6 to 10, more preferably 7 to 9.5.
When the pH of the mixed dispersion after the anion exchange resin treatment is less than 6, the remaining amount of anions is large, which may hinder the generation of gas during calcination in the subsequent process and the crystallization of the coating layer. .

The pH of the mixed dispersion after the anion exchange resin treatment does not exceed 10, and the remaining amount of anion does not decrease.
If necessary, the dispersion can be separated by filtration and dried for use.
In the present invention, it is preferable to perform the following step (o) after the step (n).

Step (o)
The dispersion obtained in step (n) is aged at 60 to 98 ° C, preferably 70 to 95 ° C.
At this aging temperature, the bonding of the coating metal oxide particles (B) to the base metal oxide particles (A) becomes stronger.
Even when the aging temperature is too high, the metal oxide particles for coating (B) may not be further strongly bonded to the metal oxide particles for substrate (A), and aggregated metal oxide particles may be obtained. .

If necessary, the dispersion can be separated by filtration, dried, and further baked for use.
Then, following the step (n) or the step (o), the following steps (p) to (t) may be performed.

Step (p)
The pH of the dispersion prepared in step (n) or step (o) is adjusted to 3 to 7, preferably 4 to 6. By adjusting the pH of the dispersion to this range, it is difficult to produce an aggregate of metal fine particles after the step (q), particularly the step (r) described later, and even if it is produced, it can be easily crushed. .

  When the pH of the dispersion is out of the above range, dehydration condensation between the particle surfaces proceeds, and the particles are dried in a hard state, and then sintered when sintered, resulting in metal oxide particles that are difficult to disintegrate. is there.

In addition, when the pH of the mixed dispersion after the anion exchange resin in the step (n) is in the range of 6 to 7, this step (p) is not necessarily performed.
The pH of the dispersion is preferably adjusted by adding an acid.

Examples of the acid include mineral acids (inorganic acids) such as hydrochloric acid, sulfuric acid and nitric acid, organic acids such as acetic acid, tartaric acid, gluconic acid and glycolic acid, and mixtures thereof.
In the present invention, organic acids such as acetic acid, gluconic acid and glycolic acid are preferably used. When these organic acids are used, even if they remain as anions, they can be removed in the firing step (r) described later. Even if the metal oxide particles partially aggregate or fuse in the firing step (r), they will be described later. It can be easily crushed in the step (s).
If necessary, it can be filtered and used.
Further, the following steps may be performed.

Step (q)
The obtained particle dispersion is dried. There is no restriction | limiting in particular as a drying method, A conventionally well-known method is employable. Although it can be air-dried at room temperature, the drying temperature is preferably in the range of 80 to 300 ° C, more preferably 100 to 200 ° C.

Step (r )
After drying, heat treatment is performed at 300 to 1200 ° C, preferably 700 to 1100 ° C.
When preparing a metal oxide particle dispersion for forming a metal oxide particle layer by heat treatment or when preparing a metal oxide particle dispersion for surface treatment of metal oxide particles, the metal oxide for coating is used. The fine particles (B) do not peel off and can be suitably used for forming a water-repellent coating.
After drying and heat treatment, crushing may be performed.

Step (s)
By crushing, loosely agglomerated particles are loosened. The pulverization may be performed when the particles strongly aggregated in the step (r) exist and the surface unevenness of the metal oxide particle layer does not fall within a predetermined range. There is no restriction | limiting in particular as a crushing method, A conventionally well-known method is employable. For example, methods such as a sand mill, an impact pulverization method, an ultrasonic homogenizer, and a nano jet mizer method can be used.
Furthermore, in this invention, you may perform isolation | separation operation after either of each process after the said process (n).

Step (t)
When particles other than the desired particle size and particles other than the desired shape remain, they are separated and removed. If such particles remain, although depending on the remaining amount, the desired surface irregularities may not be formed, and thus the water repellency may be insufficient.

  The separation method is not particularly limited as long as particles other than the desired particle diameter and particles other than the desired shape can be removed, and conventionally known methods can be employed. For example, various filters, a centrifuge, etc. are mentioned.

A metal oxide particle layer is formed on the substrate (or the surface when an adhesive layer is provided). The forming method applies a dispersion liquid as will be described later.
The thickness of the metal oxide particle layer is 48 to 720 nm, preferably 60 to 580 nm. By setting it as such a range, the water-repellent film which has a predetermined unevenness | corrugation can be formed.

Adhesive layer It may have an adhesive layer (a1) between the substrate and the metal oxide particle layer, and / or an adhesive layer (a2) between the metal oxide particle layer and an overcoat layer described later. preferable.
This makes it possible to further improve the adhesion between the base material and the metal oxide particle layer and the adhesion between the metal oxide particle layer and the overcoat layer.
The adhesive layer (a1) or (a2) is not particularly limited as long as the adhesive layer (a1) or (a2) can be higher than the adhesion with the metal oxide particle layer, and further the overcoat layer, but an organic resin-based adhesive layer may be formed. Alternatively, an inorganic oxide adhesive layer may be formed.

  Specifically, in the case of forming an organic resin-based adhesive layer, there is no particular limitation as long as the adhesion between the base material and the metal oxide particle layer, and further the overcoat layer can be improved. For example, polyester resins, polycarbonate resins, polyamide resins, polyimide resins, polyphenylene oxide resins, thermoplastic acrylic resins, vinyl chloride resins, vinyl acetate resins, silicone rubber and other thermoplastic resins, urethane resins, Examples thereof include thermosetting resins such as melamine resin, silicon resin, butyral resin, phenol resin, epoxy resin, unsaturated polyester resin, and thermosetting acrylic resin. Further, it may be a copolymer or modified body of two or more of these resins.

  These resins may be emulsion resins, water-soluble resins, and hydrophilic resins. Further alternatively, an ultraviolet curable resin or an electron beam curable resin may be used. In the case of a thermosetting resin, a curing catalyst may be included.

  Preferably, a polyfunctional (meth) acrylate resin having a functional group such as a silyl group, a hydroxyl group, an amino group, a carboxyl group, or a sulfo group can be used as the organic resin adhesive layer forming component. is there. Specifically, polyacryl such as hexaerythritol tripentaacrylate, pentaerythritol triacrylate, diethylaminomethyl methacrylate, dimethylaminomethyl methacrylate, 2-hydroxy-3-acryloyloxypropyl acrylate, methoxytriethylene glycol dimethacrylate, butoxydiethylene glycol methacrylate, etc. Resin, polyvinyl alcohol or a modified product thereof (cation modification, anion modification, silanol modification), starch or modification product thereof (oxidation, etherification), gelatin or modification product thereof, casein or modification product thereof, carboxymethyl cellulose, arabic gum, hydroxy Cellulose derivatives such as ethyl cellulose, hydroxypropyl methyl cellulose, SBR latex, N R latex, conjugated diene copolymer latex such as methylmethacrylate-butadiene copolymer, functional group-modified polymer latex, vinyl copolymer latex such as ethylene vinyl acetate copolymer, polyvinylpyrrolidone, maleic anhydride or the like It may be a copolymer, an acrylate ester copolymer, a mixture thereof, or two or more copolymers or modified products of these resins. In addition, polyfunctional (meth) acrylic acid ester resins having a functional group such as vinyl group, urethane group, epoxy group, (meth) acryloyl group, and emulsion-based fine particles can be suitably employed. Specifically, pentaerythritol tetraacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexaacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl acrylate, n-stearyl acrylate, 1,6-hexanediol dimethacrylate, perfluorooctylethyl methacrylate, trichloroethyl methacrylate, urethane acrylate, acrylic cross-linked copolymer fine particles, urethane Cross-linked copolymer fine particles, acrylic-urethane cross-linked copolymer Particles and the like and mixtures thereof.

  When forming an inorganic oxide-based adhesive layer, in addition to sols such as silica sol, silica alumina sol, antimony-doped tin oxide (ATO) sol, tin-doped indium oxide (ITO) sol, an alkali silicate aqueous solution can be used with an ion exchange resin or the like. It is possible to use an inorganic oxide made of an acidic silicic acid solution obtained by dealkalization, an organic silicon compound, or a hydrolyzate thereof.

Of these, silica sol, acidic silicate solution obtained by dealkalizing alkali silicate with an ion exchange resin, and silica derived from a hydrolyzable organosilicon compound are preferred.
In particular, a silica adhesive layer which is a hydrolyzed polycondensate of a hydrolyzable organosilicon compound represented by the following formula (2) is preferable.
R _n -SiX _4-n (2)
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, Halogen, hydrogen, n: an integer of 0 to 1)

  Here, the hydrolyzed polycondensate is a hydrolyzable organosilicon compound, a partial hydrolyzate thereof, or a hydrolyzate that has been polycondensed by heat treatment in the production process described later. I mean.

  Such hydrolyzable organosilicon compounds include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxy. Silane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, 3,3,3-trifluoropropyltri Methoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxymethyltrimethoxysila , Γ-glycidoxymethyltriethoxysilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxy Silane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, γ- (meth) acrylooxymethyltrimethoxysilane, γ- (meth) acrylooxymethyltriethoxysilane, γ- (meth) acryloxyethyltrimethoxysilane, γ- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxy Silane, γ- (meth) acrylooxypropyltrimethoxysilane, γ- (meth) a Acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, butyltrimethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilaoctyltriethoxysilane, decyltriethoxysilane, butyltriethoxysilane, isobutyl Triethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, 3-ureidoisopropylpropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctylethyltriiso Propoxysilane, trifluoropropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β ( Minoechiru) .gamma.-aminopropyltrimethoxysilane, N- phenyl--γ- aminopropyltrimethoxysilane, .gamma.-mercaptopropyltrimethoxysilane, trimethylsilanol, methyl trichlorosilane, and the like and mixtures thereof.

  Among them, n = 0 (tetrafunctional) hydrolyzable organosilicon compound, or n = 0 (tetrafunctional) hydrolyzable organosilicon compound and n = 1 (trifunctional) hydrolyzable organosilicon compound Use of the mixture provides excellent adhesion to the substrate, strength, hardness, etc., increased adhesion to the overcoat layer, and finally a substrate with a water-repellent coating with excellent strength, hardness, and water repellency. And can be suitably used for water treatment.

  The formation amount of the adhesive layer (a1) or (a2) is 1 to 200 parts by weight based on 100 parts by weight of the metal oxide particles in the metal oxide particle layer in terms of oxides, and 10 to 10 parts by weight based on the adhesive layer. It is preferable to be in the range of ˜190 parts by weight.

If the formation amount of the adhesive layer is small, the adhesiveness (adhesiveness) between the substrate and the metal oxide particle layer and the adhesiveness between the metal oxide particle layer and the overcoat layer may be insufficient.
If the amount of the adhesive layer (a1) formed is too large, the unevenness of the metal oxide particle layer may be reduced, and the water-repellent coating finally obtained may be insufficient in water repellency.
If the formation amount of the adhesive layer (a2) is too large, unevenness and fine unevenness on the surface of the metal oxide particle layer and the metal oxide particle layer may be reduced, resulting in poor water repellency of the finally obtained water-repellent coating. May be sufficient.

Overcoat layer An overcoat layer is formed on the metal oxide particle layer.
The overcoat layer is not particularly limited as long as it can bond to the metal oxide particle layer and improve water repellency, but preferably contains at least one of a fluorine-containing compound, an alkyl group-containing compound and a silicone compound.

  Examples of fluorine-containing compounds include silane derivatives such as perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctylethyltriisopropoxysilane, trifluoropropyltrimethoxysilane, and the like, 1H, 1H, 2H, 2H- Phosphonic acid derivatives such as perfluoro-n-hexylphosphonic acid, 1H, 1H, 2H, 2H-perfluoro-n-octylphosphonic acid, 1H, 1H, 2H, 2H-perfluoro-n-decylphosphonic acid, fluorotechnology Fluorosurf manufactured by NODASCREEN, etc.

  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 the like.

  Examples of the silicone compound include modified reactive silicone manufactured by Shin-Etsu Chemical, modified reactive silicone manufactured by Momentive, and the like. At this time, the modified reactive silicone preferably contains an acrylic group / (meth) acryloxy group, an epoxy group, a silanol group, a phenol group, a carboxyl group or the like as a functional group.

In the present invention, it is preferable to use a hydrolysis polycondensate of a hydrolyzable organosilicon compound represented by the following formula (3).
_{R n -SiX 4-n (3} )
(In the formula, R is a hydrocarbon group having 1 to 10 carbon atoms and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a halogen, hydrogen, n: an integer of 1 to 3)
Here, the hydrolyzable polycondensate of a hydrolyzable organosilicon compound means a hydrolyzable organosilicon compound, a partial hydrolyzate thereof, or a hydrolyzate that has been subjected to heat treatment in the production process described later. It means that it is condensed.

  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-glycidoxyethyltrimethoxysilane, γ-glyci Doxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- ( β-glycidoxyethoxy) propyltrimethoxysilane, γ- (meth) acrylooxymethyltrimethoxysilane, γ- (meth) acrylooxymethyltriethoxysilane, γ- (meth) acrylooxyethyltrimethoxysilane , Γ- (meth) acrylooxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane Ethoxysilane, γ- (meth) acrylooxypropyltriethoxysilane, Butyltrimethoxysilane, Isobutyltriethoxysilane, Hexyltriethoxysilaoctyltriethoxysilane, Decyltriethoxysilane, Butyltriethoxysilane, Isobutyltriethoxysilane, Hexyltriethoxysilane, Octyltriethoxysilane, 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-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyl Examples include diethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and the like, and mixtures thereof.

  Of these, hydrolyzable organosilicon compounds containing fluorine-substituted hydrocarbon groups such as perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctylethyltriisopropoxysilane, and trifluoropropyltrimethoxysilane. When the hydrolyzed polycondensate is contained, a film having more excellent water repellency can be obtained.

  The content of the overcoat layer in the water-repellent coating is in the range of 1 to 100 parts by weight, further 2 to 80 parts by weight as a solid content with respect to 100 parts by weight of the metal oxide particles in the metal oxide particle layer. It is preferable.

If the content of the overcoat layer is small, uneven coating may occur in some cases where the overcoat layer is not formed, sufficient water repellency may not be obtained, and the content of the overcoat layer is too large. In addition, the average height (T _F ) of the irregularities on the surface of the water-repellent film, which will be described later, and the distance (W _F ) between the convex portions are reduced, and the average height (T _FF ) of the fine irregularities on the convex portion surface In some cases, the distance (W _FF ) is decreased, and the water repellency is rather lowered.

Uneven structure The surface of the substrate with a water-repellent coating according to the present invention has an uneven structure.
The concavo-convex structure is defined by an average height (T _F ) of convex portions, an average distance between convex portions (pitch width), and a contact angle with water.

It is preferable that the average height (T _F ) of the convex portions of the concavo-convex structure is in the range of 50 to 500 nm, more preferably 50 to 400 nm. When the average height (T _F ) of the convex portions is small, the water repellency of the water repellent coating film may be insufficient.

If the average height (T _F ) of the convex portions is too large, the strength of the water-repellent film may be insufficient.
Moreover, it is preferable that the distance between average convex parts (it may be called pitch width) (W _F ) is in the range of 20 to 1000 nm, more preferably 70 to 800 nm.

If the average inter-convex distance (W _F ) is not within the above range, the water repellency of the water repellent film may be insufficient.
When the average distance between the convex portions (W _F ) is short, the water repellency of the water repellent film may be insufficient.

Even if the distance between the average convex portions (W _F ) is too large, the water-repellent coating may have insufficient water repellency.
In the present invention, the average height (T _F ) and the average distance (W _F ) between the protrusions are obtained by taking a transmission electron micrograph (TEM) of the cross section of the water-repellent coating, and measuring 50 protrusions. The height and the distance between pitches were measured, and the average value was obtained.

The average height (T _F ) of the protrusions and the average distance (W _F ) between the protrusions select the size of the metal oxide particles and disperse the metal oxide particles in the coated substrate manufacturing method described later. It is adjusted depending on the concentration of the liquid, the coating method, the amount of the adhesive layer (a2) formed, and the like.

Specifically, when the size of the metal oxide particles is large, the average height (T _F ) and the average distance between the convex portions (W _F ) tend to increase, and the concentration of the metal oxide particle dispersion liquid When the density is high, the average height (T _F ) tends to be high, and when the density is low, the average distance between convex portions (W _F ) tends to be large. When the formation amount of the adhesive layer (a2) is large, the unevenness and the fine unevenness described later are reduced.

The convex part on the surface of the water-repellent coating film of the present invention has finer irregularities on the convex part surface. The average height (T _FF ) of the convex portions of the fine irregularities is preferably in the range of 0.1 to 5 nm, more preferably 0.2 to 3 nm.

When the average height (T _FF ) of the convex portions of the fine irregularities is in the above range, a transparent film having more excellent water repellency can be obtained.
The average protrusion distance of the convex portions of the fine irregularities (W _FF) is 0.1 to 5 nm, more preferably in the range of 0.2～3Nm.

If the average inter-convex distance (W _FF ) of the convexes of fine irregularities is in the above range, a coating with more excellent water repellency can be obtained as in the case where the average height (T _FF ) is in the predetermined range. .
The average height (T _FF ) and average distance between convex portions (W _FF ) of such fine irregularities should be measured when measuring the above average height (T _F ) and average distance between convex portions (W _F ). When an arbitrary five convex portions are designated and enlarged, the average height (T _FF ) and the average inter-convex distance (W _FF ) of the fine irregularities can be measured.

The average height (T _FF ) and the average distance between convex portions (W _FF ) select the size of the metal oxide fine particles for coating and the surface coverage, and the overcoat layer is contained in the water-repellent coating. It is adjusted by the amount etc.

The water repellent coating preferably has a contact angle with water in the range of 100 to 180 °, more preferably 130 to 180 °.
This is a characteristic of the uneven structure and the overcoat layer. In order to adjust the contact angle within the above range, the metal oxide particles are selected so that the average height (T _F ) and the average inter-convex distance (W _F ) of the convex portions are within a predetermined range by the method described above. An overcoat layer may be formed.

If the contact angle of the water-repellent coating with water is in the above range, a water-repellent coating that normally repels water without water droplets adhering to the coating can be obtained. And can be suitably used for automobiles, various electronic devices, and the like that require waterproof performance, chemical resistance performance, and the like. Moreover, when a base material is a fiber or a cloth, it can also be used as waterproof clothing.
Below, the manufacturing method of the base material with a water-repellent film which concerns on this invention is demonstrated.

[Method for producing substrate with water-repellent coating]
The method for producing a substrate with a water-repellent coating according to the present invention comprises the following steps (b) to (d), the surface has an uneven structure, and the average height (T _F ) of the protrusions is 30 to It is in the range of 500 nm, the average inter-convex distance (pitch width) (W _F ) is in the range of 50 to 1000 nm, and the contact angle with water is in the range of 100 to 180 °.
(B) A step of forming a metal oxide fine particle layer by applying a metal oxide particle dispersion on a substrate (c) An overcoat layer forming coating solution is applied on the metal oxide particle layer Step of forming layer (d) Step of heat treatment Note that an adhesive layer may be provided on the surface of the substrate before forming the metal oxide fine particle layer in step (b), and the surface of the fine particle layer after forming the fine particle layer An adhesive layer may be provided.

Process (a1) to (a2)
In the present invention, the adhesive layer (a1) may be formed by applying a coating solution for forming an adhesive layer on the surface of the substrate by the step (a1) before the step (b) described later. Subsequently, the adhesive layer (a2) can also be formed by applying an adhesive layer-forming coating solution onto the metal oxide particle layer. Both the adhesive layers (a1) and (a2) may be formed.

Adhesive layer-forming coating solution As the adhesive layer-forming coating solution, there is no particular limitation as long as the substrate and the metal oxide particle layer, or the metal oxide particle layer and the overcoat layer described later can be adhered with good adhesion, The organic resin adhesive resin or inorganic oxide adhesive layer forming component as described above is preferably used.

As the dispersion medium of the coating liquid for forming the adhesive layer, the same dispersion medium as that of the metal oxide particle dispersion described later can be used.
The concentration of the coating solution for forming the adhesive layer is preferably in the range of 0.05 to 20% by weight, more preferably 0.1 to 10% by weight as the solid content.

  When the concentration of the coating solution for forming the adhesive layer is within the above range, it can be uniformly applied to the substrate or the metal oxide particle layer, although it varies depending on the coating method, functions as the adhesive layer, and has excellent adhesion. Further, a metal oxide particle layer, an overcoat layer, and a water repellent film can be formed.

  The coating liquid for forming the adhesive layer is 100 parts by weight as the oxide (solid content) of the metal oxide particles in the metal oxide particle layer, 1 to 200 parts by weight as the solid content, and further 5 to 150 parts as the solid content. A coating solution for forming an adhesive layer is used so as to be in the range of parts by weight.

If the coating amount of the coating solution for forming the adhesive layer is small, the adhesion between the substrate and the water-repellent film may be insufficient.
Even if the application amount of the coating liquid for forming the adhesive layer is too large, the surface uneven structure may be outside the predetermined range, and the water repellency of the finally obtained water-repellent film may be insufficient.

  The method for applying the coating solution for forming the adhesive layer is not particularly limited as long as it can be uniformly applied to the substrate or the metal oxide particle layer. For example, the bar coater method, the dip method, the spray method, the spinner method, the roll coat method, Examples include a gravure coating method, a slit coating method, and a curtain coating method.

  It is preferable to dry after applying the coating solution for forming the adhesive layer, and a conventionally known method can be adopted as the drying method. For example, the drying temperature substantially removes the dispersion medium of the coating solution for forming the adhesive layer. Although there is no restriction | limiting in particular if possible, it is 50-120 degreeC in general, Preferably it is 60-100 degreeC.

Furthermore, heat treatment and / or UV irradiation treatment may be performed as necessary.
Although heat processing temperature changes also with the kind of base material, it is preferable that it exists in the range of 130-400 degreeC, Furthermore, 150-200 degreeC.

UV irradiation treatment varies depending on the type of substrate, 100~1200mJ / cm ² of UV wavelengths 365nm using a high pressure mercury lamp, and it is more preferable that the irradiation in the range of 200~800mJ / cm ^2.

Step (b)
When the adhesive layer (a1) is formed on the substrate, the metal oxide particle dispersion is applied onto the adhesive layer (a1) to form a metal oxide particle layer.
As the metal oxide particle dispersion, the aforementioned metal oxide particle dispersion is used.

Examples of the dispersion medium of the dispersion medium metal oxide particle dispersion include alcohols such as water, methanol, ethanol, propanol, 2-propanol (IPA), butanol, diacetone alcohol, furfuryl alcohol, and tetrahydrofurfuryl alcohol; Esters such as methyl acetate, ethyl acetate, isopropyl acetate, propyl acetate, isobutyl acetate, butyl acetate, isopentyl acetate, pentyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, cyclohexyl acetate, ethylene glycol monoacetate, ethylene glycol, Glycols such as hexylene glycol; diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol Hydrophilic solvents including ethers such as propyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monopropyl ether, propyl acetate, isobutyl acetate, butyl acetate, isopentyl acetate , Esters such as pentyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, cyclohexyl acetate, ethylene glycol monoacetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, butyl methyl ketone, cyclohexanone, methylcyclohexanone, dipropyl ketone, methyl Ketones such as pentyl ketone and diisobutyl ketone; and polar solvents such as toluene. Furthermore, polar solvents such as N-methylpyrrolidone can also be used, and these may be used alone or in combination of two or more.

In the present invention, metal oxide particles can be used after surface treatment. As the surface treating agent, a hydrolyzable organosilicon compound is preferably used.
Hydrolyzable organosilicon compounds include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldi Ethoxysilane, 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-glycid Xymethyltriethoxysilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycid Xylpropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, γ- (meth) acrylooxymethyltrimethoxysilane, γ- (meth) acryl Rooxymethyltriethoxysilane, γ- (meth) acrylooxyethyltrimethoxysilane, γ- (meth) acrylooxyethyltriethoxysilane, γ- (meth) acrylooxypropyltrimethoxysilane, γ- (meta ) Acryloxypropyltrimethoxysilane, γ- (meth) acrylooxyp Propyltriethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, butyltrimethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilaoctyltriethoxysilane, decyltriethoxysilane, butyltriethoxysilane, isobutyl Triethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, 3-ureidoisopropylpropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethylsilanol, methyltrichlorosilane, and the like Compounds, and the like.

  As a surface treatment method with a hydrolyzable organosilicon compound, a conventionally known method can be employed. For example, a predetermined amount of a hydrolyzable organosilicon compound and a required amount of water are added to an alcohol dispersion of metal oxide particles. And an acid or alkali as a hydrolysis catalyst if necessary, and further heating if necessary.

In addition to the hydrolyzable organosilicon compound, other hydrolyzable organometallic compounds can be used in the same manner.
Examples of the hydrolyzable organometallic compound include hydrolyzable organoaluminum compounds, hydrolyzable organozircominium compounds, hydrolyzable organotitanium compounds, and the like.

In addition to the surface treatment method using the hydrolyzable organometallic compound, a Stover method, a dry treatment method, a mechanofusion method, and the like can be given.
The concentration of the metal oxide particle dispersion is preferably 0.1 to 10% by weight, more preferably 0.5 to 8% by weight as the solid content. When the concentration of the metal oxide particle dispersion is low, the distance between the convex portions becomes large, and uneven coating without a metal oxide particle layer may occur and sufficient water repellency may not be obtained.

  If the concentration of the metal oxide particle dispersion is high, it may vary depending on the coating method, but if the coatability is reduced and a uniform metal oxide particle layer cannot be formed, or the distance between the convex portions may not be adjusted. In some cases, the resulting coating film has insufficient water repellency.

  The metal oxide particle dispersion is applied, but the application method is not particularly limited as long as a metal oxide particle layer having a generally desired uneven structure can be formed with good adhesion. For example, a dipping method, a bar coater method, a spray method , Spinner method, roll coating method, gravure coating method, slit coating method, curtain coating method and the like.

  It is preferable to dry after applying the metal oxide particle dispersion, and a conventionally known method can be adopted as the drying method. For example, the drying temperature substantially removes the dispersion medium of the metal oxide particle dispersion. There is no particular limitation as long as it can be done, and it can be air-dried at room temperature. However, it is preferably about 50 to 120 ° C., preferably 60 to 100 ° C.

Step (c)
On the metal oxide particle layer or the adhesive layer (a2), an overcoat layer-forming coating solution is applied to form an overcoat layer.

As the coating solution for forming the overcoat layer, the aforementioned fluorine-containing compound, alkyl group-containing compound, silicone compound, or a partial hydrolyzate or hydrolyzate thereof is used.
In the present invention, the overcoat layer forming coating solution contains the above-described overcoat layer forming component.

As a dispersion medium for the coating liquid for forming the overcoat layer, the same dispersion medium as that for the metal oxide particle dispersion can be used.
The concentration of the overcoat layer-forming coating solution is preferably in the range of 0.05 to 20% by weight, more preferably 0.1 to 10% by weight as the solid content.

  When the concentration of the overcoat layer-forming coating solution is low, uneven coating without a part of the overcoat layer may occur, and sufficient water repellency may not be obtained. Even if the concentration of the coating solution for forming the overcoat layer is too high, the desired uneven structure may not be obtained, the water repellency may not be further improved, and the water repellency may rather be lowered.

The coating liquid for forming the overcoat layer is applied so as to have the content of the overcoat layer described above.
There are no particular restrictions on the method for applying the overcoat layer forming coating solution as long as it can be uniformly applied to the metal oxide particle layer. For example, dipping method, bar coater method, spray method, spinner method, roll coating method, gravure coating method , Slit coating method, curtain coating method and the like.

  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. For example, the drying temperature is substantially equal to the dispersion medium of the overcoat layer-forming coating solution. However, it is generally 50 to 120 ° C, preferably 60 to 100 ° C.

Step (d)
Next, heat treatment is performed.
Although heat processing temperature changes also with the kind of base material, it is preferable that it exists in the range of 130-700 degreeC, Furthermore, 150-500 degreeC.

Bonding between substrate and adhesive layer (a1), adhesive layer (a1) and metal oxide particle layer, metal oxide particle layer and adhesive layer (a2), adhesive layer (a2) and overcoat layer by drying and heat treatment Thus, a water-repellent coating excellent in adhesion to the substrate, film strength, hardness, scratch resistance and the like can be formed.
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.

[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by these Examples.
[Example 1]
Preparation of metal oxide particle (1) dispersion
Preparation of positively charged base metal oxide particles (A-1) Silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid SI-80P, average particle diameter 80 nm, surface potential -60 mV, SiO ₂ concentration 20 wt%, pH 10 .2) 150 g of a cation exchange resin (ROHMHARS Co., Ltd .: Duolite) was mixed with 750 g and stirred for 0.5 hour.

Next, after separating the cation exchange resin, 135 g of anion exchange resin (Mitsubishi Chemical Corporation: SUNUP-C) is mixed and stirred at 30 ° C. for 0.5 hour, and then the anion exchange resin is separated. As a result, 750 g of purified silica sol having a SiO ₂ concentration of 20% by weight was prepared.

Next, 5.1 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. Subsequently, 2903 g of pure water was added and diluted to prepare 3658 g of a dispersion of metal oxide particles for substrate (A-1) made of silica having a SiO ₂ concentration of 4.1 wt%. The pH of the metal oxide particle (A-1) dispersion for the substrate was 3.7.
The surface potential of the metal oxide particles (A-1) for the substrate was measured, and the results are shown in the table.

Next, 3659 g of the base metal oxide particle (A-1) dispersion made of silica having a SiO ₂ concentration of 4.1% by weight was added to a silica sol (JGC Catalysts & Chemicals Co., Ltd.) as the coating metal oxide particles (B-1). 294 g of Cataloid SN-350, average particle diameter 7 nm, surface potential -23 mV, SiO ₂ concentration 16.6 wt%, pH 3.7) were mixed and stirred at 30 ° C. for 0.5 hour. At this time, the SiO ₂ concentration of the mixed dispersion was 5.0% by weight and the pH was 3.5. Process (m)

Next, 135 g of an anion exchange resin (manufactured by Mitsubishi Chemical Co., Ltd .: SUNUP-C) was mixed in the mixed dispersion, and the mixture was stirred for 0.5 hour. Then, the anion exchange resin was separated, and the SiO ₂ concentration was measured by a rotary evaporator. A dispersion of metal oxide particles (1) composed of 10% by weight of silica was prepared. Next, it was diluted with pure water, and a leveling agent (manufactured by Nissin Kogyo Co., Ltd .: EXP-4026) was added so as to be 0.1 part by weight with respect to 100 parts by weight of the metal oxide particle (1) dispersion. Thus, a metal oxide particle (1) dispersion having a solid content concentration of 2.0% by weight was prepared. The pH of the dispersion was 9.0. Step (n)

With respect to the obtained metal oxide particles (1), the average particle diameter and the coverage were determined, and the results are shown in the table.
In addition, the calculation process of the coverage in Example 1 is shown below.
(D _A ) = 80 nm, (D _B ) = 7 nm, (S _A ) = 39.1 m ² / g
Surface area per metal oxide particle = 4π · [(80/2) × 10 ⁻⁹ + (7/2)) × 10 ⁻⁹ ] ² = 2.4 × 10 ⁻¹⁴ m ² / piece Metal for substrate per unit g Number of oxide particles (A-1) = 1 / [4/3 × πx (80/2 × 10 ⁻⁷ ) ³ x2.2] = 1.7 × 10 ¹⁵ (silica density is 2.2)
(S _C ) = 2.38 × 10 ⁻¹⁴ m ² /piece×1.7×10 ¹⁵ pieces / g = 40.3 m ² / g
Coverage ^{= (39.1m 2 / g-34m} 2 /g)/(40.3m 2 / g-34m 2 /g)=80.7%

Preparation of Adhesive Layer Forming Coating Solution (1) Modified Alcohol (Nippon Alcohol Sales Co., Ltd .: Solmix A-11, mixed alcohol of methanol, ethanol and isopropyl alcohol) 72.5 g with water 10.0 g and concentration 61 weight % Nitric acid 0.1 g was added and stirred at 25 ° C. for 10 minutes. Next, 17.4 g of tetraethoxysilane (manufactured by Tama Chemical Industry Co., Ltd .: normal ethyl silicate-A, SiO ₂ concentration 28.8 wt%) was added and stirred at 30 ° C. for 30 minutes to hydrolyze tetraethoxysilane. (Solid content concentration 5.0 wt%, molecular weight: 1000) was obtained. Next, 333.3 g of diacetone alcohol (DAA), 666.6 g of ethylene glycol monoisopropyl ether (I-PG) and mixed alcohol (manufactured by Nippon Alcohol Sales Co., Ltd .: Solmix A-11, methanol, ethanol and isopropyl alcohol 566.67 g of mixed alcohol) was added and stirred at 25 ° C. for 30 minutes to prepare a coating solution (1) for forming an adhesive layer comprising silica having a solid content concentration of 0.3% by weight.

Preparation of coating liquid for overcoat layer formation (1) Modified alcohol (manufactured by Nippon Alcohol Sales Co., Ltd .: Solmix A-11, mixed alcohol of methanol, ethanol and isopropyl alcohol), 2252.5 g, 159.0 g of water and concentration 61 3.3% by weight of nitric acid was added and stirred at 25 ° C. for 5 minutes. Then, 46.4 g of tridecafluorooctyltrimethoxysilane (manufactured by MOMENTIVE: TSL8257, solid concentration: 98%) was added, stirred at 25 ° C. for 5 minutes, and then treated at 60 ° C. for 3 hours.

Thereafter, 356.39 g of PGM and 213.91 g of DAA were added and treated at 25 ° C. for 30 minutes to prepare a coating solution for forming a fluorine-containing silica-based layer having a solid content concentration of 1.50% by weight.
Subsequently, 10 g of PGM and mixed alcohol (manufactured by Nippon Alcohol Sales Co., Ltd .: Solmix A-11, mixed alcohol of methanol, ethanol and isopropyl alcohol) were added to 100 g of fluorine-containing silica-based layer forming coating solution having a solid content concentration of 1.50% by weight. 40 g was added to prepare an overcoat layer forming coating solution (1) having a solid content concentration of 1.0%.

Manufacture of substrate (1) with water repellent coating First, a metal oxide particle (1) dispersion with a solid content concentration of 2.0% by weight was made into a glass substrate (Hamashin Co., Ltd .: FL glass, thickness: 3 mm). And a refractive index of 1.51) by a bar coater method (# 3) so that the thickness of the dry layer is as shown, and dried at 80 ° C. for 30 seconds. Next, the binder coating solution (1) having a solid concentration of 0.3% by weight was coated on the metal oxide particle (1) layer with a spin coater so as to have the content shown in the table, and 120 ° C. at 120 ° C. After drying for 2 seconds, it was cured by heating at 150 ° C. for 30 minutes.

  Next, an overcoat layer-forming coating solution (1) having a solid content concentration of 1.0% by weight was applied by the bar coater method (# 4) so as to have the content shown in the table, dried at 80 ° C. for 120 seconds, and then 150 A substrate (1) with a water-repellent coating was produced by drying and curing at 10 ° C. for 10 minutes.

Water repellent film-coated substrate (1), the composition, the average height of the concavo-convex structure (T _F), the distance between the average protrusion (W _F), the average height of the fine unevenness (T _FF), between the average protrusion The distance (W _FF ), pencil hardness, adhesion, scratch resistance, water repellency, total light transmittance and haze were measured, and the results are shown in the table. The total light transmittance and haze were measured with a haze meter (manufactured by Suga Test Instruments Co., Ltd.). The uncoated glass had a total light transmittance of 99.0% and a haze of 0.1%.
Pencil hardness, scratch resistance, water repellency and adhesion were measured by the following methods.

Pencil hardness It measured with the pencil hardness tester according to JIS-K-5600.
Evaluation criteria:
2H or more: ◎
H-2H: ○
B to H: △
B or less: ×

Using scratch-resistant # 0000 steel wool, sliding 10 times at a load of 200 g / cm ² , visually observing the surface of the film and evaluating it according to the following criteria, the results are shown in Table 1.
Evaluation criteria:
No streak injury is found: ◎
Slightly scratched streak: ○
Many scratches are found in the streak: △
The surface has been cut entirely: ×

The contact angle with water was measured with a water repellent fully automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd .: DM 700).

Adhesive water-repellent transparent coated substrate (1) The surface of the substrate (1) with 11 parallel scratches at 1mm vertical and horizontal intervals using a knife to make 100 squares, and then the cellophane tape is adhered to and peeled off. The adhesion was evaluated by classifying the number of cells remaining without peeling into the following three stages.
Number of remaining squares: ◎
Number of remaining squares 95 to 99: ○
Number of residual squares 90-94: △
Number of remaining squares: 89 or less: ×

[Example 2]
Preparation of metal oxide particle (2) dispersion liquid To the metal oxide particle (1) dispersion liquid having a solid content concentration of 10% by weight prepared in the same manner as in Example 1, 1.8 g of acetic acid aqueous solution having a concentration of 3% by weight was added. The pH of the dispersion was adjusted to 5.5 and stirred at 30 ° C. for 1 hour.

Next, the dispersion was separated by centrifugal separation, and the particles were dried at 120 ° C. for 15 hours to prepare metal oxide particles (2).
With respect to the obtained metal oxide particles (2), the average particle diameter and the coverage were measured, and the results are shown in the table.

  Next, it is dispersed in water, and then the leveling agent (manufactured by Nissin Kogyo Co., Ltd .: EXP-4026) is 0.1 parts by weight with respect to 100 parts by weight of the metal oxide particle (2) dispersion. A metal oxide particle (2) dispersion having a solid content concentration of 2% by weight was prepared.

Production of substrate with water repellent coating (2) In Example 1, a substrate with water repellent coating (2) was used in the same manner as in Example 1, except that a metal oxide particle (2) dispersion having a solid content of 2.0% by weight was used. ) Was prepared.

Water repellent film-coated substrate (2), the composition, the average height of the concavo-convex structure (T _F), the distance between the average protrusion (W _F), the average height of the fine unevenness (T _FF), between the average protrusion The distance (W _FF ), pencil hardness, adhesion, scratch resistance, water repellency, total light transmittance and haze were measured, and the results are shown in the table.

[Example 3]
Preparation of Dispersion of Metal Oxide Particles (3) Metal oxide particles (2) prepared in the same manner as in Example 2 were calcined at 1000 ° C. for 2 hours, and then metal oxide particles (3 ) Dispersed in a sand mill disperser (Shinmaru Enterprises Co., Ltd.) filled with 1015 g of 0.5 mmφ glass media, and then pulverized for 3 hours, followed by a high-speed centrifuge (Hitachi, Ltd.) After separating at 2000 rpm for 3 minutes and diluting with pure water, a leveling agent (manufactured by Nissin Kogyo Co., Ltd .: EXP-4026) is added to 0.1 parts by weight of 100 parts by weight of the metal oxide particle (3) dispersion. It added so that it might become a weight part, and the metal oxide particle (3) dispersion liquid with a solid content concentration of 2 weight% was prepared.
The obtained metal oxide particles (3) were measured for average particle diameter and coverage, and the results are shown in the table.

Production of substrate with water repellent coating (3) In Example 1 of Example 1, a substrate with water repellent coating (3) was used in the same manner except that a dispersion of metal oxide particles (3) having a solid content of 2.0% by weight was used. ) Was prepared.

For with a water-repellent film substrate (3), the composition, the average height of the concavo-convex structure (T _F), the distance between the average protrusion (W _F), the average height of the fine unevenness (T _FF), between the average protrusion The distance (W _FF ), pencil hardness, adhesion, scratch resistance, water repellency, total light transmittance and haze were measured, and the results are shown in the table.

[Example 4]
Preparation of Metal Oxide Particle (4) Dispersion Into 3659 g of the substrate metal oxide particle (A-1) dispersion made of silica having a SiO ₂ concentration of 4.1% by weight prepared in the same manner as in Example 1, Silica sol as a coating metal oxide particle (B-1) used in No. 1 (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) 184 g was mixed and stirred at 30 ° C. for 0.5 hour. At this time, the SiO ₂ concentration of the mixed dispersion was 4.7% by weight, and the pH was 3.5. Process (m)

Next, 135 g of an anion exchange resin (manufactured by Mitsubishi Chemical Co., Ltd .: SUNUP-C) was mixed in the mixed dispersion, and the mixture was stirred for 0.5 hour. Then, the anion exchange resin was separated, and the SiO ₂ concentration was measured by a rotary evaporator. A dispersion of metal oxide particles (4) comprising 10% by weight of silica was prepared, diluted with pure water, and then a leveling agent (manufactured by Nissin Kogyo Co., Ltd .: EXP-4026) was added to the metal oxide particles. (4) A metal oxide particle (4) dispersion having a solid content of 2% by weight was prepared by adding 0.1 part by weight to 100 parts by weight of the dispersion. The pH of the dispersion was 9.0. Step (n)
With respect to the obtained metal oxide particles (4), the average particle diameter and the coverage were determined, and the results are shown in the table.

Production of substrate with water repellent coating (4) In Example 1 of Example 1, a substrate with water repellent coating (4) was used except that a dispersion of metal oxide particles (4) having a solid content of 2.0% by weight was used. ) Was prepared.

Water repellent film-coated substrate (4), the composition, the average height of the concavo-convex structure (T _F), the distance between the average protrusion (W _F), the average height of the fine unevenness (T _FF), between the average protrusion The distance (W _FF ), pencil hardness, adhesion, scratch resistance, water repellency, total light transmittance and haze were measured, and the results are shown in the table.

[Example 5]
Preparation of Metal Oxide Particle (5) Dispersion Into 3659 g of substrate metal oxide particle (A-1) dispersion made of silica having a SiO ₂ concentration of 4.1% by weight prepared in the same manner as in Example 1, Silica sol as a coating metal oxide particle (B-1) used in No. 1 (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) 367 g was mixed and stirred at 30 ° C. for 0.5 hour. At this time, the SiO ₂ concentration of the mixed dispersion was 5.2% by weight, and the pH was 3.5. Process (m)

Then, the anion exchange resin in the mixed dispersion (Mitsubishi Chemical Co., Ltd.: SUNNUP-C) were mixed 135 g, and stirred for 0.5 hours, then separating the anion exchange resin, SiO ₂ concentration on a rotary evaporator A metal oxide particle (5) dispersion comprising 10% by weight of silica is prepared, diluted with pure water, and then a leveling agent (manufactured by Nissin Kogyo Co., Ltd .: EXP-4026) is added to the metal oxide particle. (5) A metal oxide particle (5) dispersion having a solid content concentration of 2% by weight was prepared by adding 0.1 part by weight to 100 parts by weight of the dispersion. The pH of the dispersion was 9.0. Step (n)
For the obtained metal oxide particles (5), the average particle diameter and the coverage were determined, and the results are shown in the table.

Production of substrate with water repellent coating (5) In Example 1 of Example 1, a substrate with a water repellent coating (5) was used in the same manner except that a metal oxide particle (5) dispersion having a solid content of 2.0% by weight was used. ) Was prepared.

Water repellent film-coated substrate (5), the composition, the average height of the concavo-convex structure (T _F), the distance between the average protrusion (W _F), the average height of the fine unevenness (T _FF), between the average protrusion The distance (W _FF ), pencil hardness, adhesion, scratch resistance, water repellency, total light transmittance and haze were measured, and the results are shown in the table.

[Example 6]
Preparation of metal oxide particle (6) dispersion
Preparation of positively charged base metal oxide particles (A-2) Silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid SI-45P, average particle size 45 nm, surface potential -60 mV, SiO ₂ concentration 20 wt%, pH 10 .2) 150 g of cation exchange resin (ROHMHARS Co., Ltd .: Duolite) was mixed with 750 g and stirred at 30 ° C. 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 stirred for 0.5 hour, and then the anion exchange resin was separated, 750 g of purified silica sol having a SiO ₂ 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, 3621 g of a dispersion of metal oxide particles for substrate (A-2) made of silica having a SiO ₂ concentration of 4.1 wt% diluted with 2903 g of pure water was prepared. The surface potential of the metal oxide particles for substrate (A-2) was measured, and the results are shown in the table.

Next, to the base metal oxide particle (A-2) dispersion 3662g made of silica having a SiO ₂ concentration of 4.1% by weight, silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid SN-350, average particle diameter 7 nm, 595 g of a surface potential of −23 mV, a SiO ₂ concentration of 16.6% by weight and a pH of 3.7) were mixed. At this time, the pH of the mixed dispersion was 3.5. Process (m)

Next, 135 g of an anion exchange resin (manufactured by Mitsubishi Chemical Co., Ltd .: SUNUP-C) was mixed in the mixed dispersion, and the mixture was stirred for 0.5 hour. Then, the anion exchange resin was separated, and the SiO ₂ concentration was measured by a rotary evaporator. A dispersion of metal oxide particles (6) comprising 10% by weight of silica was prepared, diluted with pure water, and then a leveling agent (manufactured by Nissin Kogyo Co., Ltd .: EXP-4026) was added to the metal oxide particles. (6) A metal oxide particle (6) dispersion having a solid content concentration of 2% by weight was prepared by adding 0.1 part by weight to 100 parts by weight of the dispersion. The pH of the dispersion was 9.0. Step (n)
With respect to the obtained metal oxide particles (6), the average particle diameter and the coverage were determined, and the results are shown in the table.

Production Example 1 of Substrate (6) with Water-repellent Coating In the same manner as in Example 1 except that a dispersion of metal oxide particles (6) diluted with pure water to a solid content concentration of 2.0% by weight was used. A substrate (6) with a water-repellent coating was prepared.

About base material with water-repellent coating (6), composition, average height (T _F ) of uneven structure, average distance between protrusions (W _F ), average height of fine uneven structure (T _FF ), between average protrusions The distance (W _FF ), pencil hardness, adhesion, scratch resistance, water repellency, total light transmittance and haze were measured, and the results are shown in the table.

[Example 7]
Preparation of metal oxide particle (7) dispersion
Preparation of positively charged base metal oxide particles (A-3) Silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Spherica slurry 120, average particle size 120 nm, surface potential -65 mV, SiO ₂ concentration 18 wt%, pH 10 .2) 833 g of cation exchange resin (ROHMHARS Co., Ltd .: Duolite) 150 g was mixed and stirred at 30 ° C. 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 stirred for 0.5 hour, and then the anion exchange resin was separated, 833 g of purified silica sol having a SiO ₂ concentration of 20% by weight was prepared.

Next, 3.5 g of polyaluminum chloride (manufactured by Taki Chemical Co., Ltd .: Takibaine # 1000, Al ₂ O ₃ concentration 23.55 wt%) was added to 833 g of purified silica sol, and the mixture was stirred at room temperature for 0.5 hour. Subsequently, 2826 g of pure water was added and diluted to prepare 3659 g of a dispersion of base metal oxide particles (A-3) made of silica having a SiO ₂ concentration of 4.1 wt%. The surface potential of the metal oxide particles for substrate (A-3) was measured, and the results are shown in the table.

Next, 3655 g of the base metal oxide particle (A-3) dispersion made of silica having a SiO ₂ concentration of 4.1% by weight was added to silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid SN-350, average particle diameter 7 nm, 185 g of a surface potential of −23 mV, a SiO ₂ concentration of 16.6% by weight, and a pH of 3.7) were mixed. At this time, the pH of the mixed dispersion was 3.5. Process (m)

Next, 135 g of an anion exchange resin (manufactured by Mitsubishi Chemical Co., Ltd .: SUNUP-C) was mixed in the mixed dispersion, and the mixture was stirred for 0.5 hour. Then, the anion exchange resin was separated, and the SiO ₂ concentration was measured by a rotary evaporator. A dispersion of metal oxide particles (7) composed of 10% by weight of silica was prepared, diluted with pure water, and then a leveling agent (manufactured by Nissin Kogyo Co., Ltd .: EXP-4026) was added to the metal oxide particles (1 ) A metal oxide particle (7) dispersion having a solid content of 2% by weight was prepared by adding 0.1 part by weight to 100 parts by weight of the dispersion. The pH of the dispersion was 9.0. Step (n)
With respect to the obtained metal oxide particles (7), the average particle diameter and the coverage were determined, and the results are shown in the table.

Production of substrate with water repellent coating (7) In Example 1 of Example 1, a substrate with water repellent coating (7) was used except that a dispersion of metal oxide particles (7) having a solid concentration of 2.0% by weight was used. ) Was prepared.

About base material with water-repellent coating (7), composition, average height (T _F ) of uneven structure, average distance between protrusions (W _F ), average height of fine uneven structure (T _FF ), between average protrusions The distance (W _FF ), pencil hardness, adhesion, scratch resistance, water repellency, total light transmittance and haze were measured, and the results are shown in the table.

[Example 8]
Production of metal oxide particles (8)
Preparation of positively charged metal oxide particles for coating (B-2) 17.5 g of cerium (III) sulfate octahydrate and 1765.8 g of distilled water were placed in a 5 L container and dissolved by stirring. Subsequently, the temperature was raised to 93 ° C. while stirring, and 1255 g of a 1.0% aqueous sodium hydroxide solution was added all at once, and the temperature was maintained at 93 ° C. for 6 hours with stirring. Next, when it cooled to 30 degrees C or less, white precipitate was obtained. The pH of this solution was 10.0. This solution was treated at 14000 rpm for 10 minutes using a centrifugal separator, and then the supernatant was removed. Distilled water (2884.5 g) was added to the white precipitate, and the mixture was further treated with a centrifugal separator at 14000 rpm for 10 minutes. This operation was performed three times in total, and the precipitate was washed to prepare a ceria fine particle dispersion (CeO ₂ concentration 2.1 wt%, pH 10.0). The obtained ceria fine particles were monodispersed and the average particle size was 5 nm.

Next, 75.0 g of a cation exchange resin (ROHMHARS Co., Ltd .: Duolite) was mixed with 3571.4 g of the ceria fine particle dispersion, and the mixture was stirred at 30 ° C. for 0.5 hour to obtain metal oxide particles for coating (B- 2) A dispersion was prepared.
The pH of the coating metal oxide particle (B-2) dispersion was 3.0. Further, the surface potential and average particle diameter of the coating metal oxide particles (B-2) were measured, and the results are shown in the table.

Preparation of metal oxide particle (A-4) dispersion for substrate having negative charge Silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid SI-80P, average particle diameter 80 nm, surface potential -60 mV, SiO ₂ concentration 20% by weight , PH 10.2) 750 g of cation exchange resin (ROHMHARS Co., Ltd .: Duolite) 150 g was mixed and stirred at 30 ° C. for 0.5 hour. After separating the cation exchange resin, 135 g of an anion exchange resin (Mitsubishi Chemical Corporation: SUNUP-C) is mixed and stirred at 30 ° C. for 0.5 hour, and then the anion exchange resin is separated. 750 g of purified silica sol having a SiO ₂ concentration of 20% by weight was prepared. This was diluted to 4.1% by weight to prepare a metal oxide particle (A-4) dispersion for a substrate. The pH at this time was 3.5. The surface potential of the metal oxide particles for substrate (A-4) was measured, and the results are shown in the table.

Next, 3571.4 g of the coating metal oxide particle (B-2) dispersion liquid was mixed with 3659 g of the base metal oxide particle (A-4) dispersion liquid and stirred at 30 ° C. for 0.5 hour. At this time, the pH of the mixed dispersion was 3.2. Process (n)

Thereafter, the step (b) was carried out in the same manner as in Example 1 to produce a metal oxide particle (8) dispersion having a SiO ₂ concentration of 2.0% by weight. Step (b)
With respect to the obtained metal oxide particles (8), the average particle diameter and the coverage were determined, and the results are shown in the table.

Production of substrate with water repellent coating (8) In Example 1, a substrate with water repellent coating (in the same manner as in Example 1) except that a dispersion of metal oxide particle (8) having a SiO ₂ concentration of 2.0% by weight was used. 8) was prepared.

Water repellent film-coated substrate (8), the composition, the average height of the concavo-convex structure (T _F), the distance between the average protrusion (W _F), the average height of the fine unevenness (T _FF), between the average protrusion The distance (W _FF ), pencil hardness, adhesion, scratch resistance, water repellency, total light transmittance and haze were measured, and the results are shown in the table.

[Example 9]
Preparation of metal oxide particle (9) dispersion
Preparation of coating metal oxide particles (B-3) having a positive charge Alumina sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid AP-5, average particle diameter 60 nm, surface potential 55 mV, Al ₂ O ₃ concentration 78% by weight, Metal oxide particles for coating consisting of alumina by crushing 82.7 g of pH 4.5) and 580.5 g of pure water at 2160 rpm for 180 minutes with a sand mill (manufactured by Shinmaru Enterprises Co., Ltd .: glass beads 0.5 mmφ1100 g) (B-3) A dispersion was prepared.

The pH of the coating metal oxide particle (B-3) dispersion was 4.0. Further, the surface potential and average particle diameter of the coating metal oxide particles (B-3) were measured, and the results are shown in the table.
Subsequently, the metal oxide particles for coating (B-3) were added to 3659 g of the substrate metal oxide particles (A-4) dispersion made of silica having a SiO ₂ concentration of 4.1 wt% prepared in the same manner as in Example 8. 672.6 g of the dispersion was mixed and stirred at 30 ° C. for 0.5 hour. At this time, the pH of the mixed dispersion was 3.6. Process (m)

Thereafter, the step (n) was performed in the same manner as in Example 1 to produce a dispersion of metal oxide particle (9) having a SiO ₂ .A ₂ O ₃ concentration of 10% by weight. Subsequently, it is diluted with pure water, and then a leveling agent is added so as to be 0.1 part by weight with respect to 100 parts by weight of the metal oxide particle (9) dispersion, thereby oxidizing the metal with a solid concentration of 2.0% by weight. A particle particle (9) dispersion was prepared. Step (n)
For the obtained metal oxide particles (9), the average particle diameter and the coverage were determined, and the results are shown in the table.

Manufacture of substrate (9) with water repellent coating First, a coating liquid for binding material (1) having a solid content concentration of 0.3% by weight was applied to a glass substrate (Hamashin Co., Ltd .: FL glass, thickness: 3 mm, Refractive index: 1.51) was coated on the spin coater so as to have the content shown in the table, and dried at 80 ° C for 30 seconds. Next, a dispersion of metal oxide particle (9) having a solid content concentration of 2.0% by weight was applied by the bar coater method (# 3) so that the dry layer thickness would be the front, and dried at 80 ° C. for 30 seconds. . Next, the binder coating liquid (1) having a solid content concentration of 0.3% by weight was applied onto the metal oxide particle (9) layer with a spin coater so as to have the content shown in the table, and 120 ° C. at 120 ° C. After drying for 2 seconds, it was cured by heating at 150 ° C. for 30 minutes.

  Next, an overcoat layer-forming coating solution (1) having a solid content concentration of 1.0% by weight was applied by the bar coater method (# 4) so as to have the content shown in the table, dried at 80 ° C. for 120 seconds, and then 150 A substrate (9) with a water-repellent coating was produced by drying and curing at 10 ° C. for 10 minutes.

Repellent substrate with a transparent film for (9), the composition, the average height (T _F) of the concavo-convex structure, the distance between the average protrusion (W _F), the average height of the fine unevenness (T _FF), average protrusion The distance (W _FF ), pencil hardness, adhesion, scratch resistance, water repellency, total light transmittance and haze were measured, and the results are shown in the table.

[Example 10]
Preparation of metal oxide particle (10) dispersion
A silica sol as a coating metal oxide particle (B-4) was added to 3659 g of the substrate metal oxide particle (A-1) dispersion made of silica having a SiO ₂ concentration of 4.1 wt% prepared in the same manner as in Example 1. 122 g (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid SN, average particle diameter 5 nm, surface potential −20 mV, SiO ₂ concentration 20.0 wt%, pH 3.8) was mixed and stirred at 30 ° C. for 0.5 hour. At this time, the SiO ₂ concentration of the mixed dispersion was 5.0% by weight and the pH was 3.5. Process (m)

Next, 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 at 30 ° C. for 0.5 hour, and then the anion exchange resin was separated, and a rotary evaporator was used. A dispersion of metal oxide particles (10) made of silica having a SiO ₂ concentration of 10% by weight was prepared. Subsequently, it is diluted with pure water, and then a leveling agent is added so as to be 0.1 part by weight with respect to 100 parts by weight of the metal oxide particle (10) dispersion to obtain a solid content concentration of 2.0% by weight. A metal oxide particle (10) dispersion was prepared. The pH of the metal oxide particle (10) dispersion was 9.0. Step (n)
With respect to the obtained metal oxide particles (10), the average particle diameter and the coverage were determined, and the results are shown in the table.

Production of substrate with water repellent coating (10) In Example 1 of Example 1, the substrate with water repellent coating (10) was used in the same manner except that the dispersion of metal oxide particle (10) having a solid content of 2.0% by weight was used. 10) was prepared.

Water repellent film-coated substrate (9), the composition, the average height of the concavo-convex structure (T _F), the distance between the average protrusion (W _F), the average height of the fine unevenness (T _FF), between the average protrusion The distance (W _FF ), pencil hardness, adhesion, scratch resistance, water repellency, total light transmittance and haze were measured, and the results are shown in the table.

[Example 11]
Preparation of metal oxide particle (11) dispersion
Preparation of metal oxide particles (B-5) for coating Silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid SI-50, average particle size 25 nm, surface potential -51 mV, SiO ₂ concentration 48.0 wt%, pH 10.2 ) 833 g was diluted to 20% with pure water. To this solution, 150 g of a cation exchange resin (ROHMHARS, duolite) was mixed and stirred at 30 ° C. for 0.5 hour. Next, after separating the cation exchange resin, 135 g of anion exchange resin (Mitsubishi Chemical Corporation: SUNUP-C) is mixed and stirred at 30 ° C. for 0.5 hour, and then the anion exchange resin is separated. Then, a coating metal oxide particle (B-5) dispersion having a SiO ₂ concentration of 20% by weight was prepared. At this time, the pH was 3.8 and the surface potential was -20 mV.

Subsequently, the metal oxide particles for coating (B-5) were added to 3659 g of the substrate metal oxide particles (A-1) dispersion made of silica having a SiO ₂ concentration of 4.1 wt% prepared in the same manner as in Example 1. 520 g was mixed and stirred at 30 ° C. for 0.5 hour. At this time, the SiO ₂ concentration of the mixed dispersion was 6.0% by weight and the pH was 3.5. Process (m)

135 g of anion exchange resin (manufactured by Mitsubishi Chemical Co., Ltd .: SUNNUP-C) is mixed with the mixed dispersion and stirred for 0.5 hour, then the anion exchange resin is separated, and the SiO ₂ concentration is 10 wt. A dispersion of metal oxide particles (11) consisting of 1% silica was prepared. Next, it is diluted with pure water, and then a leveling agent is added so as to be 0.1 part by weight with respect to 100 parts by weight of the metal oxide particle (11) dispersion to obtain a solid content concentration of 2.0% by weight. A metal oxide particle (10) dispersion was prepared. The pH of the dispersion was 9.0. Step (n)
For the obtained metal oxide particles (11), the coverage was determined, and the results are shown in the table.

Production of substrate (11) with water-repellent coating In Example 1, a substrate with water-repellent coating (11) was used except that a metal oxide particle (11) dispersion having a solid content of 2.0% by weight was used. ) Was prepared.

Water repellent film-coated substrate (11), the composition, the average height of the concavo-convex structure (T _F), the distance between the average protrusion (W _F), the average height of the fine unevenness (T _FF), between the average protrusion The distance (W _FF ), pencil hardness, adhesion, scratch resistance, water repellency, total light transmittance and haze were measured, and the results are shown in the table.

[Example 12]
Preparation of metal oxide particle (12) dispersion
Preparation of dispersion for positively charged metal oxide particles for substrate (A-5) In preparation of positively charged metal oxide particles for substrate (A-1) in Example 1, 750 g of purified silica sol was mixed with polyaluminum chloride ( (Taki Chemical Co., Ltd .: Takibaine # 1000, Al ₂ O ₃ concentration 23.55 wt%) was added and stirred at room temperature for 0.5 hours, followed by hydrothermal treatment at 80 ° C. for 3 hours. In the same manner, 3659 g of a base metal oxide particle (A-5) dispersion composed of silica having a SiO ₂ concentration of 4.1% by weight was prepared. The pH of the metal oxide particle (A-5) dispersion for the substrate was 3.7. The surface potential of the metal oxide particles for substrate (A-5) was measured, and the results are shown in the table.

Next, the same silica sol as used in Example 1 as the coating metal oxide particles (B-1) was added to 3659 g of the substrate metal oxide particles (A-5) dispersion composed of silica having a SiO ₂ concentration of 4.1 wt%. (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) 367 g was mixed, and then the mixed dispersion was 150 ° C. The mixture was hydrothermally treated for 3 hours and then cooled to 30 ° C. At this time, the SiO ₂ concentration of the mixed dispersion was 5.2% by weight and the pH was 3.5. Process (m)

Next, 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 at 30 ° C. for 0.5 hour, and then the anion exchange resin was separated, and a rotary evaporator was used. A dispersion of metal oxide particles (12) made of silica having a SiO ₂ concentration of 10% by weight was prepared. Subsequently, it is diluted with pure water, and then a leveling agent is added so as to be 0.1 part by weight with respect to 100 parts by weight of the metal oxide particle (12) dispersion, thereby oxidizing the metal with a solid concentration of 2.0% by weight. A particle particle (12) dispersion was prepared. The pH of the dispersion was 9.0. Step (n)

Production of substrate with water repellent coating (12) In Example 1 of Example 1, a substrate with water repellent coating (12) was used except that a dispersion of metal oxide particles (12) having a solid content of 2.0% by weight was used. ) Was prepared.

Water repellent film-coated substrate (12), the composition, the average height of the concavo-convex structure (T _F), the distance between the average protrusion (W _F), the average height of the fine unevenness (T _FF), between the average protrusion The distance (W _FF ), pencil hardness, adhesion, scratch resistance, water repellency, total light transmittance and haze were measured, and the results are shown in the table.

[Example 13]
Production Example 1 of Substrate with Water Repellent Coating (13) In Example 1 except that the coating solution for forming an overcoat layer (1) having a solid content concentration of 1.0% by weight was applied so as to have the content shown in the table. Thus, a substrate (13) with a water-repellent coating was prepared.

Repellent substrate with a transparent film for (13), the composition, the average height (T _F) of the concavo-convex structure, the distance between the average protrusion (W _F), the average height of the fine unevenness (T _FF), average protrusion The distance (W _FF ), pencil hardness, adhesion, scratch resistance, water repellency, total light transmittance and haze were measured, and the results are shown in the table.

[Example 14]
Production Example 1 of substrate (14) with water-repellent coating In the same manner as in Example 1 except that the coating solution for forming an overcoat layer (1) having a solid content concentration of 1.0% by weight was applied to the content shown in the table. Thus, a substrate (14) with a water-repellent coating was prepared.

Repellent substrate with a transparent film for (14), the composition, the average height (T _F) of the concavo-convex structure, the distance between the average protrusion (W _F), the average height of the fine unevenness (T _FF), average protrusion The distance (W _FF ), pencil hardness, adhesion, scratch resistance, water repellency, total light transmittance and haze were measured, and the results are shown in the table.

[Example 15]
Production of water repellent coated substrate (15) A water repellent coated substrate (15) was prepared in the same manner as in Production Example 1 except that the coating liquid (1) for forming an adhesive layer was not applied and dried.

Concerning water-repellent transparent coated substrate (15), composition, average height of uneven structure (T _F ), average distance between protrusions (W _F ), average height of fine uneven structure (T _FF ), average protrusion The distance (W _FF ), pencil hardness, adhesion, scratch resistance, water repellency, total light transmittance and haze were measured, and the results are shown in the table.

[Example 16]
Production of substrate (16) with water repellent coating First, a metal oxide particle (1) dispersion having a solid content concentration of 2.0% by weight prepared in the same manner as in Example 1 was added to a polyester resin substrate (Unitika Ltd.). ) Product: PC0.5, Thickness: 0.5mm, Refractive index: 1.60), coated with bar coater method (# 3) so that the dry layer thickness is the front, and dried at 80 ° C for 30 seconds did. Next, the binder coating solution (1) having a solid concentration of 0.3% by weight was coated on the metal oxide particle (1) layer with a spin coater so as to have the content shown in the table, and 120 ° C. at 120 ° C. After drying for 2 seconds, it was cured by heating at 150 ° C. for 30 minutes.

  Then, using a silicone water-repellent material (Momentive Co., Ltd .: TSW8251; solid content concentration: 3.3% by weight) as the overcoat layer-forming coating solution (2), the bar coater method ( It was coated in # 4), dried at 80 ° C. for 120 seconds, dried and cured at 150 ° C. for 10 minutes to produce a substrate (16) with a water-repellent coating.

About base material with water repellent coating (16), composition, average height of uneven structure (T _F ), average distance between protrusions (W _F ), average height of fine uneven structure (T _FF ), between average protrusions The distance (W _FF ), pencil hardness, adhesion, scratch resistance, water repellency, total light transmittance and haze were measured, and the results are shown in the table.

[Example 17]
Production of water-repellent coated substrate (17) In Example 1, instead of a glass substrate (Hamashin Co., Ltd .: FL glass, thickness: 3 mm, refractive index: 1.51), a stainless steel substrate ( A substrate (17) with a water-repellent coating was produced in the same manner except that Iwasaki Shoten Co., Ltd. (SUS304, thickness 1 mm) was used.

About base material with water repellent coating (17), composition, average height of uneven structure (T _F ), average distance between protrusions (W _F ), average height of fine uneven structure (T _FF ), between average protrusions The distance (W _FF ), pencil hardness, adhesion, scratch resistance, water repellency, total light transmittance and haze were measured, and the results are shown in the table.

[Comparative Example 1]
Preparation of dispersion of metal oxide particles (R1) Pure water was added to the dispersion of metal oxide particles for substrate (A-1) prepared in the same manner as in Example 1, and then the leveling agent was oxidized to metal for substrates. A metal oxide particle (R1) dispersion having a solid content concentration of 2% by weight was prepared by adding 0.1 part by weight to 100 parts by weight of the product particle (A-1) dispersion.

Production of substrate with water repellent coating (R1) In Example 1 of Example 1, a substrate with water repellent coating (R1) was used in the same manner except that a metal oxide particle (R1) dispersion having a solid content of 2.0% by weight was used. ) Was prepared.

Water repellent film-coated substrate (R1), the composition, the average height of the concavo-convex structure (T _F), the distance between the average protrusion (W _F), the average height of the fine unevenness (T _FF), between the average protrusion The distance (W _FF ), pencil hardness, adhesion, scratch resistance, water repellency, total light transmittance and haze were measured, and the results are shown in the table.

[Comparative Example 2]
Preparation of metal oxide particle (R2) dispersion Silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: SN-350, average particle diameter 7 nm, SiO ₂ concentration 16.6 wt%, surface potential −23 mV, pH 3.7) with water Was added to prepare a silica sol having a solid concentration of 2% by weight.
Subsequently, the same amount of the metal oxide particle (R1) dispersion having a solid content concentration of 2% by weight prepared in the same manner as in Comparative Example 1 was mixed to obtain a metal oxide particle (R2) dispersion having a solid content concentration of 2% by weight. Prepared.

Production of substrate with water repellent coating (R2) In Example 1, a substrate with water repellent coating (R2) was prepared in the same manner as in Example 1 except that a metal oxide particle (R2) dispersion having a solid content concentration of 2.0% by weight was used. ) Was prepared.

Water repellent film-coated substrate (R2), the composition, the average height of the concavo-convex structure (T _F), the distance between the average protrusion (W _F), the average height of the fine unevenness (T _FF), between the average protrusion The distance (W _FF ), pencil hardness, adhesion, scratch resistance, water repellency, total light transmittance and haze were measured, and the results are shown in the table.

[Comparative Example 3]
Preparation of metal oxide particle (R3) dispersion
Preparation of positively charged metal oxide particles for substrate (RA-3) Silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid SI-50, average particle size 25 nm, surface potential -51 mV, SiO ₂ concentration 48.0 wt% , PH 10.2) 833 g was diluted to 20% with pure water. To this solution, 150 g of a cation exchange resin (ROHMHARS Co., Ltd .: Duolite) was 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 stirred for 0.5 hour, and then the anion exchange resin was separated, A substrate metal oxide particle (RA-1) having a SiO ₂ concentration of 20% by weight was prepared. At this time, the pH was 3.8 and the surface potential was -20 mV.

Next, 5.1 g of polyaluminum chloride (manufactured by Taki Chemical Co., Ltd .: Takibaine # 1000, Al ₂ O ₃ concentration of 23.55 wt%) was added to form a metal oxide particle for a substrate having a solid concentration of 20 wt% ( RA-3) A dispersion was prepared. At this time, the pH of the dispersion became 3.7.

The average particle diameter and surface potential of the obtained metal oxide particles for substrates (RA-3) were measured, and the results are shown in the table.
Subsequently, 2908 g of pure water was added to 750 g of the base metal oxide particle (RA-3) dispersion having a solid concentration of 20% by weight to dilute to adjust the solid concentration to 4.1% by weight. 241.0 g of silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: SN-350, average particle diameter 7 nm, SiO ₂ concentration 16.6 wt%, surface potential −23 mV, pH 3.7) was mixed as oxide fine particles, and 30 ° C. For 0.5 hour.
At this time, the solid content concentration of the mixed dispersion was 4.8% by weight and the pH was 3.5. Process (m)

Next, 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 at 30 ° C. for 0.5 hour, and then the anion exchange resin was separated, and a rotary evaporator was used. A dispersion of metal oxide particles (R3) composed of silica having a SiO ₂ concentration of 10% by weight was prepared. Next, it is diluted with pure water, and then a leveling agent is added so as to be 0.1 parts by weight with respect to 100 parts by weight of the metal oxide particle (R3) dispersion, thereby oxidizing the metal with a solid concentration of 2.0% by weight. A product particle (R3) dispersion was prepared. The pH of the dispersion was 9.0. Step (n)
For the obtained metal oxide particles (R3), the average particle diameter and the coverage were determined, and the results are shown in the table.

Production of substrate with water repellent coating (R3) In Example 1, a substrate with water repellent coating (R3) was prepared in the same manner as in Example 1 except that a metal oxide particle (R3) dispersion with a solid content of 2.0% by weight was used. ) Was prepared.
Water repellent film-coated substrate (R3), the composition, the average height of the concavo-convex structure (T _F), the distance between the average protrusion (W _F), the average height of the fine unevenness (T _FF), between the average protrusion The distance (W _FF ), pencil hardness, adhesion, scratch resistance, water repellency, total light transmittance and haze were measured, and the results are shown in the table.

[Comparative Example 4]
Preparation of metal oxide particle (R4) dispersion
Preparation of positively charged metal oxide particles (RA-4) for a substrate Pure silica particles (manufactured by JGC Catalysts & Chemicals Co., Ltd .: True Ryukyu SW-1.0, average particle diameter 1000 nm, SiO ₂ concentration 100% by weight) Water was added to prepare 3657 g of a silica particle dispersion having a SiO ₂ concentration of 4.1% by weight. At this time, the surface potential of the silica particles was −70 mV, and the pH of the dispersion was 6.0.

Next, 2.1 g of polyaluminum chloride (manufactured by Taki Chemical Co., Ltd .: Takibaine # 1000, Al ₂ O ₃ concentration 23.55 wt%) was added to form a metal oxide particle for a substrate having a solid concentration of 20 wt% ( RA-4) A dispersion was prepared. At this time, the pH of the dispersion became 3.7. The average particle diameter and surface potential of the obtained metal oxide particles for substrate (R4) were measured, and the results are shown in the table.

Next, 1.88 g of silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: SN-350, average particle diameter 7 nm, SiO ₂ concentration 16.6 wt%, surface potential −23 mV, pH 3.7) as coating metal oxide fine particles. Mix and stir at 30 ° C. for 0.5 hour. At this time, the solid content concentration of the mixed dispersion was 4.1% by weight, and the pH was 3.7.

135 g of anion exchange resin (manufactured by Mitsubishi Chemical Co., Ltd .: SUNNUP-C) is mixed with the mixed dispersion and stirred for 0.5 hour, then the anion exchange resin is separated, and the SiO ₂ concentration is 10 wt. A dispersion of metal oxide particles (R4) composed of 1% silica was prepared. Next, it is diluted with pure water, and then a leveling agent is added so as to be 0.1 part by weight with respect to 100 parts by weight of the metal oxide particle (R4) dispersion, thereby oxidizing the metal with a solid content concentration of 2.0% by weight. A product particle (R4) dispersion was prepared. The pH of the dispersion was 9.0. Step (n)
The obtained metal oxide particles (R4) were measured for average particle diameter and coverage, and the results are shown in the table.

Production of substrate with water repellent coating (R4) In Example 1, a substrate with water repellent coating (R4) was prepared in the same manner as in Example 1 except that a metal oxide particle (R4) dispersion having a solid content of 2.0% by weight was used. ) Was prepared.
Repellent transparent film substrate with the (R4), the composition, the average height (T _F) of the concave-convex structure, the distance between the average protrusion (W _F), the average height of the fine unevenness (T _FF), average protrusion The distance (W _FF ), pencil hardness, adhesion, scratch resistance, water repellency, total light transmittance and haze were measured, and the results are shown in the table.

[Comparative Example 5]
Production of substrate with water repellent coating (R5) In Example 1, a solid content concentration of 0. 0 was prepared in the same manner as in Example 1 without forming a metal oxide particle layer and an adhesive layer on the nonwoven fabric (1). 3% overcoat layer forming coating solution (1) was applied by the bar coater method (# 4) so as to have the contents shown in the table, then dried at 80 ° C. for 120 seconds, then dried at 150 ° C. for 10 minutes. Cured to produce a substrate with water repellent coating (R5).

Water repellent film-coated substrate (R5), the composition, the average height of the concavo-convex structure (T _F), the distance between the average protrusion (W _F), the average height of the fine unevenness (T _FF), between the average protrusion The distance (W _FF ), pencil hardness, adhesion, scratch resistance, water repellency, total light transmittance and haze were measured, and the results are shown in the table.

[Comparative Example 6]
Production of substrate with water repellent coating (R6) In Example 1, a solid content concentration of 3.3 prepared in the same manner as in Example 16 without forming a metal oxide particle layer and an adhesive layer on a glass substrate. The coating solution for forming an overcoat layer (2) by weight is applied by the bar coater method (# 4) so as to have the content shown in the table, then dried at 80 ° C. for 120 seconds and then dried at 150 ° C. for 10 minutes. Cured to produce a water repellent coated substrate (R6).

Water repellent film-coated substrate (R6), the composition, the average height of the concavo-convex structure (T _F), the distance between the average protrusion (W _F), the average height of the fine unevenness (T _FF), between the average protrusion The distance (W _FF ), pencil hardness, adhesion, scratch resistance, water repellency, total light transmittance and haze were measured, and the results are shown in the table.

Claims (17)

A substrate and a water-repellent coating on the surface of the substrate;
The water-repellent coating comprises a particle layer comprising metal oxide particles obtained by coating the surface of the metal oxide particles for substrate (A) with the metal oxide particles for coating (B), and an overcoat layer on the metal oxide particle layer The surface of the water-repellent coating has a concavo-convex structure, and the average height (T _F ) of the convex portions is in the range of 50 to 500 nm,
The average distance between protrusions (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 in the range of 100 to 180 °. A substrate with a water-repellent coating. The substrate with a water-repellent coating according to claim 1, wherein the metal oxide particles (A) for the substrate are spherical particles, and the average particle diameter (D _A ) is in the range of 40 to 600 nm. The substrate with water-repellent coating according to claim 1, wherein the coating metal oxide fine particles (B) have an average particle diameter (D _B ) in the range of 4 to 60 nm. 2. The coverage represented by the following formula (1) of the metal oxide particles for base (A) by the metal oxide particles for coating (B) is in the range of 30 to 100%. The base material with a water-repellent coating as described.
Coverage (%) = [[Measured Specific Surface Area of Metal Oxide Particles (S _A ) −Measured Specific Surface Area of Metal Oxide Particles for Substrate (S _M )] / [Calculation When 100% Covered Specific surface area (S _C ) -measured specific surface area of metal oxide particles for substrate (S _M )]] × 100 (1)
(Where (S _C ) = surface area per metal oxide particle × number of particles per unit weight (1 g),
Surface area per metal oxide particle = 4π · [(D _A ) / 2 + (D _B ) / 2] ² ,
Number of metal oxide particles for substrate (A) per unit weight (1 g) = 1 / [4/3 · π [(D _A ) / 2] ³ · d, d are metal oxide particles for substrate (A) Represents the particle density (g / ml). ) The ratio (D _B ) / (D _A ) between the average particle size (D _B ) and the average particle size (D _A ) is in the range of 0.007 to 0.5. The base material with a water-repellent coating as described. The base metal oxide particles (A) and the coating metal oxide particles (B) are SiO ₂ , Al ₂ O ₃ , Sb ₂ O ₅ , ZrO ₂ , TiO ₂ , Fe ₂ O ₃ , CeO ₂ , and It is at least one selected from these composite oxides or mixtures (provided that the metal oxide particles for substrate (A) and the metal oxide fine particles for coating (B) may be the same). The substrate with a water-repellent coating according to claim 1, wherein 2. The substrate with a water-repellent coating according to claim 1, wherein both the metal oxide particles for base (A) and the metal oxide fine particles for coating (B) are SiO ₂ .   The substrate with water-repellent coating according to claim 1, wherein the overcoat layer comprises at least one of a fluorine-containing compound, an alkyl group-containing compound, and a silicone compound. The substrate with water-repellent coating according to claim 8, wherein the overcoat layer is a hydrolyzed polycondensate of a hydrolyzable organosilicon compound represented by the following formula (1).
_{R n -SiX 4-n (1} )
(In the formula, R is a hydrocarbon group having 1 to 10 carbon atoms and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a halogen, hydrogen, n: an integer of 1 to 3) The amount of the overcoat layer formed is in the range of 1 to 100 parts by weight as SiO ₂ with respect to 100 parts by weight of the metal oxide particles of the metal oxide particle layer as a solid content. Base material with water repellent coating.   The adhesive layer (a1) between the base material and the metal oxide particle layer or an adhesive layer (a2) between the metal oxide particle layer and an overcoat layer to be described later. 2. A substrate with a water-repellent coating according to 1. The surface of the convex part of the concave-convex structure further has fine irregularities, the average height (T _FF ) of the fine convex part is in the range of 0.1 to 5 nm, and the average distance between the fine convex parts (W _FF ) is The base material with a water-repellent coating according to claim 1, which is smaller than an average distance (W _F ) between the convex portions and in a range of 0.1 to 5 nm. It consists of the following steps (b) to (d), the surface has a concavo-convex structure, the average height (T _F ) of the convex portions is in the range of 30 to 500 nm, and the average convex portion distance (pitch width) (W _F ) is in the range of 50 to 1000 nm, and the method for producing a substrate with a water-repellent coating having a contact angle with water in the range of 100 to 180 °;
(B) A dispersion of metal oxide particles in which the surface of the metal oxide particles for substrate (A) is coated with the metal oxide particles for coating (B) is applied onto the substrate to form a metal oxide particle layer. (C) The process of apply | coating the coating liquid for overcoat layer formation on the said metal oxide particle layer, and forming the overcoat layer (d) The process of heat-processing. The method for producing a substrate with a water-repellent coating according to claim 13, wherein the following step (a1) is performed before the step (b);
(A1) A step of forming an adhesive layer (a1) by applying an adhesive layer-forming coating solution on the substrate surface. The method for producing a substrate with a water-repellent coating according to claim 13, wherein the following step (a2) is performed after the step (b);
(A2) A step of forming an adhesive layer (a2) by applying an adhesive layer-forming coating solution on the metal oxide particle layer.   The method for producing a substrate with a water-repellent coating according to claim 13, wherein the concentration of the metal oxide particle dispersion is in the range of 0.1 to 10% by weight as a solid content.   With respect to 100 parts by weight of the metal oxide particles in the metal oxide particle layer formed in the step (b), the overcoat layer forming coating solution is applied as a solid content so as to be 1 to 100 parts by weight. The method for producing a substrate with a water-repellent coating according to claim 13.