JPH11269657A - Process for producing silica based film coated article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for producing excellent silica based film coated articles without requiring firing and pretreating and a process for rapidly and safely producing the functional film coated articles having excellent durability with the silica based film described above as a ground surface film. SOLUTION: The articles coated with the silica based film are produced by applying a coating liquid which is prepd. by dissolving an acid and silicon aloxide in an alcohol and contains 0.010 to 3 wt.%, in terms of silica, at least either one of the silicon aloxide and its hydrolyzate (inclusive of its partial hydrolyzate), 0.0010 to 1.0N acid and 0 to 10 wt.% water on a base material. The Organosilane having a hydrolyzable group and a functional functioning group or its hydrolyzate (inclusive of its partial hydrolyzate) is applied on this silica based film as a ground surface film, by which the functional film coated articles are produced.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an article in which a silica-based film is coated on the surface of a substrate such as glass, ceramics, plastics or metal, an article coated with a silica-based film, and a liquid composition for coating a silica-based film. And a method for producing an article in which a functional film is coated on the silica-based film, and a functional film-coated article.

[0002]

2. Description of the Related Art When providing a functional film on the surface of glass or other base material, the bonding strength between the base material and the functional film is improved, and when the base material contains an alkali component, diffusion of the alkali component is performed. Various techniques for providing a silica or other oxide base film between a base material and a functional film have been known for the purpose of preventing the occurrence of a problem and improving the durability of the functional film.

[0003] As a method of providing the oxide underlayer,
Sol-gel method (Japanese Patent Publication No. Hei 4-20781, JP-A-Hei 2-3)
No. 11332), a method of applying a solution in which chlorosilane is dissolved in a non-aqueous solvent (Japanese Patent Application Laid-Open No. 5-86353, Japanese Patent No. 2525536 (Japanese Patent Application Laid-Open No. 5-238787)).
No.)), a CVD method, a vapor deposition method, and the like.

[0004]

In these methods, the main purpose is to increase the number of hydroxyl groups on the surface of the base film in order to improve the bonding strength with the functional film. However, the hydroxyl groups on the surface of the undercoating film easily adsorb water contained in the air, and once the water is adsorbed, it is difficult to remove it easily.
(See Japanese Patent Publication No. Hei 4-20781, Japanese Patent Laid-Open Publication No. Hei 2-311332, and Japanese Patent Laid-Open Publication No. Hei 5-2387.)
No. 81) or a long-time treatment (the above-mentioned Japanese Patent Application Laid-Open No. 5-86353) was required even when heating was not required.

Further, a method of forming an oxide underlayer film (see Japanese Patent Application Laid-Open No. Hei 2-111332, Japanese Patent No. 25255)
In No. 36), the strength of the underlying film itself is low only by coating at room temperature.
Baking at about 00 to 600 ° C. was indispensable. Further, when the base material contains an alkali, it is necessary to form an oxide base film having a thickness of 100 nm or more in order to prevent the diffusion of the alkali during firing. However, when the thickness of the base film is large, there are problems that the film thickness tends to be non-uniform, appearance defects such as reflection unevenness are likely to occur, and the manufacturing cost is increased.

Further, a method of applying a solution of tetrachlorosilane dissolved in a non-aqueous solvent such as perfluorocarbon, methylene chloride, and hydrocarbon (Japanese Patent No. 252).
No. 5536), although a silica base film can be obtained at room temperature, scratch resistance is low. The chlorosilyl group has extremely high reactivity, and preparation and storage of the coating solution must be performed in an environment containing no water, which is not preferable in terms of production cost.

The present invention solves the above-mentioned problems of the prior art, and does not require a treatment such as sintering which leads to an increase in the production cost, and provides a silica-based film-coated article excellent as a base film and a function excellent in durability. It is an object of the present invention to provide a method for easily and easily producing an article coated with a conductive film.

[0008]

In order to solve the above-mentioned problems, in the present invention, an alcohol solution comprising a low-concentration silicon alkoxide and a high-concentration volatile acid is applied to a substrate and dried at room temperature. By coating a silica-based film having a strong and alkoxyl group on the surface of the base material, and further coating an organosilane having a hydrolyzable group and a functional functional group on the silica-based film. The functional film was firmly bonded to the substrate.

That is, the present invention provides a method for producing a silica-based film-coated article in which a coating solution comprising an alcohol solution containing a silicon alkoxide and an acid is applied to a substrate, wherein the coating solution comprises: (A) a silicon alkoxide and a hydrolyzate thereof. 0.010 to 3% by weight (in terms of silica) of at least one of decomposed products (including partially hydrolyzed products), (B) 0.0010 to 1.0 acid, and (C) water 0 to 10% by weight % Of a silica-based film-coated article characterized in that the article contains silica. When the component (A) contains both a silicon alkoxide and a hydrolyzate thereof (including a partial hydrolyzate), the weight% of the component (A) is the total value thereof.

In the present invention, the silicon alkoxide used for the coating solution is not particularly limited, and examples thereof include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane. A small silicon alkoxide, for example, a tetraalkoxysilane having an alkoxyl group having 3 or less carbon atoms is preferably used because a dense film is easily formed. Polymers of these tetraalkoxysilanes having an average degree of polymerization of 5 or less are also preferably used.

The kind of the acid catalyst used in the coating solution is selected from the group consisting of volatile acids such as hydrochloric acid, hydrofluoric acid, nitric acid, acetic acid, formic acid, and trifluoroacetic acid, from the viewpoint that they are volatilized by drying at room temperature and do not remain in the film. Acids are preferred, with hydrochloric acid having high volatility and being relatively easy to handle being particularly preferred.

There is no particular limitation on the alcohol solvent used in the above-mentioned coating solution. For example, methanol, ethanol, 1-propanol, 2-
Propanol, butyl alcohol, amyl alcohol and the like, among which methanol,
Chain-type saturated monohydric alcohols having 3 or less carbon atoms, such as ethanol, 1-propanol and 2-propanol, are preferably used because of their high evaporation rate at room temperature.

[0013] Inside a coating solution consisting of an alcohol solution containing silicon alkoxide, acid, and water (for dissolving the acid, impurities in the solvent, those coming from the humidity of the atmosphere, etc.), during preparation, storage and After the application, the hydrolysis reaction represented by the formula (1) is performed between the silicon alkoxide and water using the acid as a catalyst. In the formula, R is an alkyl group.

Embedded image (-Si-OR) + (H ₂ O) → (−Si-OH) + (ROH) (1)

Further, the silanol group (-
(Si-OH) form a siloxane bond (-Si-O-Si-) by a dehydration condensation reaction as shown in the formula (2).

## STR2 ## (-Si-OH) + (- Si-OH) → (-Si-O-Si -) + (H 2 O) (2)

In a coating solution comprising an alcohol solution containing a silicon alkoxide, an acid and water, as shown in the above formula (1), whether or not the alkoxy group of the silicon alkoxide undergoes a hydrolysis reaction, Whether the groups (-Si-OH) undergo a dehydration condensation reaction as shown in the above formula (2) in the coating solution depends on the acid concentration of the solution, the concentration of the silicon alkoxide or its hydrolyzate, and the amount of water. Depends greatly on The lower the concentration of silicon alkoxide and the amount of water, the more difficult the reaction of the above formula (1) to occur, and consequently the more difficult the reaction of the above formula (2). Also, the acid concentration of the solution is in the range of 0 to 3 in pH. , The reaction of the above formula (1) occurs quickly, but the reaction of the above formula (2) hardly occurs.

In the present invention, the silicon alkoxide in the coating solution is suppressed before the application by the above-mentioned dehydration-condensation reaction to keep the polymerization degree as low as possible, and the coating solution is applied to the surface of the substrate and dried. Occasionally, the reaction of the above formulas (1) and (2) occurs rapidly to form a siloxane bond, so that a dense film can be formed at room temperature. When a silicon alkoxide is hydrolyzed and polycondensed in a solution as in the prior art, the solution is applied to the surface of the base material, and becomes a bond between polymers when the solution is dried. Baking and hardening were necessary to form a dense film without forming a film. Therefore,
In the present invention, silicon alkoxide and its hydrolyzate (including partial hydrolyzate) in the coating liquid
Is preferably a monomer or a polymer of less than 20 mer. However, when the total of the monomer and the polymer less than the 20-mer accounts for 80% by weight or more based on the whole silicon alkoxide and its hydrolyzate (including the partial hydrolyzate), the 20-mer or more May be contained.

In the present invention, by keeping the concentration of the acid catalyst in the coating solution at 0.0010 to 1.0 N, the pH of the coating solution becomes 0 to 3, especially
Is about 2, the hydrolysis reaction of the remaining alkoxyl group of the above formula (1) and the dehydration condensation reaction of the above formula (2) are less likely to occur in the coating liquid before application, and the coating liquid was applied. Immediately after these reactions proceed rapidly. The preferred concentration of the acid in the coating solution is 0.01
１．０1.0.

The acid added as a catalyst preferably has a high concentration of at least 0.3 times the water content in order to maintain the concentration of the acid in the coating solution. That is, when the acid in the form of an aqueous solution is used, it is preferably a high-concentration acid having a concentration of 23.1% or more, for example, a hydrochloric acid aqueous solution of about 6.3 N or more. When an acid dissolved in ethanol is added as a catalyst, if the ethanol solution contains, for example, 0.5% by weight of water, the concentration of the acid in the ethanol solution is 0.15%.
It is preferable that the content be not less than 0.3% by weight (for example, 0.3 times 0.5% by weight), for example, 0.04 N or more for hydrochloric acid.

Further, silicon alkoxide and its hydrolyzate (including partial hydrolyzate) in the coating solution
Is preferably as low as possible, in combination with the pH of the coating solution, the hydrolysis reaction of the remaining alkoxyl group of the above formula (1) and the dehydration condensation reaction of the formula (2) before the application. This is preferable because it hardly occurs in the coating liquid. However, if the concentration is too low, the thickness of the silica film becomes too small, for example, the film thickness becomes less than 5 nm, and it becomes difficult to uniformly cover the base material. There is a tendency that the ability to prevent the diffusion of the polymer is reduced and the durability is deteriorated. When a functional film is coated thereon, the functional film cannot be firmly bonded to the silica film. When the total concentration of silicon alkoxide and its hydrolyzate (including partial hydrolyzate) exceeds 3% by weight, the thickness of the obtained silica film exceeds 300 nm, and the film is easily damaged and does not become a strong film. Therefore, the range of the total concentration of silicon alkoxide and its hydrolyzate (including partial hydrolyzate) (including a polymer of less than 20 mer) in the coating liquid is 0.010 to 3% by weight in terms of silica. And a preferable range is 0.010 to 0.6% by weight.

Further, silicon alkoxide and its hydrolyzate (including partial hydrolyzate) in the coating liquid
Is preferably kept relatively high, the concentration of the acid catalyst in the coating solution is also kept relatively high. Specifically, the coating liquid is obtained by converting (A) silicon alkoxide and its hydrolyzate (including partial hydrolyzate) and (B) acid in terms of silica into “(B)
It is preferable that the content of (component (defined) / (A) component (% by weight) "be 0.010 or more, and more preferably 0.03 or more.

When a large amount of water is present in the coating solution, the hydrolysis reaction of silicon alkoxide is promoted in the solution, and the dehydration condensation reaction is apt to occur. Therefore, the concentration of water in the coating solution is preferably as low as possible. Accordingly, the concentration of water in the coating liquid is 0 to 10% by weight, preferably 0 to 2% by weight.

By maintaining the concentration of water in the coating solution in this manner, maintaining the pH of the coating solution and maintaining the total concentration of silicon alkoxide and its hydrolyzate (including partial hydrolyzate) in the coating solution. Together with this, the hydrolysis reaction of the remaining alkoxyl group of the above formula (1) and the dehydration condensation reaction of the formula (2) are less likely to occur in the coating solution before coating, which is preferable. Even when the concentration of water in the coating liquid is zero, the hydrolysis reaction is not hindered because the water in the air is absorbed by the coating film after being applied to the substrate. But,
Since a normal alcohol solvent originally contains a small amount of water, and an acid is often added in the form of an aqueous solution, the concentration of water in the coating liquid is usually 0.1% by weight or more.

When the concentration of the acid catalyst in the coating solution is kept relatively low, it is preferable to keep the content of water in the coating solution relatively high. When the content is kept relatively low, it is preferable to keep the concentration of the acid catalyst in the coating solution relatively high. Specifically, the coating liquid is
The (B) acid and (C) water are combined with [(B) component (prescribed) ×
(C) (component (% by weight)] is preferably 0.0020 or more. For example, when the concentration of the acid catalyst in the coating liquid is less than 0.003N and the concentration of water is zero or too low, the hydrolysis reaction tends to be insufficient only by absorbing water from the air into the coating film. Therefore, it is preferable that about 2.0% by weight or more of water is contained in the coating liquid having a concentration of the acid catalyst of, for example, 0.0010N.

When a solution in which the silicon alkoxide and the acid are dissolved in the alcohol solvent in the above ratio is stirred, the silicon alkoxide mainly forms a hydrolyzate in the solution by the reaction of the above formula (1), and the above formula (1) 2)
, A part of the hydrolyzate undergoes a dehydration condensation reaction. A coating solution is thus prepared, in which silicon alkoxide is present in the form of a monomer (including a hydrolyzate) or a polymer of less than 20 mer.

When the coating liquid is applied to a substrate, the specific surface area of the applied liquid in the form of a film increases, so that the alcohol solvent in the film rapidly evaporates, and the silicon alkoxide and its hydrolysis are removed. (Including partial hydrolyzate) in the coating film suddenly increased, and the hydrolysis reaction and dehydration condensation reaction (2)
(Including further polycondensation reaction of a polymer of less than 0-mer) occurs rapidly, and a large number of siloxane bonds (..Si-O-Si ..) are formed in the coating film. A highly dense film mainly composed of silica and having a thickness of 5 to 300 nm is formed, which has a strong bond with the film. Thus, in the present invention, the reactivity at the time of film formation is high, and a reaction is performed at room temperature to form a very dense film, and subsequent baking is not necessary.

If a large number of siloxane bonds are already present in the coating solution prior to coating by a dehydration condensation reaction and a polymer having a polymerization degree of 20 or more is contained as in the prior art, the resulting silica film will Although a siloxane bond exists, the bond between the substrate surface and the silica film is not so strong because the siloxane bond connecting the substrate surface and the silica film is not generated so much. Conventionally, firing at a higher temperature is required to strengthen the bond.

Further, according to the present invention, the hydrolysis reaction and the dehydration condensation reaction of the partially hydrolyzed silicon alkoxide which has not been completely hydrolyzed in the coating liquid simultaneously proceed in the coating film. Alkoxyl groups remain on the surface of the formed silica film without being hydrolyzed. As described later, when the silica film is used as a base film and a functional film is coated thereon, the adhesion of the functional film Can be improved. In order to form a dense silica film by a conventional sol-gel method, the dehydrated and condensed silica film usually needs to be heated at 500 to 600 ° C.

In the present invention, a dense silica film is formed simply by applying natural or forced drying at room temperature or at a temperature of 150 ° C. or lower for 30 seconds to 5 minutes after the application of the coating solution. If the coating film is heated at a temperature of 150 ° C. or more, the silica film does not become denser and the adhesion of the functional film coated on the silica film cannot be improved.

Whether or not the alkoxyl group remains on the silica film surface can be determined by measuring the contact angle of a static water droplet on the silica film surface. As will be shown later in the examples, the contact angle of static water droplets on the surface of the silica film according to the present invention is 20 to 40 degrees. On the other hand, for example, a silica film is formed by a conventional sol-gel method, and 5
When firing at 00 to 600 ° C., the value of the contact angle of the static water droplet is several degrees or less. The reason why the static water droplet contact angle is low is that, although the alkoxyl groups remain on the surface of the silica film before the calcination, the calcination decomposes the alkoxyl groups and increases the hydroxyl groups on the silica film surface to make them hydrophilic. It is thought that it is due to doing.

Even if a functional film solution containing an organosilane is coated on a silica film having a hydroxyl group on the surface as a base film, the surface of the silica base film is usually coated before the organosilane is coated in a normal environment. Because the water in the air is bonded to the hydroxyl groups of the water and the water has been adsorbed on the surface of the underlayer,
This makes it difficult to form a chemical bond between the silica base film and the organosilane at room temperature.

In the present invention, a large amount of alkoxyl groups remain on the surface of the silica film, and the number of hydroxyl groups is small. Therefore, it is considered that moisture in the air is prevented from adsorbing on the surface of the underlayer. Therefore, when a functional film solution containing an organosilane is applied to the silica base film, a reaction between an alkoxyl group of the silica base film and a silanol group (a hydroxyl group or a hydrolyzed functional group) of the organosilane causes
At room temperature, a chemical bond can be formed between the silica base film and the organosilane, and the functional film can be firmly attached to the silica base film.

Oxide base, glass and ceramics,
Alternatively, it is difficult to form a chemical bond between the applied organosilanes as described above with respect to the surface of a substrate of a metal or plastics that has been subjected to hydrophilic treatment. By forming the remaining silica base film on the surface of these substrates,
The functional film can be firmly adhered to the substrate. When this silica base film is heated to a high temperature, the remaining alkoxyl group disappears and a hydroxyl group is formed instead, so that when a functional film to be coated thereon is to be firmly attached, The silica underlayer should not be preheated to temperatures above 150 ° C.

The silica film formed according to the present invention has a very excellent surface smoothness. Therefore, the functional film obtained by applying the functional organosilane on the base of the silica film also has very excellent surface smoothness. That is, the surfaces of the silica film and the functional film have an arithmetic average roughness (Ra) of 0.5 nm or less, particularly 0.1
0 to 0.5 nm, and ten-point average roughness (Rz) = 5.0
nm or less, especially 1.0 to 5.0 nm.
The surface roughnesses Ra and Rz are determined by using an atomic force microscope (AF
M) (Seiko Electronics Co., Ltd., scanning probe microscope "SPI3700", cantilever; silicon "S"
JIS defined in two dimensions using "I-DF20")
B0601 can be measured by a three-dimensionally extended method. In this case, the measurement area of the sample is a square of 1 μm × 1 μm, the number of measurement points is 512 × 256, the scanning speed is 1.02 Hz, the surface shape is measured by DFM (cyclic contact mode), correction by a low-pass filter, Leveling correction of the measured data was performed (a curved surface was obtained and fitted by least-squares approximation to correct the inclination of the data, and further, distortion in the Z-axis direction was removed), and the surface roughness Ra and Rz value were calculated.

The functional film coated on the silica-based film according to the present invention exhibits excellent water repellency, excellent low friction resistance, excellent rolling property of water droplets, excellent antifouling property, and excellent durability. One of the reasons is presumed to be due to the excellent smoothness of the surface of the functional film coated on the silica film having excellent smoothness. The reason why the excellent smoothness of the silica film is obtained is presumed as follows. That is, in the coating liquid before application, silicon alkoxide is uniformly dissolved in a solvent in the form of a monomer (including a hydrolyzate) or a polymer of less than 20 mer, and after application, It is presumed that due to the effect of the presence of the acid catalyst at a high concentration and the rapid increase in the concentration of the silicon alkoxide (including the hydrolyzate), excellent smoothness can be obtained for forming a dense silica film at room temperature.

On the other hand, when a solution in which a chlorosilyl group-containing compound such as tetrachlorosilane is dissolved in a non-aqueous solvent is applied instead of the silicon alkoxide used in the present invention, the reactivity of the chlorosilyl group-containing compound is reduced. Due to the very high degree, the reaction becomes non-uniform, and the surface roughness of the obtained film is, for example, arithmetic mean roughness (Ra)
= 7.9 nm and ten-point average roughness (Rz) = 29.8 nm, and the film has poorer smoothness than the present invention.

Although the above description has been made with reference to a film-coated article composed of silica alone, the present invention can also be applied to a film-coated article composed mainly of silica. That is, as a membrane component,
An oxide other than silicon, such as aluminum, zirconium, titanium, and cerium, is added, and a silica-based multi-component oxide film is formed by substituting up to 30% by weight of the above silica, usually 1 to 30% by weight in terms of oxide. By doing
Further, the durability can be improved. Above all, aluminum and zirconium strengthen the underlying film itself,
Further, it is preferable because the bond with the functional film is strengthened.
If the amount of the oxide other than silicon is less than 1% by weight, no effect can be obtained, and if it is more than 30% by weight, the denseness of the film is impaired and the film does not become strong.

It is preferable to add these oxides in the form of a chelate obtained by chemically modifying the alkoxide of these metals with β-diketone, acetic acid, trifluoroacetic acid, ethanolamine or the like. In particular, when chemically modified with acetylacetone, a kind of β-diketone, and added,
This is preferable because the stability of the solution is excellent and a relatively strong film is formed.

In the production of the silica-based film-coated article according to the present invention, the coating solution comprising the above alcohol solution is prepared by:
The coating is performed by applying the coating on a substrate surface such as glass, ceramics, plastics or metal at room temperature and normal pressure, and naturally or forcibly drying at room temperature and normal pressure or at a temperature of 150 ° C. or less for 30 seconds to 5 minutes. It is.

Since a hydrophilic group such as a hydroxyl group is present on the surface of a substrate such as glass, ceramics and metal, a coating film is formed on the substrate when the above-mentioned coating solution is applied. However, depending on the type of plastics substrate, the surface thereof has few hydrophilic groups and poor wettability with alcohol, so that the coating liquid may be repelled on the substrate surface to make it difficult to form a coating film. In the case of the above-mentioned base material having a small number of hydrophilic groups on the surface, the surface is treated in advance with a plasma or corona atmosphere containing oxygen to make the surface hydrophilic, or the surface of the base material is placed in an atmosphere containing oxygen. At 200
It is preferable to irradiate ultraviolet rays having a wavelength of about 300 nm to perform hydrophilic treatment, and then perform silica-based film coating treatment.

The method of applying the coating liquid for forming a silica-based film is not particularly limited, but includes, for example, dip coating, flow coating, spin coating, bar coating, roll coating, spray coating, hand coating, brushing, and the like. A coating method is exemplified.

According to the present invention, glass, ceramics,
A dense and hard silica-based film can be formed on the surface of a base material such as metal or plastic without heating to a high temperature. It also has the ability to block alkali from the base material, or is useful as a base film for improving the bonding strength between the base material and the functional film. On the silica-based film, for example, a hydrolyzable group and Water repellency, oil repellency, antifogging, antifouling, low friction resistance by applying organosilane having a functional functional group or its hydrolyzate (including partial hydrolyzate) or other coating In addition, functional films such as antireflection and other optical films, conductive films, semiconductor films, and protective films can be formed.

The hydrolyzable group of the organosilane is not particularly limited, but includes halogen, hydrogen, alkoxyl, acyloxy, isocyanate and the like. In particular, an alkoxyl group is preferable because the reaction is not extremely violent and handling such as storage is relatively easy.

For example, the method for coating the water-repellent / oil-repellent functional film is not particularly limited, but a fluoroalkyl group as a water-repellent functional group and an organosilane containing a hydrolyzable group are used. A processing method is preferred.

Examples of the organosilane having a fluoroalkyl group include CF ₃ (CF ₂ ) ₁₁ (CH ₂ ) ₂ SiCl ₃ ,
CF ₃ (CF ₂ ) ₁₀ (CH ₂ ) ₂ Si (Cl) ₃ , CF ₃ (C
F ₂ ) ₉ (CH ₂ ) ₂ SiCl ₃ , CF ₃ (CF ₂ ) ₈ (CH ₂ )
₂ SiCl ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃ , CF
₃ (CF ₂ ) ₆ (CH ₂ ) ₂ SiCl ₃ , CF ₃ (CF ₂ ) ₅ (C
H ₂ ) ₂ SiCl ₃ , CF ₃ (CF ₂ ) ₄ (CH ₂ ) ₂ SiC
l ₃ , CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ SiCl ₃ , CF ₃ (C
F ₂ ) ₂ (CH ₂ ) ₂ SiCl ₃ , CF ₃ CF ₂ (CH ₂ ) ₂ Si
Perfluoroalkyl group-containing trichlorosilane such as Cl ₃ , CF ₃ (CH ₂ ) ₂ SiCl ₃ ; CF ₃ (CF ₂ ) ₁₁
(CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₁₀ (C
H ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ S
i (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₈ (CH ₂ ) ₂ Si (OC
_{H 3) 3, CF 3 (} CF 2) 7 (CH 2) 2 Si (OCH 3) 3,
CF ₃ (CF ₂ ) ₆ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF
₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (C
F ₂ ) ₄ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ )
₃ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₂ (C
H ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ CF ₂ (CH ₂ ) ₂ Si (O
CH ₃ ) ₃ , CF ₃ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF
_{3 (CF 2) 1 1 (} CH 2) 2 Si (OC 2 H 5) 3, CF 3 (C
F ₂ ) ₁₀ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₉
(CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₈ (C
_{H 2) 2 Si (OC 2} H 5) 3, CF 3 (CF 2) 7 (CH 2) 2
Si (OC ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₆ (CH ₂ ) ₂ Si (O
C ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC
_{2 H 5) 3, CF 3} (CF 2) 4 (CH 2) 2 Si (OC
_{2 H 5) 3, CF 3} (CF 2) 3 (CH 2) 2 Si (OC
_{2 H 5) 3, CF 3} (CF 2) 2 (CH 2) 2 Si (OC
_{2 H 5) 3, CF 3} CF 2 (CH 2) 2 Si (OC 2 H 5) 3, C
Perfluoroalkyl group-containing trialkoxysilanes such as F ₃ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ ; CF ₃ (CF ₂ )
₁₁ (CH ₂ ) ₂ Si (OCOCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₁₀
(CH ₂ ) ₂ Si (OCOCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₉ (C
H ₂ ) ₂ Si (OCOCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₈ (C
H ₂ ) ₂ Si (OCOCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₇ (C
H ₂ ) ₂ Si (OCOCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₆ (C
H ₂ ) ₂ Si (OCOCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₅ (C
H ₂ ) ₂ Si (OCOCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₄ (C
H ₂ ) ₂ Si (OCOCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₃ (C
H ₂ ) ₂ Si (OCOCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₂ (C
H ₂ ) ₂ Si (OCOCH ₃ ) ₃ , CF ₃ CF ₂ (CH ₂ ) ₂ Si
(OCOCH ₃ ) ₃ , CF ₃ (CH ₂ ) ₂ Si (OCOC
Perfluoroalkyl group-containing trisiloxysilane such as H ₃ ) ₃ ; CF ₃ (CF ₂ ) ₁₁ (CH ₂ ) ₂ Si (NC
_{O) 3, CF 3 (CF} 2) 10 (CH 2) 2 Si (NCO) 3,
CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (NCO) ₃ , CF ₃ (C
F ₂ ) ₈ (CH ₂ ) ₂ Si (NCO) ₃ , CF ₃ (CF ₂ )
₇ (CH ₂ ) ₂ Si (NCO) ₃ , CF ₃ (CF ₂ ) ₆ (C
H ₂ ) ₂ Si (NCO) ₃ , CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si
(NCO) ₃ , CF ₃ (CF ₂ ) ₄ (CH ₂ ) ₂ Si (NC
O) ₃ , CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ Si (NCO) ₃ , C
F ₃ (CF ₂ ) ₂ (CH ₂ ) ₂ Si (NCO) ₃ , CF ₃ CF ₂
(CH ₂ ) ₂ Si (NCO) ₃ , CF ₃ (CH ₂ ) ₂ Si (NC
O) ₃ , such as a perfluoroalkyl group-containing triisocyanate silane.

By treating with an organosilane containing an alkyl group, a functional film having water repellency or low friction resistance can be obtained. Although not particularly limited, an organosilane containing a linear alkyl group having 1 to 30 carbon atoms and a hydrolyzable group can be preferably used.

Examples of the organosilane containing an alkyl group include CH ₃ (CH ₂ ) ₃₀ SiCl ₃ and CH ₃ (CH ₂ ) ₂₀ S.
iCl ₃ , CH ₃ (CH ₂ ) ₁₈ SiCl ₃ , CH ₃ (CH ₂ ) ₁₆
SiCl ₃ , CH ₃ (CH ₂ ) ₁₄ SiCl ₃ , CH ₃ (CH ₂ )
_{12 SiCl 3, CH 3 (CH} 2) 1 0 SiCl 3, CH 3 (C
H ₂ ) ₉ SiCl ₃ , CH ₃ (CH ₂ ) ₈ SiCl ₃ , CH ₃ (C
H ₂ ) ₇ SiCl ₃ , CH ₃ (CH ₂ ) ₆ SiCl ₃ , CH ₃ (C
H ₂ ) ₅ SiCl ₃ , CH ₃ (CH ₂ ) ₄ SiCl ₃ , CH ₃ (C
H ₂ ) ₃ SiCl ₃ , CH ₃ (CH ₂ ) ₂ SiCl ₃ , CH ₃ CH
₂ SiCl ₃ , (CH ₃ CH ₂ ) ₂ SiCl ₂ , (CH ₃ CH ₂ )
₃ SiCl, CH ₃ SiCl ₃ , (CH ₃ ) ₂ SiCl ₂ , (C
Alkyl-containing chlorosilanes such as H ₃ ) ₃ SiCl;
CH ₃ (CH ₂ ) ₃₀ Si (OCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₂₀
Si (OCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₁₈ Si (OCH ₃ ) ₃ ,
CH ₃ (CH ₂ ) ₁₆ Si (OCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₁₄
Si (OCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₁₂ Si (OCH ₃ ) ₃ ,
CH ₃ (CH ₂ ) ₁₀ Si (OCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₉ S
i (OCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₈ Si (OCH ₃ ) ₃ , C
H ₃ (CH ₂ ) ₇ Si (OCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₆ Si
(OCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₅ Si (OCH ₃ ) ₃ , CH
₃ (CH ₂ ) ₄ Si (OCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₃ Si (O
CH ₃ ) ₃ , CH ₃ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CH ₃ C
H ₂ Si (OCH ₃ ) ₃ , (CH ₃ CH ₂ ) ₂ Si (OC
H ₃ ) ₂ , (CH ₃ CH ₂ ) ₃ SiOCH ₃ , CH ₃ Si (OC
H ₃ ) ₃ , (CH ₃ ) ₂ Si (OCH ₃ ) ₂ , (CH ₃ ) ₃ SiO
CH ₃ , CH ₃ (CH ₂ ) ₃₀ Si (OC ₂ H ₅ ) ₃ , CH ₃ (C
_{H 2) 20 Si (OC 2} H 5) 3, CH 3 (CH 2) 1 8 Si (OC
_{2 H 5) 3, CH 3} (CH 2) 16 Si (OC 2 H 5) 3, CH
₃ (CH ₂ ) ₁₄ Si (OC ₂ H ₅ ) ₃ , CH ₃ (CH ₂ ) ₁₂ Si
(OC ₂ H ₅ ) ₃ , CH ₃ (CH ₂ ) ₁₀ Si (OC ₂ H ₅ ) ₃ ,
CH ₃ (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₃ , CH ₃ (CH ₂ ) ₈ S
i (OC ₂ H ₅ ) ₃ , CH ₃ (CH ₂ ) ₇ Si (OC ₂ H ₅ ) ₃ ,
CH ₃ (CH ₂ ) ₆ Si (OC ₂ H ₅ ) ₃ , CH ₃ (CH ₂ ) ₅ S
i (OC ₂ H ₅ ) ₃ , CH ₃ (CH ₂ ) ₄ Si (OC ₂ H ₅ ) ₃ ,
CH ₃ (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , CH ₃ (CH ₂ ) ₂ S
i (OC ₂ H ₅ ) ₃ , CH ₃ CH ₂ Si (OC ₂ H ₅ ) ₃ , (CH
₃ CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₂ , (CH ₃ CH ₂ ) ₃ SiOC _{2
H 5, CH 3 Si (OC} 2 H 5) 3, (CH 3) 2 Si (OC 2 H
₅ ) ₂ , (CH ₃ ) ₃ SiO ₂ H ₅ Alkyl group-containing alkoxysilane such _{as; CH 3 (CH 2) 30} Si (OCOC
_{H 3) 3, CH 3 (} CH 2) 20 Si (OCOCH 3) 3, CH 3
(CH ₂ ) ₁₈ Si (OCOCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₁₆ S
i (OCOCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₁₄ Si (OCOCH
₃ ) ₃ , CH ₃ (CH ₂ ) ₁₂ Si (OCOCH ₃ ) ₃ , CH
₃ (CH ₂ ) ₁₀ Si (OCOCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₉ S
i (OCOCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₈ Si (OCOC
_{H 3) 3, CH 3 (} CH 2) 7 Si (OCOCH 3) 3, CH 3
(CH ₂ ) ₆ Si (OCOCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₅ Si
(OCOCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₄ Si (OCOC
_{H 3) 3, CH 3 (} CH 2) 3 Si (OCOCH 3) 3, CH 3
(CH ₂ ) ₂ Si (OCOCH ₃ ) ₃ , CH ₃ CH ₂ Si (OC
OCH ₃ ) ₃ , (CH ₃ CH ₂ ) ₂ Si (OCOCH ₃ ) ₂ ,
(CH ₃ CH ₂ ) ₃ SiOCOCH ₃ , CH ₃ Si (OCOC
_{H 3) 3, (CH 3} ) 2 Si (OCOCH 3) 2, (CH 3) 3
Alkyloxysilanes containing alkyl groups such as SiOCOCH ₃ ; CH ₃ (CH ₂ ) ₃₀ Si (NCO) ₃ , CH ₃ (C
H ₂ ) ₂₀ Si (NCO) ₃ , CH ₃ (CH ₂ ) ₁₈ Si (NC
O) ₃ , CH ₃ (CH ₂ ) ₁₆ Si (NCO) ₃ , CH ₃ (CH
₂ ) ₁₄ Si (NCO) ₃ , CH ₃ (CH ₂ ) ₁₂ Si (NCO)
₃ , CH ₃ (CH ₂ ) ₁₀ Si (NCO) ₃ , CH ₃ (CH ₂ ) ₉
Si (NCO) ₃ , CH ₃ (CH ₂ ) ₈ Si (NCO) ₃ , C
H ₃ (CH ₂ ) ₇ Si (NCO) ₃ , CH ₃ (CH ₂ ) ₆ Si
(NCO) ₃ , CH ₃ (CH ₂ ) ₅ Si (NCO) ₃ , CH ₃
(CH ₂ ) ₄ Si (NCO) ₃ , CH ₃ (CH ₂ ) ₃ Si (NC
O) ₃ , CH ₃ (CH ₂ ) ₂ Si (NCO) ₃ , CH ₃ CH ₂ S
i (NCO) ₃ , (CH ₃ CH ₂ ) ₂ Si (NCO) ₂ , (C
H ₃ CH ₂ ) ₃ SiNCO, CH ₃ Si (NCO) ₃ , (C
Alkyl group-containing isocyanate silanes such as H ₃ ) ₂ Si (NCO) ₂ and (CH ₃ ) ₃ SiNCO can be exemplified.

Further, by treating with a polyalkylene oxide group and an organosilane having a hydrolyzable group in the molecule, the critical tilt angle at which water droplets start rolling is low, and dirt is hardly adsorbed or adhered. A functional film can be obtained.

The polyalkylene oxide groups include
A polyethylene oxide group, a polypropylene oxide group and the like are mainly used. Examples of the organosilane having these groups include [alkoxy (polyalkyleneoxy) alkyl] trialkoxysilane, N- (triethoxysilylpropyl) -O-polyethylene oxide urethane, [alkoxy (polyalkyleneoxy) alkyl] trichlorosilane And organosilanes such as N- (trichlorosilylpropyl) -O-polyethylene oxide urethane, and more specifically, [methoxy (polyethyleneoxy) propyl] trimethoxysilane and [methoxy (polyethyleneoxy) propyl] trimethoxysilane. Ethoxysilane, [butoxy (polypropyleneoxy)
Propyl] trimethoxysilane and the like are preferably used.

By dissolving these organosilanes in an alcohol solvent and applying a solution hydrolyzed with an acid catalyst onto the silica-based film (base film), the surface of the base film can be treated without any particular heat treatment. A dealcoholization reaction occurs between the alkoxyl group and the silanol group of the organosilane, and the base film and the organosilane are bonded via a siloxane bond. Further, when the reactivity of the hydrolyzable functional group of the organosilane is high, for example, when the organosilane has a chloro group, an isocyanate group, an acyloxy group, and the like, a silanol or a trace amount present together with the alkoxyl group on the base film surface. By reacting with water, a bond between the base film and the organosilane is formed, so that the organosilane can be applied as it is without dilution, or it can be applied as perfluorocarbon, methylene chloride, hydrocarbon, silicone, or the like. A liquid simply diluted with a non-aqueous solvent may be applied. By using a silica-based film having an alkoxyl group remaining on the surface as a base film, a functional film can be firmly adhered to a substrate.

The coating method of the functional film is not particularly limited, as in the case of the silica-based film coating treatment, but may be flow coating, roll coating, spray coating, hand coating, or the like.
A brush coating method and the like can be mentioned.

[0051]

Embodiments of the present invention will be described below.

[Example 1] In 98.6 g of ethanol (manufactured by Nacalai Tesque), 0.4 g of tetraethoxysilane (manufactured by Shin-Etsu Silicone), concentrated hydrochloric acid (35% by weight, manufactured by Kanto Kagaku)
1 g was added with stirring to obtain a silica membrane treatment liquid. The contents of tetraethoxysilane (in terms of silica), hydrochloric acid and water in this treatment liquid are as shown in Table 1.

Next, CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si
1 g of (OCH ₃ ) ₃ (heptadecafluorodecyltrimethoxysilane, manufactured by Toshiba Silicone) was dissolved in 98 g of ethanol, and 1.0 g of 0.1 N hydrochloric acid was further added thereto, followed by stirring for 1 hour to obtain a water-repellent agent. Was.

A washed soda-lime silicate glass substrate (3
(00 × 300 mm), the above-mentioned silica film treatment liquid was applied by flow coating at a humidity of 30% and room temperature, and dried for about 1 minute to cover the surface of the glass substrate with a silica film having a thickness of about 40 nm. When the hardness of this silica film was measured by pencil hardness, the film was not damaged even when the film was scratched with a pencil of “H” core. In addition, the above silica film treatment solution is about 10 at room temperature.
The same results were obtained when used after standing for days.

Thereafter, 3 ml of the above-mentioned water repellent is applied to a cotton cloth on the surface of the glass substrate coated with the silica film, and the excessively adhered water repellent is wiped off with a new cotton cloth. A treated glass was obtained.

Using a contact angle meter (CA-DT, manufactured by Kyowa Interface Science), the weight of the water-repellent glass was 2
The initial static water droplet contact angle (hereinafter simply referred to as contact angle) was measured as mg. The smoothness of the obtained film was measured by using an atomic force microscope (SPI3700, manufactured by Seiko Instruments Inc.) in a cyclic contact mode to calculate the surface roughness Ra and Rz value. did. As a friction test, a dry cloth was attached to a reciprocating abrasion tester (manufactured by Shinto Kagaku), and the surface of the water-repellent film was measured under a load of 0.3 kg / cm ^2.
After sliding back and forth 000 times, the contact angle was measured. The contact angle of the silica film surface before the application of the water repellent was also measured for reference. The contact angle of the clean glass substrate itself is about several degrees or less. Table 2 shows the measurement results.

The surface of the water-repellent film before the friction test was visually observed to determine the presence or absence of film unevenness. Table 2 shows “OK” when there was no film unevenness, and “NG” when there was film unevenness. Respectively ". As shown in Table 2, the contact angle of the silica film surface was 30 degrees, the initial contact angle after the water-repellent treatment was 108 degrees, and the contact angle after the friction test was 95 degrees. The surface roughness of the silica film is
Ra = 0.4 nm, Rz = 2.9 nm, and the roughness of the film surface after the water-repellent treatment was Ra = 0.3 nm, Rz = 2.8.
nm. The surface roughness of the washed soda-lime silicate glass substrate before coating with the silica film is Ra =
0.7 nm and Rz = 8.0 nm.

Example 2 A water-repellent treatment was carried out in the same manner as in Example 1 except that tetraethoxysilane (manufactured by Tokyo Chemical Industry) was used instead of tetraethoxysilane used for preparing the silica film treating solution in Example 1. A glass was obtained. Table 1 shows the composition of the silica film treatment liquid, and Table 2 shows the thickness, various contact angles, surface roughness, and the like of the silica film. As shown in Table 2, the contact angle of the silica film surface before applying the water repellent was 31 degrees, the initial contact angle after the water repellent treatment was 108 degrees, and the contact angle after the friction test was 97 degrees.
The surface roughness of the silica film is Ra = 0.3 nm, Rz = 2.
8 nm, and the roughness of the film surface after the water-repellent treatment was Ra =
0.3 nm, Rz = 2.7 nm.

Example 3 A water-repellent treated glass was obtained in the same manner as in Example 1, except that the application of the silica film treating solution was changed to the spray method. As shown in Table 2, the contact angle of the silica film surface before applying the water repellent was 30 degrees, the initial contact angle after the water repellent treatment was 108 degrees, and the contact angle after the friction test was 95 degrees. The surface roughness of the silica film was Ra = 0.4 nm, Rz = 3.0 n.
m, and the roughness of the film surface after the water-repellent treatment is Ra = 0.4.
nm, Rz = 2.9 nm.

Example 4 9.8 g of acetylacetone, 64.8 g of ethanol, aluminum tri-sec
-Butoxide (25.4 g, manufactured by Kanto Chemical Co., Ltd.) was dissolved to obtain an alumina raw material liquid of 5% by weight in terms of oxide.

0.12 g of the above alumina raw material liquid, 0.33 g of tetraethoxysilane, 1 g of concentrated hydrochloric acid and ethanol 9
8.5 g was mixed to obtain a silica-based membrane treatment liquid. Table 1 shows the composition of this silica-based membrane treatment solution.

A water-repellent treated glass was obtained and measured in the same manner as in Example 1, except that the above silica-based film treating solution was used instead of the silica treating solution of Example 1. Silica membrane thickness,
Table 2 shows various contact angles, surface roughness, and the like. As shown in Table 2, the contact angle of the silica-based film surface before applying the water repellent was 31 degrees, the initial contact angle after the water repellent treatment was 106 degrees, and the contact angle after the friction test was 104 degrees. The surface roughness of the silica film was Ra = 0.4 nm and Rz = 3.3 nm, and the surface roughness of the film after the water-repellent treatment was Ra = 0.4 nm and Rz =
3.0 nm.

Example 5 4.1 g of acetylacetone, 78.6 g of ethanol, zirconium-tetra-n-
17.4 g of butoxide (manufactured by Kanto Chemical Co., Ltd.) was dissolved to obtain a zirconia raw material liquid of 5% by weight in terms of oxide.

0.12 g of the above zirconia raw material liquid, 0.33 g of tetraethoxysilane, 1 g of concentrated hydrochloric acid and 9 parts of ethanol
8.5 g was mixed to obtain a silica-based membrane treatment liquid. Table 1 shows the composition of this silica-based membrane treatment solution.

A water-repellent treated glass was obtained and measured in the same manner as in Example 1 except that the above-mentioned silica-based film treating solution was used instead of the silica film treating solution of Example 1. Table 2 shows the thickness, various contact angles, surface roughness, and the like of the silica-based film. As shown in Table 2, the contact angle of the silica-based film surface before the application of the water-repellent agent was 29 degrees, the initial contact angle after the water-repellent treatment was 107 degrees, and the contact angle after the friction test was 103 degrees. The surface roughness of the silica film was Ra = 0.4 nm and Rz = 3.4 nm, and the surface roughness of the film after the water-repellent treatment was Ra = 0.4 nm and Rz =
3.2 nm.

Examples 6 to 9 Ethanol (manufactured by Nacalai Tesque), Tetraethoxysilane (manufactured by Shin-Etsu Silicone)
And concentrated hydrochloric acid (35% by weight, manufactured by Kanto Chemical Co.) at a ratio shown in Table 3 to obtain a silica membrane treatment liquid. Table 1 shows the composition of this silica film treatment solution.

A water-repellent treated glass was obtained and measured in the same manner as in Example 1 except that the above-mentioned silica film treating solution was used instead of the silica film treating solution of Example 1. Silica membrane thickness,
Table 2 shows various contact angles, surface roughness, and the like.

[Examples 10 to 13] CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (O) used in the preparation of the water-repellent treatment liquid in Example 1
In Example 10, CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ (Tridecafluoro) was used instead of CH ₃ ) ₃ (Heptadecafluorodecyltrimethoxysilane, manufactured by Toshiba Silicone Co., Ltd.). Octyltrimethoxysilane, manufactured by Toshiba Silicone Co., Ltd.), and in Example 11, CF ₃ (CF ₂ ) ₃ (C
H _{2) 2} SiCl ₃ to (nonafluorohexyl trichlorosilane, (manufactured by Chisso Corporation)), Example 12, CF ₃ (C
_{H 2) 2 Si (OCH 3} ) 3 ( trifluoropropyl trimethoxysilane, the Chisso), Example 13, CF
Water-repellent treated glass was obtained in the same manner as in Example 1, except that ₃ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ (trifluoropropyltrimethoxysilane, manufactured by Chisso) was used. Table 2 shows various contact angles and the like. As shown in Table 2, the initial contact angle after the water-repellent treatment was 80 to 107 degrees, and the contact angle after the friction test was 75 to 97 degrees, and a water-repellent film having excellent wear resistance was obtained.

[Examples 14 to 18] CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (O) used in the preparation of the water-repellent treatment liquid in Example 1
CH ₃ ) ₃ (Heptadecafluorodecyltrimethoxysilane, manufactured by Toshiba Silicone) was replaced with alkylsilane to obtain a water-repellent and low-friction resistance glass in the same manner as in Example 1. Table 4 shows the composition of the treatment solution for the water repellent and low friction resistance film.

The contact angles of these water repellent and low friction resistance glasses were measured at the initial stage and after the friction test. Further, a dry cloth was attached to a wear coefficient measuring instrument (manufactured by Shinto Kagaku), and the coefficient of friction between the film surface and the dry cloth was measured. Table 5 shows the measurement results. As shown in Table 5, the difference between the initial contact angle after the water-repellent treatment and the contact angle after the friction test was very small, and almost no deterioration in the water-repellent performance was observed. Also,
The coefficient of friction with a dry cloth is 0.22 to 0.25, 0.36 when treated with an organosilane having a fluoroalkyl group as in Example 1, and 0.
A glass having a smaller coefficient of friction than that of No. 42 was obtained.
The friction coefficient after the friction test was almost the same as before the friction test.

Example 19 CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC) used for preparing the water-repellent treatment liquid in Example 1
H ₃ ) ₃ (Heptadecafluorodecyltrimethoxysilane, manufactured by Toshiba Silicone) was replaced with [methoxy (polyethyleneoxy) propyl] trimethoxysilane (manufactured by Chisso Corporation, content: 90%, molecular weight: 460-590, ethylene oxide unit number: 6- Except for changing to 9), in the same manner as in Example 1, the critical inclination angle at which water droplets start rolling is low, and
A functional film to which dirt is hardly adsorbed or adhered was obtained.

The contact angle of the functional film was 38 degrees. In addition, the critical tilt angle, which is a measure of the ease with which water droplets roll, is such that the obtained functional membrane-treated glass sample is horizontally placed, a 5 mm diameter water droplet is placed thereon, and the glass plate is gradually tilted. It was 4 degrees as determined by measuring the angle of inclination from the horizontal when the water droplet began to roll, and was 4 degrees, and a surface on which the water droplet could easily roll was obtained. Further, the contact angle after the friction test was 38 degrees, the critical inclination angle after the friction test was 4 degrees, and almost the same performance as before the friction test was maintained.

[Comparative Example 1] To 99 g of ethanol (manufactured by Nacalai Tesque), 0.05 g of tetraethoxysilane (manufactured by Shin-Etsu Silicone), and concentrated hydrochloric acid (35% by weight, manufactured by Kanto Chemical) 1
g was added with stirring to obtain a silica membrane treatment liquid. Table 1 shows the composition of this silica film treatment solution.

A water-repellent treated glass was obtained and measured in the same manner as in Example 1 except that the above-mentioned silica film treating solution was used in place of the silica film treating solution of Example 1. Silica membrane thickness,
Table 2 shows various contact angles, surface roughness, and the like. As shown in Table 2, the contact angle of the silica film surface before applying the water repellent was 2
9 °, the initial contact angle after the water repellent treatment was 105 °, and the contact angle after the friction test was 60 °, indicating that the water repellency after the friction test was reduced. The surface roughness of the silica film is Ra =
0.5 nm and Rz = 6.2 nm, and the roughness of the film surface after the water-repellent treatment was Ra = 0.5 nm and Rz = 6.0 nm. Rz of both the silica film and the water-repellent film is 5.0n
m, which indicates that the film has poor smoothness.

[Comparative Example 2] To 95 g of ethanol (manufactured by Nacalai Tesque), 4 g of tetraethoxysilane (manufactured by Shin-Etsu Silicone) and 1 g of concentrated hydrochloric acid (35% by weight, manufactured by Kanto Kagaku) were added with stirring. I got Table 1 shows the composition of this silica film treatment solution.

A water-repellent treated glass was obtained and measured in the same manner as in Example 1 except that the above-mentioned silica film treating solution was used instead of the silica film treating solution of Example 1. Silica membrane thickness,
Table 2 shows various contact angles, surface roughness, and the like. As shown in Table 2, the contact angle of the silica film surface before applying the water repellent was 2
5 °, the initial contact angle after the water repellent treatment was 110 °, and the contact angle after the friction test was 80 °, indicating that the water repellency after the friction test was reduced. The surface roughness of the silica film is Ra =
0.9 nm and Rz = 8.8 nm, and the roughness of the film surface after the water-repellent treatment was Ra = 0.8 nm and Rz = 9.0 nm. Ra and Rz of the silica film and the water-repellent film both exceed 0.5 nm and 5.0 nm, respectively, indicating that the film has poor smoothness. Further, unevenness was observed in the obtained water repellent film.

Comparative Example 3 To 99.1 g of ethanol (manufactured by Nacalai Tesque), 0.4 g of tetraethoxysilane (manufactured by Shin-Etsu Silicone) and 0.5 g of 0.1 N hydrochloric acid were added with stirring, and a silica membrane treating solution was added. I got Table 1 shows the composition of this silica film treatment solution.

A water-repellent treated glass was obtained and measured in the same manner as in Example 1 except that the above-mentioned silica film treating solution was used instead of the silica film treating solution of Example 1. Silica membrane thickness,
Table 2 shows various contact angles, surface roughness, and the like. As shown in Table 2, the contact angle of the silica film surface before applying the water repellent was 2
The initial contact angle after the water repellency treatment was 4 degrees, the contact angle after the friction test was 70 degrees, and the water repellency after the friction test was lowered. The surface roughness of the silica film is Ra =
0.8 nm, Rz = 11.0 nm, and the roughness of the film surface after the water-repellent treatment was Ra = 0.8 nm, Rz = 10.5 n
m, the surface roughness of each of the silica film and the water-repellent film exceeded Ra = 0.5 nm and Rz = 5.0 nm, and the surface smoothness of the film was poor.

Comparative Example 4 In 89.6 g of ethanol (manufactured by Nacalai Tesque), 0.4 g of tetraethoxysilane (manufactured by Shin-Etsu Silicone), concentrated hydrochloric acid (35% by weight, manufactured by Kanto Chemical)
20 g was added with stirring to obtain a silica membrane treatment liquid.
Table 1 shows the composition of this silica film treatment solution.

A water-repellent treated glass was obtained and measured in the same manner as in Example 1 except that the above-mentioned silica film treating solution was used instead of the silica film treating solution of Example 1. Table 2 shows the thickness, various contact angles, surface roughness and the like of the silica film. As shown in Table 2, the contact angle of the silica film surface before applying the water-repellent agent was 32 degrees, the initial contact angle after the water-repellent treatment was 107 degrees, the contact angle after the friction test was 87 degrees, and the contact angle after the friction test was It can be seen that the water repellency of the sample decreases. In addition, film thickness unevenness was observed in the obtained film. The surface roughness of the silica film is Ra = 0.7n
m, Rz = 9.8 nm, the roughness of the film surface after the water-repellent treatment is
Ra = 0.7 nm and Rz = 8.9 nm, all of which exceeded Ra = 0.5 nm and Rz = 5.0 nm, and the film surface was inferior in smoothness.

Comparative Example 5 0.4 g of tetraethoxysilane (manufactured by Shin-Etsu Silicone), 29.6 g of ethanol (manufactured by Nacalai Tesque), a methanol solution of hydrochloric acid (10% by weight,
70 g (manufactured by Tokyo Kasei) was added with stirring to obtain a silica membrane treatment liquid. Table 1 shows the composition of this silica film treatment solution.

A water-repellent treated glass was obtained and measured in the same manner as in Example 1 except that the above-mentioned silica film treating solution was used instead of the silica film treating solution of Example 1. Table 2 shows the thickness, various contact angles, surface roughness and the like of the silica film. As shown in Table 2, the contact angle of the silica film surface before applying the water repellent was 30 degrees, the initial contact angle after the water repellent treatment was 108 degrees, the contact angle after the friction test was 88 degrees, and after the friction test. It can be seen that the water repellency of the sample decreases. In addition, film thickness unevenness was observed in the obtained film. The surface roughness of the silica film is Ra = 0.7n
m, Rz = 8.8 nm, and the roughness of the film surface after the water-repellent treatment is
Ra = 0.7 nm and Rz = 7.8 nm, all of which exceeded Ra = 0.5 nm and Rz = 5.0 nm, and the smoothness of the film surface was poor.

Comparative Example 6 To 86.25 g of ethanol (manufactured by Nacalai Tesque), 0.4 g of tetraethoxysilane (manufactured by Shin-Etsu Silicone), 1 g of concentrated hydrochloric acid (35% by weight, manufactured by Kanto Kagaku), and 12.35 g of water Was added with stirring to obtain a silica membrane treatment liquid. Table 1 shows the composition of this silica film treatment solution.

A water-repellent treated glass was obtained and measured in the same manner as in Example 1 except that the above-mentioned silica film treating solution was used instead of the silica film treating solution of Example 1. Table 2 shows the thickness, various contact angles, surface roughness and the like of the silica film. As shown in Table 2, the contact angle of the silica film surface before applying the water repellent was 32 degrees, the initial contact angle after the water repellent treatment was 109 degrees, the contact angle after the friction test was 86 degrees, and the contact angle after the friction test was It can be seen that the water repellency of the sample decreases. In addition, film thickness unevenness was observed in the obtained film. The surface roughness of the silica film is Ra = 0.6 n
m, Rz = 9.8 nm, the roughness of the film surface after the water-repellent treatment is
Ra = 0.7 nm, Rz = 10.8 nm, and both exceeded Ra = 0.5 nm and Rz = 5.0 nm;
The smoothness of the film surface was poor.

Comparative Example 7 Ethyl silicate (average degree of polymerization: about 5) hydrolyzate (average molecular weight: 408.5, 96% ethanol (manufactured by Nacalai Tesque), "HAS-1")
0 "(manufactured by Colcoat Co., Ltd., silica content 10% by weight) was mixed to obtain a silica membrane treatment liquid. Table 1 shows the composition of this silica film treatment solution. This silica film treatment liquid was flow coated on a washed glass substrate (300 × 300 mm) at room temperature and a room temperature of 30% at room temperature, and dried for about 1 minute. Thereafter, the substrate was fired at 600 ° C. for 1 hour to obtain a silica film. When the hardness of the silica film before firing was measured by pencil hardness,
The membrane was scratched when the membrane was scratched with the pencil of the "B" lead. The baked silica film was not damaged even when the film was scratched with a pencil of “H” core.

Further, the silica-coated glass was subjected to ultrasonic cleaning in pure water for 10 minutes, dried, and treated in the same manner as in Example 1 to obtain a water-repellent glass. As shown in Table 2, the contact angle of the silica film surface before applying the water repellent was 2 degrees,
The initial contact angle after the water repellent treatment was 106 degrees, and the contact angle after the friction test was 50 degrees, indicating that the water repellency after the friction test was significantly reduced. The surface roughness of the silica film is Ra =
The roughness of the film surface after the water repellent treatment was 0.9 nm, Rz = 12.1 nm, Ra = 0.8 nm, Rz = 10.3 nm, and both exceeded Ra = 0.5 nm and Rz = 5.0 nm. And the smoothness of the film surface was poor.

Comparative Example 8 A water repellent and low friction resistance glass was obtained in the same manner as in Example 15 except that the silica film coating step in Example 15 was not performed. Table 5 shows various contact angles.
Are shown below. As shown in Table 5, the initial contact angle after the water-repellent treatment was 95 degrees, which was equal to the value for the glass of Example 15; (90 degrees), resulting in a film having poor abrasion resistance. The friction coefficient after the friction test was 0.45, and the low friction resistance function was lost due to the friction.

Comparative Example 9 A water-repellent and low frictional resistance glass glass was obtained in the same manner as in Example 19, except that the silica film coating step in Example 19 was not performed. The contact angle of this functional film is 38 degrees, the critical tilt angle is 4 degrees,
Both were equal to the measured values in Example 19. However, the contact angle after the friction test was 22 degrees, and the critical inclination angle was 25 degrees. The decrease in the contact angle and the increase in the critical inclination angle were remarkable, and the wear resistance was poor.

[0089]

[Table 1] ================================= Tetraalkoxysilane Aluminum Trisilconium Tetra Hydrochloride Water PHOTOPHOTO PHOTOXITE (SiO ( ₂ conversion) (Al ₂ O ₃ conversion) (ZrO ₂ conversion) (% by weight) (% by weight) (% by weight) (Normal) (% by weight) −−−−−−−−−−−−−−−−−− −−−−−−−−−−−−−−−−−− Example 1 0.12 0 0 0.09 0.7 Example 2 0.16 0 0 0.09 0.7 Example 3 0.12 0 0 0.09 0.7 Example 4 0.095 0.006 0 0.09 0.8 Example Example 5 0.095 0 0.006 0.09 0.8 Example 6 0.014 0 0 0.05 0.5 Example 7 0.058 0 0 0.005 0.5 Example 8 0.58 0 0 0.2 2.0 Example 9 2.3 0 0 0.5 5.0 −−−−−−−−−−−−− −−−−−−−−−−−−−−−−−−−−−−− Comparative Example 1 0.003 0 0 0.09 0.7 Comparative Example 2 4.3 0 0 0.09 0.6 Comparative Example 3 0.12 0 0 0.0004 0.5 Comparative Example 4 0.12 0 0 2.0 13.0 Comparative Example 5 0.12 0 0 2.0 0.5 Comparative example 6 0.12 0 0 0.09 13.0 Comparative example 7 0.12 0 0 0.00003 0.3 ============================== ===

[0090]

Table 2 Silica-based film Water-repellent treated glass Thickness Contact angle-------------------------------S----- Surface roughness Initial after friction test Surface roughness Appearance Ra / Rz Contact angle Contact angle Ra / Rz (nm) (degree) (nm) / (nm) (degree) (degree) (nm) / (nm) −−− −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Example 1 40 30 0.4 / 2.9 108 95 95 0.3 / 2.8 OK Example 2 40 31 0.3 / 2.8 108 97 0.3 / 2.7 OK Example 3 40 30 0.4 / 3.0 108 95 0.4 / 2.9 OK Example 4 40 31 0.4 / 3.3 106 104 0.4 / 3.0 OK Example 5 35 29 0.4 / 3.4 107 103 103 0.4 / 3.2 OK Example 6 15 28 0.4 / 3.2 106 93 0.4 / 3.0 OK Example 7 30 30 0.3 / 3.3 107 91 0.3 / 3.2 OK Example 8 100 28 0.3 / 2.8 108 98 0.3 / 2.7 OK Example 9 250 27 0 . 3 / 2.4 108 90 0.3 / 2.3 OK Example 10 40 30 0.4 / 2.9 107 97 0.3 / 2.8 OK Example 11 Same as above 101 90 0.3 / 2.8 OK Example 12 〃 〃 ９５ 95 88 0.3 / 2.8 OK Example 13 〃 〃 ８０ 80 75 0.3 / 2.8 OK −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Comparative Example 1 5 or less 29 0.5 / 6.2 105 60 0.5 / 6.0 OK Comparative Example 2 300 25 0.9 / 8.8 110 80 0.8 / 9.0 NG Comparative Example 3 45 24 0.8 / 11.0 110 70 0.8 / 10.5 OK Comparative Example 4 40 32 0.7 / 9.8 107 87 87 0.7 / 8.9 NG Comparative Example 5 40 30 0.7 / 8.8 108 88 0.7 / 7.8 NG Comparative Example 6 40 32 0.6 / 9.8 109 86 0.7 / 10.8 NG Comparative Example 7 40 2 0.9 / 12.1 106 50 0.8 / 10.3 OK −−−−−−−− −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−

[0091]

[Table 3] ====================== Ethanol Tetraethoxysilane Concentrated Hydrochloric Acid (g) (g) (g) ----------- −−−−−−−−−−−−−− Example 6 99.5 0.05 0.5 Example 7 99.3 0.2 0.05 Example 8 96.0 2.0 2.0 Example 9 87.0 8.0 5.0 ============= =========

[0092]

[Table 4] =============================== Alkylsilane 0.1N-hydrochloric acid ethanol (g) (g) (g) Example 14 n-octatedecyltrimethoxysilane 111 98 Example 15 n-todecyl Trimethoxysilane 1 198 Example 16 n-octyltriethoxysilane 1 1 9 Example 17 n-pentyltriethoxysilane 1 1 98 Example 18 trimethylethoxysilane 1 1 98 =========== ====================

[0093]

Table 5 Initial contact angle Initial coefficient of friction Initial frictional coefficient Contact after frictional test---------------------------------------- Angle Friction coefficient after friction test (degrees) (degrees) --- --- --- --- --- --- --- --- -------- 14 95 0.23 94 0.24 ------------------------------------------------------------------------------------- 15 Example 0 90 0------------------------------------ .22 90 0.23 Comparative Example 8 95 0.23 55 0.45 ----------------------------------------------- −−− Example 16 88 0.24 87 0.22 Example 17 80 0.25 78 0.23 Example 18 60 0.25 60 0.25 −−−−−−−−−−−−−−− −−−−−−−−−−−−−−−−−−−−−−−−−−

[0094]

According to the present invention as described above,
By applying an alcohol solution comprising a low-concentration silicon alkoxide and a high-concentration volatile acid to a substrate and drying at room temperature, an article coated with a dense and strong silica film can be obtained. Further, by applying this silica film as a base film and applying an organosilane having a hydrolyzable group and a functional functional group to the base film, a functional coated article having excellent durability can be obtained by treatment at normal temperature.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Takashi Sunada, 3-5-11, Doshumachi, Chuo-ku, Osaka-shi Inside Japan Sheet Glass Co., Ltd. (72) Hiroaki Kobayashi 3-5-11, Doshomachi, Chuo-ku, Osaka-shi Japan Sheet Glass Co., Ltd. (72) Inventor Hiroaki Yamamoto 3-5-1, Doshomachi, Chuo-ku, Osaka-shi Japan Sheet Glass Co., Ltd. (72) Inventor Eiji Ogawa 3-5-11, Doshu-cho, Chuo-ku, Osaka, Japan Sheet Glass Co., Ltd.

Claims (28)

[Claims] 1. A method for producing a silica-based film-coated article in which a coating solution comprising an alcohol solution containing a silicon alkoxide and an acid is applied to a substrate, wherein the coating solution comprises: (A) a silicon alkoxide and a hydrolyzate thereof ( 0.010 to 3% by weight (in terms of silica), (B) acid 0.0010 to 1.0N, and (C) water 0 to 10% by weight. A method for producing a silica-based film-coated article, comprising: 2. The coating liquid comprises: (A) at least one of silicon alkoxide and its hydrolyzate (including partial hydrolyzate) in terms of silica;
2. The silica-based membrane-coated article according to claim 1, comprising (B) an acid so that “(B) component (normative) / (A) component (% by weight)” is 0.010 or more. Method. 3. The coating liquid contains the (B) acid and (C) water so that the ratio of ((B) component (normal) × (C) component (% by weight)] is 0.0020 or more. A method for producing the silica-based film-coated article according to claim 1 or 2. 4. The coating liquid comprises: (A) at least one of silicon alkoxide and a hydrolyzate thereof (including a partial hydrolyzate) of 0.010 to 0.6% by weight (in terms of silica); The method for producing a silica-based membrane-coated article according to any one of claims 1 to 3, wherein the method comprises (1) an acid of 0.010 to 1.0N, and (C) 0 to 2% by weight of water. 5. The coating solution according to claim 1, wherein said coating solution has a water content of 0.1%.
The method for producing a silica-based film-coated article according to any one of claims 1 to 4, wherein an acid having a concentration three times or more and a silicon alkoxide are dissolved in an alcohol. 6. The silica-based film according to claim 1, wherein the silicon alkoxide of the component (A) is tetramethoxysilane or tetraethoxysilane, and the component (B) is hydrochloric acid. A method for producing a coated article. 7. A maximum of 30% by weight of the component (A) is a chelate of an alkoxide of a metal other than silicon having β-diketone, acetic acid, trifluoroacetic acid or ethanolamine as a ligand in terms of oxide. A method for producing a silica-based membrane-coated article according to any one of claims 1 to 6. 8. The method for producing a silica-based membrane-coated article according to claim 7, wherein the β-diketone of the ligand is acetylacetone. 9. The method according to claim 7, wherein the metal alkoxide is an alkoxide of aluminum or zirconium. 10. The method according to claim 1, wherein the coating liquid has a pH of 0 to 3. 11. The method for producing an article coated with a silica-based film according to claim 1, wherein the film of the coating liquid applied to the substrate is dried at room temperature or at a temperature of 150 ° C. or lower. 12. The method according to claim 11, wherein the coating liquid is applied to the surface of the base material such that the applied film has a thickness of 5 to 300 nm after drying. 13. The method according to claim 1, wherein the substrate is a transparent glass plate. 14. A silica-based film-coated article having a static water droplet contact angle of 20 to 40 degrees obtained by the method according to any one of claims 1 to 13. 15. Arithmetic mean roughness (Ra) of a surface obtained by the method according to claim 1.
A silica-based film-coated article having a ten-point average roughness (Rz) of not less than 0.10 nm and not more than 0.5 nm and not more than 1.0 nm and not more than 5.0 nm. 16. A base material and a silica-based coating containing silicon oxide as a main component and coated on the surface of the base material by a sol-gel method, and the surface of the coating has an arithmetic average roughness (Ra) =
A silica-based film-coated article having a roughness of 0.10 nm or more and 0.5 nm or less and a ten-point average roughness (Rz) of 1.0 nm or more and 5.0 nm or less. 17. A method for coating a silica-based film obtained by the method according to any one of claims 1 to 13,
A method for producing a functional film-coated article further comprising applying a functional film composition. 18. The composition for a functional film contains at least one of a hydrolyzable functional group, an organosilane having a functional functional group, and a hydrolyzate thereof (including a partial hydrolyzate). A method for producing the functional film-coated article according to claim 17. 19. The method according to claim 18, wherein the hydrolyzable functional group is an alkoxyl group. 20. The method according to claim 17, wherein the composition for a functional film is a composition for forming a water-repellent film. 21. The composition for forming a water-repellent film, comprising at least one of an organosilane containing an alkoxyl group and a fluoroalkyl group in a molecule and a hydrolyzate thereof (including a partial hydrolyzate). Item 21. A method for producing the functional film-coated article according to Item 20. 22. The method for producing a functional film-coated article according to claim 17, wherein the composition for a functional film is a composition for forming a water-repellent and low friction resistance film. 23. The composition for forming a water-repellent and low-frictional-resistance film comprises at least one of an organosilane containing an alkoxyl group and an alkyl group in a molecule and a hydrolyzate thereof (including a partial hydrolyzate). Claim 2 including
3. A method for producing the functional film-coated article according to 2. 24. The method for producing a functional film-coated article according to claim 17, wherein the composition for a functional film is a film-forming composition having excellent rolling properties of water droplets and having an antifouling property. 25. A composition for forming a film having excellent rolling properties of water droplets and antifouling properties, comprising an organosilane containing an alkoxyl group and a polyalkylene oxide group in a molecule and a hydrolyzate thereof (partially hydrolyzed). (Including decomposition products)
The method for producing a functional film-coated article according to claim 24, comprising at least one of the following. 26. A functional film-coated article obtained by the method according to any one of claims 17 to 25. 27. A functional film-coated article obtained by the method according to any one of claims 17 to 25,
The surface of the film has an arithmetic average roughness (Ra) = 0.10 nm
Above, 0.5 nm or less and ten-point average roughness (Rz) =
A functional film-coated article having a roughness of 1.0 nm or more and 5.0 nm or less. 28. (A) at least one of silicon alkoxide and its hydrolyzate (including partial hydrolyzate) 0.010 to 3% by weight (in terms of silica); (B) acid 0.0010 to 1 And (C) 0 to 10% by weight of water and (D) the remainder of the alcohol.